Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
  • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
  • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • D—TEXTILES; PAPER
  • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
  • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
  • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
  • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
  • D02G3/04—Blended or other yarns or threads containing components made from different materials
  • D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B16/04—Macromolecular compounds
  • C04B16/06—Macromolecular compounds fibrous
  • C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B16/0641—Polyvinylalcohols; Polyvinylacetates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B16/04—Macromolecular compounds
  • C04B16/06—Macromolecular compounds fibrous
  • C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B16/065—Polyacrylates; Polymethacrylates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B7/00—Hydraulic cements
  • C04B7/02—Portland cement
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F216/04—Acyclic compounds
  • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
  • C08F8/16—Lactonisation
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
  • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
  • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
  • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/52—Constituents or additives characterised by their shapes
  • C04B2235/5208—Fibers
  • C04B2235/5212—Organic
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/52—Constituents or additives characterised by their shapes
  • C04B2235/5208—Fibers
  • C04B2235/5268—Orientation of the fibers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/16—Synthetic fibres, other than mineral fibres
  • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D10B2321/06—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D10B2321/08—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

• the present invention relates to a convergent yarn, a hydraulic composition and a molded product.
• a matrix containing a hydraulic material for the purpose of improving mechanical strength such as bending strength and toughness of a molded product which is a cured product of a hydraulic material typified by concrete and cement mortar, and suppressing cracks. It is known to incorporate reinforcing fibers therein. However, it is extremely difficult to uniformly disperse the fibers in the matrix, and the fibers may be entangled with each other during the kneading of the fiber and the hydraulic material to form an agglomerate (fiber ball). Then, it becomes difficult to exert the reinforcing effect of the fibers.
• Patent Document 1 describes a convergent yarn that is hardened with a water-soluble converging agent and has a defibration degree of 20% or more in a concrete molded product.
• Patent Document 2 discloses a convergent yarn that is converged with a water-soluble polymer resin and has a defibration degree at pH 12 of 50% or more.
• Patent Document 1 a water-soluble polymer having a film-forming ability is used as a water-soluble sizing agent.
• a water-soluble polymer having a film-forming ability is used as a water-soluble sizing agent.
• the fibers are bundled by using a water-soluble polymer having a high film-forming ability, it is difficult to increase the defibration degree and the strength of the molded body cannot be sufficiently increased. If the kneading time of the convergent yarn, the hydraulic material, and water is increased to increase the defibration, the defibration is improved by applying shearing force, but the fibers are easily damaged and a fiber ball is formed. It is easy to be done. As a result of these, the strength of the obtained molded article decreases.
• Patent Document 2 attention is paid to the degree of defibration under an alkaline condition of pH 12, but a certain kneading time or more is required until the pH of the matrix becomes 12 or more, and as a result, the defibrated fibers are Fiber balls are easily formed, and the strength of the molded product cannot be sufficiently increased.
• a converging yarn in which a plurality of fibers are integrated by a converging agent has a structural unit (X) derived from an unsaturated carboxylic acid or a derivative thereof in an amount of 0.1 to 10 mol% when the amount of all monomer units is 100 mol %, and has a saponification degree of 85.
• Convergent yarn which is a modified polyvinyl alcohol having a mol% or more.
• the modified polyvinyl alcohol has the structural unit (X) represented by the formula (X1): [In Formula (X1), X is a hydrogen atom or a methyl group]
• Ratio of molar amount of structural unit represented by formula (X1) to total molar amount of structural unit represented by formula (X1) and structural unit represented by formula (X2) in modified polyvinyl alcohol (X1/(X1+X2)) is a convergent yarn according to the above [5], which is 0.65 to 1.0.
• the convergent yarn of the present invention has a high degree of fiber disintegration and a low degree of coagulation of disentangled fibers when it is used by kneading with a hydraulic material such as cement.
• the converging yarn of the present invention is a converging yarn in which a plurality of fibers are integrated by a converging agent, and the converging agent comprises structural units (X) derived from an unsaturated carboxylic acid or a derivative thereof as all monomer units.
• the modified polyvinyl alcohol has a content of 0.1 to 10 mol% and a saponification degree of 85 mol% or more when the amount is 100 mol %.
• the converging yarn of the present invention includes a plurality of fibers and the above specific converging agent, and the plurality of fibers are integrated by the converging agent.
• the fact that the plurality of fibers are integrated by the sizing agent means that the plurality of fibers are bonded to each other by the sizing agent and bundled.
• the sizing agent contained in the sizing fiber of the present invention is a modified polyvinyl alcohol, and the modified polyvinyl alcohol comprises a structural unit (X) derived from an unsaturated carboxylic acid or a derivative thereof as a total monomer unit of the modified polyvinyl alcohol.
• the modified polyvinyl alcohol has a content of 0.1 to 10 mol% and a saponification degree of 85 mol% or more when the amount is 100 mol %.
• the modified polyvinyl alcohol represents polyvinyl alcohol modified with a structural unit (X) derived from an unsaturated carboxylic acid or a derivative thereof, and the modified polyvinyl alcohol is a structural unit derived from a vinyl ester-based monomer. , And at least a structural unit (X) derived from an unsaturated carboxylic acid or a derivative thereof.
• the modified polyvinyl alcohol may contain a structural unit other than the above structural units as long as the effects of the present invention are not impaired.
• the amount of the structural unit (X) derived from the unsaturated carboxylic acid or its derivative is 0.1 to 10 mol% when the amount of all monomer units contained in the modified polyvinyl alcohol is 100 mol %.
• the bundling yarn is usually used by being dispersed in a hydraulic composition containing at least a hydraulic material and water, and the molded composition is obtained by curing the hydraulic composition. By dispersing the fibers contained in the bundling yarn in a single fiber state as uniformly as possible in the matrix of the hydraulic composition without damaging the fibers, it is possible to enhance the reinforcing effect of the hydraulic material by the fibers. It is thought to be possible.
• the hydraulic composition is produced, for example, by mixing the convergent yarn and the hydraulic material in a dry state and gradually adding water while stirring the mixture. Then, by adding water, the sizing agent is dissolved, and due to the shearing force due to stirring, the bundled fibers are loosened and disentangled. From the viewpoint of facilitating to increase the mechanical strength of the molded product by uniformly dispersing the fibers contained in the converging yarn in a single fiber state in the matrix of the hydraulic composition without damaging the fibers, a converging agent is used. It is considered that it is very important for the fiber to dissolve quickly in water and the fiber to be defibrated quickly and sufficiently.
