Classifications

• • 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
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/53—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
• • 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
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
• • D—TEXTILES; PAPER
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  • 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
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
• • D—TEXTILES; PAPER
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  • 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
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/61—Polyamines polyimines
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  • 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
  • D06M2101/02—Natural fibres, other than mineral fibres
  • D06M2101/04—Vegetal fibres
  • D06M2101/06—Vegetal fibres cellulosic
  • D06M2101/08—Esters or ethers of cellulose
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  • 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
• • D—TEXTILES; PAPER
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  • 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
  • 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
  • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M2101/32—Polyesters
• • D—TEXTILES; PAPER
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  • 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
  • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M2101/34—Polyamides

Definitions

• the present invention relates to surface-modified fibers that have excellent adhesion to resins and concrete, a method for producing the same, and molded articles made from the surface-modified fibers.
• Synthetic fibers such as polyvinyl alcohol and polyamide are excellent in strength and durability, as well as being lightweight and inexpensive. Therefore, they are used as fibers for reinforcing concrete and the like for the purpose of improving the strength of buildings and preventing cracks.
• the synthetic fibers are also used as fibers for reinforcing automobile tires, oil brake hoses, etc. When the fibers are used for this purpose, they need to be firmly bonded to the rubber, so surface-modified fibers with modified surfaces are used.
• Patent Document 1 discloses a fiber coated with branched polyethyleneimine in a ratio of about 0.2 to about 20% by mass based on the total weight of the coated fiber.
• Patent Document 2 describes a reinforcing fiber having a surface modification layer that covers at least a portion of the surface of the fiber, the surface modification layer being characterized in that it contains a specific polyamine compound.
• the surface-modified fibers described above show a certain level of performance in terms of adhesion, etc., but there is room for improvement. Specifically, the fiber described in Patent Document 1 does not have sufficient adhesive strength, and improvement is desired, while the fiber described in Patent Document 2 has the problem of discoloration due to being treated at a relatively high temperature. In addition, chemical fibers generally have extremely low adhesiveness and adhesion to resins, so the development of a method to improve these properties is desired.
• the present invention was made in consideration of the above-mentioned problems of the conventional art, and provides a surface-modified fiber that has excellent adhesion to resin and concrete and can suppress discoloration, a manufacturing method thereof, and a molded body using the surface-modified fiber.
• the present invention relates to the following [1] to [6].
• [1] A surface-modified fiber having a fiber and a surface-modified layer covering at least a part of the surface of the fiber,
• the surface-modified fiber characterized in that the surface-modified layer contains a compound having a hydrogen-bonding functional group, and the amount of the surface-modified layer is 0.01 to 2.5 parts by mass per 100 parts by mass of the fiber used as the raw material.
• the hydrogen-bonding functional group is one or more selected from a hydroxy group, a carboxy group, a salt of a carboxy group, an ester of a carboxy group, an acid anhydride of a carboxy group, a carbonyl group, an aldehyde group, an acetal of an aldehyde group, an amino group, and an amide group.
• the hue parameter (YI) of the surface-modified fiber is 0 to 50, The surface-modified fiber according to any one of items 1 to 3.
• the present invention provides a surface-modified fiber that has excellent adhesion to resin and concrete and suppresses discoloration, a method for producing the same, and a molded body using the surface-modified fiber.
• the surface-modified fiber of the present invention is a surface-modified fiber having a fiber and a surface-modified layer covering at least a part of the surface of the fiber,
• the surface modification layer contains a compound having a hydrogen-bonding functional group, and the amount of the surface modification layer is