• the solubility of the sizing agent in water becomes too low, and thus the fibers are dispersed as single fibers in the hydraulic material and the water matrix. Hard to do. Furthermore, when kneading the convergent yarn with the hydraulic material and water, it is necessary to defibrate the fibers by shearing force, so the fibers themselves are bent and buckling portions are likely to occur. When a buckling portion is formed in the fiber, the fiber having the buckling portion serves as a nucleus to easily form a fiber ball. As a result, the mechanical strength of the obtained molded article cannot be sufficiently increased.
• the solubility of the sizing agent in water to the sizing agent becomes too high, so that the swelling agent easily swells due to water in the air, and thus the modified polyvinyl alcohol.
• the performance as a sizing agent (particularly the adhesiveness of fibers) becomes insufficient. Therefore, it is considered that the fibers are likely to be damaged when the convergent yarn and the hydraulic material such as cement are dry-mixed before the production of the hydraulic composition.
• a bending portion also called a buckling portion is generated in the fiber, and a fiber ball is likely to be formed with the fiber having the buckling portion as a core. As a result, sufficient mechanical strength of the molded product cannot be obtained.
• the amount of the structural unit (X) is preferably 0.5 to 10 mol %, more preferably from the viewpoint of easily increasing the fiber disentanglement, easily decreasing the fiber cohesion, and easily enhancing the reinforcing effect of the molded body with the fibers. It is 1 to 9.5 mol %, particularly preferably 2 to 9 mol %.
• the amount of the structural unit (X) derived from the unsaturated carboxylic acid or its derivative contained in the modified polyvinyl alcohol may be determined from the 1 H-NMR peak of the modified polyvinyl alcohol, or the modified polyvinyl alcohol is produced. It may be determined from the charging ratio of the monomer at that time.
• the saponification degree of the modified polyvinyl alcohol is 85 mol% or more.
• the degree of saponification is less than 85 mol%, the modified polyvinyl alcohol has insufficient solubility in water, so that the fiber cannot be swiftly and sufficiently defibrated. Further, in order to defibrate the fibers, high shearing force and kneading for a long time are required. As a result, even if the defibration degree can be improved, the fibers are damaged or fiber balls are easily formed. As a result, a sufficient reinforcing effect of the obtained molded body cannot be obtained.
• the degree of saponification of the modified polyvinyl alcohol facilitates rapid defibration of the fibers, facilitates increasing the defibration of the fibers, and lowers the degree of fiber cohesion. Therefore, it is preferably 88 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and particularly preferably 98 mol% or more.
• the upper limit of the degree of saponification may be 100 mol% or less, and from the viewpoint of improving the solubility in water by reducing the crystallinity of the modified polyvinyl alcohol, it is preferably 99.9 mol% or less, more preferably 99.8 mol%. It is as follows.
• the degree of saponification can be measured by the method described in JIS K 6726 (1994).
• the viscosity average degree of polymerization of the modified polyvinyl alcohol is preferably 100 to 5,000, more preferably 100 to 4,000, and further preferably 300 to 3,500.
• the viscosity average degree of polymerization is equal to or higher than the above lower limit, it is easy to enhance the converging property of the fiber as the converging agent.
• the viscosity average degree of polymerization is less than or equal to the above upper limit, the solubility of the modified polyvinyl alcohol in water can be improved, and the fiber can be quickly and sufficiently defibrated.
• the viscosity average degree of polymerization can be measured by the method described in JIS K 6726 (1994).
• the PVA saponified until the saponification degree becomes 99.5 mol% or more has an intrinsic viscosity [ ⁇ ] (liter/liter/liter) measured at 30° C. in water.
• Examples of the unsaturated carboxylic acid which gives the structural unit (X) contained in the modified polyvinyl alcohol include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, phthalic acid, maleic acid and itaconic acid. Examples of these derivatives include alkyl esters of the above-mentioned ethylenically unsaturated carboxylic acids, metal salts and the like.
• the modified polyvinyl alcohol used as the sizing agent may have one type of structural unit or two or more types of structural units as the structural unit (X) derived from the unsaturated carboxylic acid or its derivative. Or may have a further structural unit.
• the unsaturated carboxylic acid or its derivative is preferably (meta) from the viewpoint of easily increasing the defibration degree of the fiber when the convergent yarn is kneaded with the hydraulic material and using it, and easily decreasing the cohesion degree of the defibrated fiber.
• (meth)acrylic used in the present specification means “acrylic and/or methacrylic”.
• Examples of the (meth)acrylic acid alkyl ester include esters of (meth)acrylic acid and a linear or branched alcohol having 1 to 5 carbon atoms, and specific examples thereof include (meth)acrylic acid methyl ester. , (Meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid pentyl ester and the like.
• Examples of the metal salt of (meth)acrylic acid include alkali metal salts of (meth)acrylic acid. Examples of the alkali metal element include lithium, sodium and potassium.
• the modified polyvinyl alcohol used as a sizing agent in the sizing yarn of the present invention is usually a plurality of structural units derived from a vinyl ester monomer, which is a monomer, and a plurality of structural units derived from an unsaturated carboxylic acid or a derivative thereof.
• the amount of the structural unit (X) having at least (X) and derived from an unsaturated carboxylic acid or a derivative thereof is 0.1 to 10 mol% when the amount of all monomer units is 100 mol %. Is.
• the structural unit (X) derived from the unsaturated carboxylic acid or its derivative contained in the modified polyvinyl alcohol most of the structural unit derived from the vinyl ester monomer is adjacent to the structural unit (X) in consideration of the above molar ratio. It is thought that it exists.
• the structural unit (X) and the structural unit derived from the vinyl ester-based monomer may exist as separate structural units (monomer units), but at least a part of the plurality of structural units (X) May be contained by forming a ring-closed structural unit with a hydroxyl group contained in a structural unit derived from an adjacent vinyl ester-based monomer.
• the structural unit (X) also includes a structural unit (X) derived from an unsaturated carboxylic acid or a derivative thereof, for example, a structural unit in which a carboxyl group and the like and a hydroxyl group included in a structural unit derived from vinyl alcohol are closed. It is a structural unit containing a structural unit derived from an unsaturated carboxylic acid or a derivative thereof.
• the ring-closed structural unit is not regarded as one structural unit, but the structural unit corresponding to the monomer is used.
• the modified polyvinyl alcohol contained in the sizing agent is a structural unit (X) derived from an unsaturated carboxylic acid or a derivative thereof, and/or a vinyl ester-based unit in which the structural unit (X) is adjacent. It has a structural unit derived from a monomer and a closed structural unit.
• the modified polyvinyl alcohol when not dissolved in water, has a performance as a sizing agent, in particular, a fiber sizing property. Are better.
• Polyvinyl alcohol modified with the structural unit (X) has a high solubility in water due to a carboxyl group or the like. Therefore, a sizing agent containing such a modified polyvinyl alcohol as a sizing agent has a sizing agent rapidly when mixed with water. It has a feature that it dissolves and a quick and sufficient defibration of fibers can be obtained.
• the required promptness may differ depending on the usage amount of the converging yarn, the application of the hydraulic material, etc., but in the examples of the present specification, for example, a very short time of about several tens of seconds.
• the defibration property when kneading is performed is evaluated.
• a structural unit (X) derived from an unsaturated carboxylic acid or a derivative thereof and/or a structural unit derived from a vinyl ester-based monomer adjacent to the structural unit (X).
• Such a ring-closed structure has a very high ring-opening property particularly when dissolved in water in an alkaline environment, and the modified polyvinyl alcohol having the structural unit (X) after ring-opening has a high solubility in water. Therefore, a sizing fiber containing such a modified polyvinyl alcohol as a sizing agent has a feature that the sizing agent is quickly dissolved when mixed with water, and quick and sufficient defibration of fibers can be easily achieved.
• the modified polyvinyl alcohol is a structural unit (X) derived from an unsaturated carboxylic acid or a derivative thereof, from the viewpoint of easily increasing the fiber defibration degree of the convergent yarn and suppressing the fiber aggregation.
• the structural unit represented by the formula (X2) is a structural unit derived from at least one selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid alkyl ester and (meth)acrylic acid metal salt.
• the structural unit (X2) is closed with the structural unit derived from the adjacent vinyl ester-based monomer, the structural unit (X1) becomes the structural unit (X1).
• the modified polyvinyl alcohol contains, as the structural unit (X), the structural unit represented by the formula (X1) and/or the structural unit represented by the formula (X2), the convergent yarn is a hydraulic material such as cement, and the like.
• the modified polyvinyl alcohol may include one type of structural unit represented by the formula (X1) or may include two types of structural unit represented by the formula (X1). Further, the modified polyvinyl alcohol may include one type of structural unit represented by the formula (X2), or may include two or more types of structural unit represented by the formula (X2).
• the modified polyvinyl alcohol contains, in addition to one or more types of structural units represented by formula (X1) and/or one or more types of structural units represented by formula (X2), other structural units. May be
• the modified polyvinyl alcohol contains the structural unit represented by the formula (X1) and/or the structural unit represented by the formula (X2), it is represented by the structural unit represented by the formula (X1) and the formula (X2).
• the ratio (X1/(X1+X2)) of the molar amount of the structural unit represented by the formula (X1) to the total molar amount of the structural unit is preferably 0.65 or more and 1.0 or less, more preferably 0.70. Or more and 0.99 or less, more preferably 0.85 or more and 0.99 or less, and particularly preferably 0.90 or more and 0.99 or less.
• the content ratio of the structural unit represented by the formula (X1) is at least the above lower limit, the performance as a sizing agent is likely to be enhanced, and, for example, fiber damage during dry mixing of sizing yarn and hydraulic material is suppressed. It's easy to do.
• the content (molar amount) of the structural unit (X1) and the structural unit (X2) contained in the modified polyvinyl alcohol may be determined from the peak of 1 H-NMR of the modified polyvinyl alcohol, or the modified polyvinyl alcohol is produced. It may also be determined from the charging ratio of the monomers used.
• the modified polyvinyl alcohol contains at least a structural unit represented by the formula (X1).
• the amount of the structural unit represented by the formula (X1) is preferably 0.1 to 10 mol%, more preferably 100 mol% when the amount of all the monomer units of the modified polyvinyl alcohol is 100 mol%. Is 0.5 to 10 mol %, more preferably 1 to 9.5 mol %, and particularly preferably 2 to 9 mol %.
• the amount of the structural unit represented by the formula (X1) is within the above range, the performance as the sizing agent (for example, the adhesiveness of the fiber) is easily enhanced, and for example, when the sizing fiber and the hydraulic material are dry-mixed.
• the modified polyvinyl alcohol is obtained by copolymerizing a vinyl ester monomer and a carbonyl group-containing monomer (unsaturated carboxylic acid or its derivative) by a known method, saponifying the resulting copolymer by a known method, and then performing a washing treatment. It can be obtained by heat treatment. Furthermore, the modified polyvinyl alcohol can be efficiently obtained by neutralizing by acid treatment after the saponification, washing treatment and heat treatment.
• Examples of vinyl ester-based monomers used for the production of modified polyvinyl alcohol include vinyl acetate, vinyl propionate, vinyl formate, etc., but vinyl acetate is preferably used from the economical point of view.
• Examples of the carbonyl group-containing monomer used for producing the modified polyvinyl alcohol include acrylic acid, methacrylic acid, and alkyl esters of these carboxylic acids.
• alkyl ester methyl ester, ethyl ester and the like are preferably used.
• carboxylic acid salts obtained by partially or completely neutralizing these carboxylic acids and esters are also suitably used.
• the method of heat treatment is not particularly limited, but it is preferable to use, for example, a hot air dryer or a rotary dryer.
• the heating temperature is preferably 60 to 150°C, more preferably 80 to 150°C.
• the heating time is preferably 1 to 10 hours, more preferably 2 to 8 hours.
• the fibers contained in the convergent yarn of the present invention are not particularly limited, but include polyvinyl alcohol (hereinafter sometimes referred to as PVA) fiber, polyolefin fiber, polyamide fiber (including aramid fiber), acrylic fiber. , Synthetic fiber such as polybenzoxazole fiber, polyester fiber, rayon fiber (polynosic fiber, solvent-spun cellulose fiber, etc.), metal fiber, glass fiber and the like.
• PVA polyvinyl alcohol
• polyolefin fiber polyamide fiber (including aramid fiber)
• acrylic fiber including aramid fiber
• Synthetic fiber such as polybenzoxazole fiber, polyester fiber, rayon fiber (polynosic fiber, solvent-spun cellulose fiber, etc.), metal fiber, glass fiber and the like.
• the PVA-based fiber is a fiber containing a vinyl alcohol-based polymer, and in view of mechanical performance, adhesiveness with a hydraulic material and alkali resistance, the fiber may contain the vinyl alcohol-based polymer in an amount of 30% by mass or more.
• the content is preferably 60% by mass or more, more preferably 80% by mass or more.
• the fibers contained in the convergent yarn of the present invention are preferably PVA-based fibers from the viewpoint of easily increasing the strength of the obtained molded product.
• the fiber is a PVA-based fiber, it has high hydrophilicity for the reason of the molecular structure, and the hydroxyl group of the fiber and Ca of the cement are bonded, so that the affinity between the fiber and the cement is improved, and the chemical adhesive force is easily enhanced. ..
• the structure around the fibers is likely to be rich in calcium hydroxide, it is easy to increase the frictional resistance between the fibers and the cement.
• the vinyl alcohol-based polymer constituting the PVA-based fiber may be a homopolymer of vinyl alcohol, or may be a copolymer of vinyl alcohol and another monomer as long as the effect of the present invention is not impaired. It may be modified or modified. From the viewpoint of easily increasing the mechanical strength, alkali resistance, hot water resistance, etc. of the fiber, a modified polyvinyl alcohol-based resin which is optionally contained when the amount of all monomer units constituting the vinyl alcohol-based polymer is 100 mol% The total amount of the structural units derived from the monomer and the amount of the optional monomer other than vinyl alcohol is preferably 30 mol% or less, more preferably 10 mol% or less.
• the viscosity average degree of polymerization of the vinyl alcohol-based polymer constituting the PVA-based fiber is preferably 1,000 or more, more preferably 1,500 or more, from the viewpoint of easily improving the mechanical strength, alkali resistance and hot water resistance of the fiber. is there. From the viewpoint of easily reducing the production cost of the vinyl alcohol-based polymer, the viscosity average degree of polymerization is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less.
• the method of measuring the viscosity average degree of polymerization is as described above for the modified polyvinyl alcohol.
• the degree of saponification of the vinyl alcohol polymer constituting the PVA fiber is preferably 99 mol% or more, more preferably 99.5 mol% or more, and further preferably from the viewpoint of heat resistance, durability, and dimensional stability of the fiber. It is 99.8 mol% or more.
• the upper limit of the degree of saponification is 100 mol% or less.
• the method for measuring the degree of saponification is as described above for the modified polyvinyl alcohol.
• the fibers contained in the convergent yarn of the present invention may be fibers made of one type of polymer or may be composite fibers made of two or more types of polymers.
• Examples of the shape of the composite fiber include a sea-island type, a core-sheath type, and a side-by-side type.
• the fiber length of the fibers contained in the convergent yarn of the present invention is preferably 6 mm or more, more preferably 8 mm or more, still more preferably 10 mm or more, preferably 60 mm or less, more preferably 50 mm or less, further preferably 40 mm or less. is there.
• the fiber length of the polyvinyl alcohol-based fiber is not more than the above upper limit, the entanglement of the fibers is further suppressed, and the dispersibility of the fiber in the molded body of the hydraulic composition is further increased. Further, since the fibers follow the expansion and contraction of the molded body of the hydraulic composition, the reinforcing performance of the hydraulic material is further improved.
• the fiber length of the polyvinyl alcohol fiber is not less than the above lower limit, the adhesion of the fiber to the hydraulic material becomes high, and the reinforcing performance for the hydraulic material is further excellent.
• the aspect ratio of the fibers contained in the convergent yarn of the present invention is preferably 50 to 2,500, more preferably 60 to 2,000, still more preferably 60 to 1,000, still more preferably 60 to 900, and particularly preferably. Is 70 to 800.
• the aspect ratio is not less than the above lower limit, it is easy to enhance the reinforcing effect by adding fibers.
• the aspect ratio is not more than the above upper limit, it is easy to suppress the entanglement of the disentangled fibers contained in the matrix containing the hydraulic material, and it is easy to enhance the reinforcing performance for the hydraulic material.
• the aspect ratio means the ratio (L/D) of the fiber length (L) and the fiber diameter (D), and is defined in JIS L1015 “Chemical fiber staple test method (8.5.1)”.
• the fiber length can be calculated according to the above formula and the ratio can be calculated from the ratio to the fiber diameter.
• the average fiber diameter of the fibers contained in the convergent yarn of the present invention is preferably 3 to 900 ⁇ m, more preferably 4 to 800 ⁇ m, and further preferably 5 to 700 ⁇ m.
• the average fiber diameter of the fibers can be obtained by measuring the fiber diameters of a plurality of fibers with an optical microscope and calculating the average value thereof, and may be measured, for example, by the method described in Examples.
• the tensile strength of the fibers contained in the convergent yarn of the present invention is preferably 5 cN/dtex or more, more preferably 8 cN/dtex or more, further preferably 10 cN/dtex or more, particularly preferably 11 cN/dtex or more.
• the upper limit of the tensile strength of the fiber contained in the convergent yarn of the present invention is not particularly limited, but is, for example, 30 cN/dtex or less. The tensile strength of the fiber is measured according to JIS L1013.
• the converging yarn of the present invention may contain other components in addition to the fiber and the converging agent as long as the effects of the present invention are not impaired.
• other components include oil agents.
• examples of the oil agent include hydrocarbon oil and silicone oil.
• the converging yarn of the present invention contains at least fibers and modified polyvinyl alcohol as a converging agent.
• the fiber content in the bunching yarn is preferably 85 to 99.5% by mass, more preferably 88 to 99% by mass, and particularly preferably 90 to 98% by mass, based on the total mass of the bunching yarn.
• the content of the fibers is within the above range, it is easy to disperse in the hydraulic composition at the time of mixing, and it is easier to further improve the strength of the molded body.
• the content of the sizing agent in the sizing yarn is preferably 0.01 to 15% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 15% by mass, based on the total mass of the sizing yarn. %, particularly preferably 1 to 12% by weight, very particularly preferably 1 to 10% by weight, particularly preferably 2 to 10% by weight.
• the content of the sizing agent in the sizing yarn is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass, based on the mass of the fibers contained in the sizing yarn.
• % Or more still more preferably 1% by mass or more, particularly preferably 2% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less.
• the content of the sizing agent is preferably 0.01 to 15% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass based on the mass of the fiber contained in the sizing fiber. It may be 15% by weight, particularly preferably 1-12% by weight, very particularly preferably 1-10% by weight and particularly preferably 2-10% by weight.
• the content of the sizing agent is not less than the above lower limit, it is easy to prevent defibration of the fibers when mixing the hydraulic material and the sizing fibers in a dry state, and as a result, it is easy to prevent damage to the fibers. Further, when the content is less than or equal to the above upper limit, the defibration degree of the fiber when kneading the convergent yarn with the hydraulic material and water is likely to be improved.
• the fiber defibration of the convergent yarn of the present invention is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
• the upper limit of the fiber disentanglement may be 100% or less.
• the fiber defibration degree in this specification is a ratio of the defibrated fibers after kneading a convergent yarn with a hydraulic material and water for 30 seconds.
• aggregate, cement and converging yarn are dry mixed in a mass ratio of 50:50:1.5 aggregate:cement:convergent yarn, and then 0.4 based on the mass of cement in the mixture.
• the ratio of the amount of disentangled convergent yarns was calculated when the amount of fibers contained in the mixture was 100%,
• the fiber defibration degree can be measured. Specifically, it may be measured by the method described in Examples.
• the defibration degree of the fiber after kneading with the hydraulic material and water for 30 seconds is not less than the above lower limit, damage to the fiber is easily suppressed, a fiber ball is hard to be formed, and mechanical strength of a finally obtained molded body is obtained. Easy to improve.
• the fiber cohesion of the convergent yarn of the present invention is preferably 10% or less, more preferably 8% or less, and further preferably 5% or less.
• the lower limit of the fiber disentanglement may be 0% or more.
• the fiber cohesion in the present specification is the ratio of the amount of fiber balls after kneading the convergent yarn with the hydraulic material and water for 3 minutes.
• aggregate, cement and converging yarn are dry mixed in a mass ratio of 50:50:1.5 aggregate:cement:convergent yarn, and then 0.4 based on the mass of cement in the mixture.
• the degree of fiber cohesion can be measured. Specifically, it may be measured by the method described in Examples. When the degree of cohesion of the fiber after kneading with the hydraulic material and water for 3 minutes is not more than the above upper limit, it is easy to improve the mechanical strength of the finally obtained molded body.
• the method for producing the fiber contained in the convergent yarn of the present invention is not particularly limited, and general melt spinning, solution spinning, dry spinning and the like can be used.
• the fibers contained in the convergent yarn of the present invention can be produced, for example, by the following method. For example, when the fiber is a PVA-based fiber, a vinyl alcohol-based polymer is made into a water-containing chip having a concentration of 40 to 60% by mass, heated and melted by an extruder, and defoamed. Then, a crosslinking agent is added to the aqueous vinyl alcohol polymer solution.
• cross-linking agent examples include ammonium sulfate, sulfuric acid, ammonium phosphate, phosphoric acid, hydrochloric acid, nitric acid, acetic acid and oxalic acid, but from the viewpoint of not corroding pipes, giving off a bad odor, and not foaming fibers, ammonium sulfate is used. Is preferred.
• the addition amount of the cross-linking agent is preferably 0.5 to 10% by mass based on the mass of the vinyl alcohol polymer.
• the temperature of the spinning dope is preferably 90 to 140°C. The spinning dope containing such a cross-linking agent is pressurized and discharged into the air from the nozzle hole to perform dry spinning.
• the nozzle hole may have a circular shape, or may have an irregular shape other than the circular shape, such as a flat shape, a cross shape, a T shape, a Y shape, an L shape, a triangular shape, a square shape, or a star shape.
• the spinning method may be any of a wet method, a dry-wet method, and a dry method.
• the drying temperature is usually 100° C. or lower, and it is preferable that the drying is completely performed under the temperature condition of 100° C. or higher when the drying is performed to some extent.
• Stretching is usually carried out at a stretching temperature of 200 to 250°C, preferably 220 to 240°C.
• the draw ratio is usually 5 times or more, preferably 6 times or more.
• Stretching is carried out in a hot-air type stretching furnace for about 20 seconds to 3 minutes.
• the fiber thus drawn is subjected to a heat treatment in order to achieve a constant length or shrinkage, if necessary.
• the fiber thus obtained may be crimped if necessary, or may be coated with an oil agent.
• the cross-linking agent added to the spinning dope reacts with the OH group of the polyvinyl alcohol during the drawing to cause cross-linking.
• the modified fiber is applied to the obtained fiber as a sizing agent.
• the amount of the sizing agent applied is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1% by mass, based on the mass of the fiber. % Or more, particularly preferably 2% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less.
• the content of the sizing agent is preferably 0.01 to 15% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass based on the mass of the fiber contained in the sizing fiber.
• the coating method is not particularly limited, but a method of coating a solution (preferably an aqueous solution) containing the sizing agent is preferable from the viewpoint of easily adding the sizing agent uniformly to the fibers.
• concentration of the sizing agent in the solution may be appropriately set according to the coating device, the desired content of the sizing agent, the viscosity of the solution, and the like.
• the step of applying the sizing agent to the fibers may be any step after the spinning step. The application may be performed by roller touch, crow mouth and the like.
• the sizing fiber of the present invention can be obtained by drying and removing the solvent (for example, water) after the application.
• the drying conditions are not particularly limited, and the temperature and time may be appropriately set so that the solvent used is volatilized.
• the solution containing the sizing agent may be mixed with other components such as an oil agent to produce the sizing yarn of the present invention.
• the cutting method is not particularly limited, and examples thereof include a side cut method, a water jet method, a laser cut method, a disc blade cut method, an ultrasonic wave cut method, and a scissor cut method.
• the side cut method, the laser cut method, and the water jet method are preferable from the viewpoint of easily suppressing damage to the fiber end portion.
• a hydraulic composition can be obtained by mixing the convergent yarn of the present invention with a cement component, an aggregate and water.
• a molded body such as mortar concrete can be produced by curing the hydraulic composition.
• the molded product produced using the convergent yarn of the present invention has a low number of fiber balls and high mechanical strength, and is therefore useful as various building materials such as wall materials and roof materials.
• the present invention also provides a hydraulic composition containing at least the convergent yarn of the present invention, a cement component, an aggregate and water, and a molded product obtained by curing the hydraulic composition.
• a plurality of fibers are integrated by a converging agent.
• the converging yarn of the present invention is Alternatively, a plurality of fibers may be included in a separated state. Therefore, that the hydraulic composition and the molded product include the convergent yarn of the present invention means that the convergent yarn of the present invention in a state in which a plurality of fibers are integrated by a converging agent is, at least in part, a plurality of fibers. May be contained in the hydraulic composition and the molded product in a state of being integrated by the sizing agent, or by using a sizing yarn in a state in which a plurality of fibers are integrated by the sizing agent.
• the hydraulic composition may be produced, and the sizing agent may be dissolved in the hydraulic composition and the molded product, and a plurality of fibers may be contained in a separated state.
• a cement component As the hydraulic material contained in the hydraulic composition, a cement component can be mentioned.
• the cement component include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, Portland cement such as moderate heat Portland cement, alumina cement, blast furnace cement, silica cement, and fly ash cement. You may use these cements individually or in combination of 2 or more types.
• aggregate As the aggregate contained in the hydraulic composition, various aggregates can be used as necessary. Examples of such aggregates include fine aggregates, lightweight aggregates, and coarse aggregates. You may use these aggregates individually or in combination of 2 or more types.
• the fine aggregate may be fine aggregate having a particle size of 5 mm or less, for example, sands having a particle size of 5 mm or less; silica stone, fly ash, blast furnace slag, volcanic ash-based shirasu, various sludges, rock minerals, etc. Fine aggregates obtained by pulverizing or granulating the above inorganic material can be mentioned. You may use these fine aggregates individually or in combination of 2 or more types. Examples of sands include sands such as river sand, mountain sand, sea sand, crushed sand, silica sand, slag, glass sand, iron sand, ash sand, calcium carbonate, and artificial sand. You may use these fine aggregates individually or in combination of 2 or more types.
• Coarse aggregate is an aggregate that contains 85% by mass or more of particles having a particle diameter of 5 mm or more.
• the coarse aggregate may be composed of particles having a particle size of more than 5 mm.
• Examples of the coarse aggregate include various types of gravel, artificial aggregate (blast furnace slag, etc.), recycled aggregate (recycled aggregate of construction waste, etc.), and the like. These coarse aggregates may be used alone or in combination of two or more.
• lightweight aggregates include natural lightweight aggregates such as volcanic gravel, expanded slag and charcoal shell, and artificial lightweight bones such as expanded pearlite, expanded perlite, expanded black stone, vermiculite, shirasu balloon and fly ash microballoon. There are materials. These lightweight aggregates may be used alone or in combination of two or more kinds.
• the hydraulic composition may include functional aggregate in addition to the above aggregate.
• the functional aggregates include colored aggregates, hard aggregates, elastic aggregates, and aggregates having a specific shape.
• the layered silicate for example, , Mica, talc, kaolin
• alumina for example, silica and the like.
• the ratio of the functional aggregate to the aggregate can be appropriately set according to each type.
• the mass ratio of the aggregate to the functional aggregate is , 99/1 to 70/30, preferably 98/2 to 75/25, and more preferably 97/3 to 80/20. You may use these functional aggregates individually or in combination of 2 or more types.
• the mass ratio (aggregate (S)/cement component (C)) of the total amount (S) of the aggregate and the cement component (C) is preferably 1/10 to 5/1, more preferably 1/8 to 4/ It may be 1, more preferably 1/6 to 3/1.
• the amount of the convergent yarn of the present invention added to the hydraulic composition can be appropriately set according to the type of fibers contained in the convergent yarn of the present invention, the fiber length, the aspect ratio, and the like.
• the amount of fibers is preferably 1 to 70 kg/m 3 , more preferably 2 to 40 kg/m 3 , and further preferably 3 to, based on the volume of the finally obtained molded body. It may be added in an amount so as to be 30 kg/m 3 .
• the amount of fibers is preferably 1 to 70 kg/m 3 , more preferably 2 to 40 kg/m 3 , based on the volume of the finally obtained molded body. More preferably, the amount may be 2 to 30 kg/m 3 .
• the amount of the bundled yarns added is within the above range, the reinforcing effect of the fibers is further enhanced, and the entanglement of the fibers due to the excessive fiber content is easily suppressed, and the reinforcing effect of the fibers is further improved.
• the hydraulic composition may optionally contain various admixtures.
• admixtures include AE agents, superplasticizers, water reducing agents, high performance water reducing agents, AE water reducing agents, high performance AE water reducing agents, thickeners, water retention agents, water repellents, swelling agents, curing accelerators, Examples include setting retarders, polymer emulsions [acrylic emulsions, ethylene-vinyl acetate emulsions, and SBR (styrene-butadiene rubber) emulsions].
• the admixture may be contained alone or in combination of two or more kinds.
• the polymer emulsion can not only strengthen the brittleness of the finally obtained molded product, but also strengthen the adhesive force between the components in the molded product. Furthermore, by combining the polymer emulsion, not only can the water impermeability of the molded article be improved, but also excessive drying can be suppressed.
• the hydraulic composition may optionally include a water-soluble polymer substance.
• the water-soluble polymer substance include cellulose ethers such as methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and hydroxypropyl methyl cellulose, polyvinyl alcohol, polyacrylic acid, and lignin sulfonate. These water-soluble polymer substances may be used alone or in combination of two or more.
• the number of fiber balls contained in the finally obtained molded body is preferably 0 to 5, more preferably 0 to 1.
• the resulting molded body has higher mechanical strength and is excellent in bending strength, compression strength and the like.
• the fiber ball is caused by poor mixing of the fiber and the cement component in the hydraulic composition, and is formed by intertwining the fibers with each other and has a ball-like shape.
• the number of fiber balls can be measured by the method described in the examples.
• the slump loss of the molded body is preferably 6 cm or less, more preferably 4 cm or less, and further preferably 2 cm or less.
• the lower limit value of the slump loss is not particularly limited, but is usually 1 cm or more.
• the slump loss can be measured by performing a slump test in accordance with the slump test method for concrete according to JIS A1101.
• the molded product can be obtained by curing a hydraulic composition containing the convergent yarn of the present invention, water, a cement component, an aggregate, and, if necessary, various admixtures and the like within a range that does not impair the effects of the present invention. it can.
• the hydraulic composition is kneaded by a kneading means such as a known or conventional mixer.
• a kneading means such as a known or conventional mixer.
• the kneading order of the constituent materials can also be carried out without particular limitation, but in order to suppress the physical impact on the fibers as small as possible, the composition of the hydraulic composition, the water/cement component ratio (W/ It is appropriately adjusted according to C) and the like.
• the water/cement component ratio (W/C) in the hydraulic composition is appropriately adjusted according to the constitution of the hydraulic composition and the like, but is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, More preferably, it is 30 to 40% by mass.
• the method for supplying the convergent yarn of the present invention to the hydraulic composition is not particularly limited.
• various quantitative supply devices for example, a vibration feeder, a screw feeder, a belt feeder, etc.
• a vibration feeder for example, a vibration feeder, a screw feeder, a belt feeder, etc.
• the method for adding fibers to disperse the fibers is not particularly limited as long as the fibers can be dispersed in a state where the fibers do not substantially exist as a fiber aggregate.
• examples of the mixer or kneader with high stirring performance include double-arm kneader, pressure kneader, Erich mixer, super mixer, planetary mixer, Banbury mixer, continuous A mixer or a continuous kneader can be used.
• the hydraulic composition containing fibers may be put into a mold and vibration may be applied as necessary.
• the vibration is usually applied by vibrating the formwork. By applying vibration, the hydraulic composition can be distributed more evenly inside the mold.
• the frequency of vibration is preferably 10 to 1000 Hz, more preferably 20 to 900 Hz, and further preferably 30 to 800 Hz.
• the amplitude is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 18 ⁇ m, and further preferably 1 to 15 ⁇ m.
• the hydraulic composition placed in the mold may be pressed by a press using a top molding die or roll.
• the pressure at the time of pressing can be appropriately set depending on the state of the kneaded hydraulic composition, the form of the mold, etc., but is preferably 10 to 150 MPa, more preferably 20 to 140 MPa, further preferably 30 to 130 MPa. ..
• the pressure is 10 MPa or more, the materials are sufficiently integrated, and when the pressure is 150 MPa or less, the fibers are less likely to be damaged by the pressure from the aggregate, and the decrease in the fiber strength and the durability of the mold are avoided. be able to.
• ⁇ Pressing may be performed while heating as needed.
• the heating temperature is preferably 40 to 90°C, more preferably 45 to 85°C, and further preferably 50 to 80°C.
• a molded body After molding into a prescribed shape, a molded body can be obtained by curing the hydraulic composition by curing in an atmosphere at 100°C or lower.
• the use of the hydraulic composition containing the convergent yarn of the present invention is not particularly limited, and a molded product for any use can be manufactured.
• molded articles include blocks, floor panels, wall panels, partitions, roofing materials, roof tiles, and the like.
• ⁇ Average fiber diameter of fiber> 100 fibers were randomly taken out, and the fiber diameter at the central portion in the length direction of each fiber was measured by an optical microscope, and the average value was taken as the average fiber diameter.
• the aspect ratio means the ratio (L/D) between the fiber length (L) and the fiber diameter (D).
• the average fiber length was calculated according to JIS L1015 “Chemical fiber staple test method (8.5.1)”, and the aspect ratio of the fiber was calculated by the ratio with the average fiber diameter.
• the defibrated fibers and the undefibrated convergent yarns were separately collected with tweezers, dried at 100° C. for 24 hours, and then the mass of the defibrated fibers (W a g ), and the mass (W b g) of the undefibrated convergent yarn were measured.
• ⁇ Number of buckling parts 50 g of the molded body was immersed in 500 ml of a 5% by mass aqueous hydrochloric acid solution at 20° C. to dissolve the cement in the molded body. Then, 20 fibers contained in the molded body were taken out with tweezers. The fibers taken out were immersed in a dye aqueous solution containing a blue dye at 80° C. for 30 minutes. Here, when the fiber has a bent portion (buckling portion), the buckling portion is dyed blue in the dyeing step. The dyed fibers were taken out, spread on a slide glass so that the fibers did not overlap each other as much as possible, and then a cover glass was placed on the slide glass to give an evaluation sample.
• This evaluation sample was enlarged and observed with a video microscope manufactured by KEYENCE CORPORATION, and the number of dyed portions existing in each fiber was counted. The number of the 20 fibers was counted, and the average value of the obtained numbers was used as the number of buckling portions per fiber (pieces/piece).
• ⁇ Bending strength of molded body> A strip-shaped test piece having a width of 5 cm and a length of 16 cm was cut out from the molded body. The test piece was put in a dryer adjusted to 40° C. for 72 hours in order to adjust the water content at the time of measuring the flexural strength to obtain a flexural strength measurement sample. The bending strength was measured in accordance with JIS A1408 with an autograph AG5000-B manufactured by Shimadzu Corporation under the conditions of a test speed (loading head speed) of 2 mm/min, a center loading method, and a bending span of 100 mm. ..
• PVA fiber 1 polyvinyl alcohol fiber (Kuraray Co., Ltd., vinylon (registered trademark)), tensile strength 14 cN/dtex, average fiber diameter 14 ⁇ m
• PVA fiber 2 polyvinyl alcohol fiber (Kuraray Co., Ltd., vinylon (registered trademark)), tensile strength 12 cN/dtex, average fiber diameter 38 ⁇ m
• ⁇ PP fiber polypropylene fiber, fiber strength 5.4 cN/dtex, average fiber diameter 17 ⁇ m
• (Convergent) -Acrylic acid-modified PVA1 viscosity average polymerization degree 1,500, saponification degree 99.5 mol%, content of structural unit (X) derived from acrylic acid 5 mol%, content of structural unit (X1) 4.8 Mol%, the content of the structural unit (X2) is 0.2 mol%, the ratio of (X1) to the total amount of the structural units (X1) and (X2) is 0.96, and the structural units (X1) and (X2) are Modified polyvinyl alcohol/acrylic acid modified PVA2 in which both functional groups X and Y are hydrogen atoms: viscosity average polymerization degree 1,500, saponification degree 99.5 mol%, content of structural unit (X) derived from acrylic acid 12 mol %, structural unit (X1) content 11.5 mol %, structural unit (X2) content 0.5 mol %, ratio of (X1) to total amount of structural units (X1) and (X2) Is 0.96, and the functional groups X and Y in the structural
• Modified polyvinyl alcohol/maleic acid modified PVA viscosity average polymerization degree 1,300, saponification degree 97 mol%
• Modified polyvinyl alcohol/itaconic acid-modified PVA having a content of the structural unit (X) derived from maleic acid of 4 mol%: a viscosity average polymerization degree of 620, a saponification degree of 77 mol%, and a structural unit (X) derived from itaconic acid modification Content of 1 mol% of modified polyvinyl alcohol/unmodified PVA1: viscosity average polymerization degree of 500, unmodified polyvinyl alcohol/saponification degree of 88 mol% unmodified PVA2: viscosity average polymerization degree of 1,700, saponification degree of 98 mol% Modified polyvinyl alcohol
• cement ⁇ Ordinary Portland cement (made by Taiheiyo Cement Co., Ltd.) (aggregate) ⁇ No. 6 silica sand (manufactured by Toyo Materialan Co., Ltd.)
• Example 1 Completely saponified PVA having a viscosity average degree of polymerization of 1,700 (manufactured by Kuraray Co., Ltd.) was dissolved in water at a concentration of 16.5% by mass, and 1.6% by mass of boric acid was added to the mass of the PVA. Then, a spinning dope was prepared. The spinning dope is wet-spun in a coagulation bath of sodium hydroxide 11 g/L and Glauber's salt 350 g/L at 70° C., and is subjected to roller drawing, neutralization, wet heat drawing, washing with water, and drying, and then fiber production in the same manner. In the heat treatment step in the process, the film was dry-heated and wound at 235° C.
• Example 2 Convergent yarn 2 was obtained in the same manner as in Example 1 except that PVA fiber 2 was used instead of PVA fiber 1, and the amount of acrylic acid-modified PVA 1 attached to PVA fiber 2 was changed as shown in Table 1.
• Example 3 Polypropylene ("Y2000GV” manufactured by Prime Polymer Co., Ltd.) was put into an extruder of a melt spinning device, melt-kneaded, and discharged from a spinneret to produce an undrawn yarn at a speed of 800 m/min. Then, the undrawn yarn was introduced into a hot air oven having a temperature of 128° C. and drawn 4.6 times to obtain PP fibers having an average fiber diameter of 17 ⁇ m and a fiber strength of 5.4 cN/dtex. A sizing agent was attached to the obtained PP fiber in the same manner as in Example 1. After that, the yarn was cut to obtain a convergent yarn 3 having an aspect ratio of 353.
• Y2000GV manufactured by Prime Polymer Co., Ltd.
• Example 4 Convergent yarn 4 was obtained in the same manner as in Example 1 except that maleic acid-modified PVA was used as the sizing agent instead of acrylic acid-modified PVA1.
• Example 5 Convergent yarn 5 was obtained in the same manner as in Example 1 except that the amount of the acrylic acid-modified PVA1 attached to the PVA fiber 1 was changed as shown in Table 1.
• Convergent yarn 6 was obtained in the same manner as in Example 1 except that unmodified PVA1 was used as the sizing agent instead of the acrylic acid-modified PVA1.
• Convergent yarn 7 was obtained in the same manner as in Example 1 except that PVA fiber 2 was used as the fiber instead of PVA fiber 1, and unmodified PVA1 was used as the sizing agent instead of acrylic acid-modified PVA1.
• Convergent yarn 9 was obtained in the same manner as in Example 1 except that unmodified PVA2 was used as the sizing agent instead of acrylic acid-modified PVA1.
• Convergent yarn 10 was obtained in the same manner as in Example 1 except that itaconic acid-modified PVA was used as the sizing agent instead of acrylic acid-modified PVA1.
• a kneaded product was prepared for each of the obtained converging yarns 1 to 11 according to the following method.
• Converging yarn, No. 6 silica and ordinary Portland cement are put into a turbo mixer (manufactured by Taiheiyo Kiko Co., Ltd.) in such an amount that the mass ratio of converging yarn: No. 6 silica: ordinary Portland cement is 1.5:50:50.
• they were mixed for 6 minutes in a dry state under the condition of 500 times/minute.
• water was added so that the mass ratio of water/normal Portland cement was 0.4, and the mixture was kneaded for 2 minutes under the condition of 400 times/minute using the reciprocating rotary agitator, and kneaded product 1 to I got 11.
• a molded body was obtained from each of the obtained kneaded products 1 to 11 according to the following method.
• the kneaded product obtained by the kneading step was filled in a mold having a width of 50 cm and a length of 180 cm with a target thickness of 10 mm.
• the kneaded product filled in the mold was pressed using a vibration press machine while applying a vibration of 200 Hz and an amplitude of 1 ⁇ m at a pressure of 40 MPa.
• the kneaded product was kept in an environment of a temperature of 50° C. and a humidity of 98% for 24 hours.
• the molded body after the primary curing was wrapped in a compress and cured for 28 days in an environment of a temperature of 20° C. and a humidity of 60% to obtain molded bodies 1 to 11.
• the convergent yarns 1 to 11 obtained in the above Examples and Comparative Examples were measured for the fiber defibration degree and the fiber cohesion degree after kneading with the hydraulic material according to the above measuring method.
• the number of buckling parts and the bending strength of the molded body of the molded body obtained according to the above method were measured according to the above measuring method. The results obtained are shown in Table 1.
• the convergent yarn of the present invention had a high degree of fiber disintegration and little fiber aggregation when kneaded with a hydraulic material such as cement. Further, the convergent yarn of the present invention had a small number of buckling portions of fibers in the molded body, and was excellent in the reinforcing effect of the cured product of the hydraulic composition. Therefore, it was confirmed that the convergent yarn of the present invention is suitable as a reinforcing convergent yarn added to a hydraulic material.
• Examples 1 to 3 and 5 using the modified polyvinyl alcohol having a specific amount of the structural unit (X1) and the structural unit (X2) have a high sizing property of the fiber as the sizing agent due to the structural unit (X1).
• the fibers are difficult to be unraveled during dry mixing of the convergent yarn and the hydraulic material, and the occurrence of buckling portions of the fibers is suppressed during dry mixing, and as a result, the fibers aggregate when mixed in the hydraulic composition. Easy to suppress.
• the structural unit (X1) is ring-opened and a part of the structural unit is changed to a more water-soluble structural unit (X2), so that the fiber is rapidly defibrated and the fiber is unwound. Higher fineness. As a result, the bending strength of the molded body was improved.
• unmodified polyvinyl alcohol is used as the sizing agent as in Comparative Examples 1, 2 and 4, the defibration degree of the fibers when kneaded in the hydraulic composition is low and the bending strength of the molded article is insufficient. there were.
• Comparative Example 2 in which fibers having a large average fiber diameter were used, compared to the case in Comparative Example 1 in which fibers having a small average fiber diameter were used, when the convergent yarn and the hydraulic material were dry-mixed, the fibers were Since it became easy to be loosened, buckling of the fiber was likely to occur during dry mixing, and as a result, the degree of fiber aggregation was increased. Further, in the case of the bunching yarn using a small amount of unmodified polyvinyl alcohol as the bunching agent as in Comparative Example 3, the amount of the bunching agent is small, and thus a large amount of bare fibers are included.
• the sizing agent When the itaconic acid-modified PVA having a low degree of saponification or the acrylic acid-modified PVA2 having a high content of the structural unit (X) derived from an unsaturated carboxylic acid is used as the sizing agent as in Comparative Examples 5 and 6, the water of the sizing agent is used. It is considered that the performance as a sizing agent is deteriorated due to the increased solubility in sucrose. Such fibers are likely to be damaged during the dry mixing of the convergent yarn and the hydraulic material to cause a buckling portion.
• the convergent yarn according to the present invention has a high defibration degree of fibers when kneaded with a hydraulic material such as cement, and has little aggregation of the fibers, and therefore has an excellent reinforcing effect on the molded body of the hydraulic material, and It can be suitably used as a reinforcing yarn to be added to the composition.

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• 2019
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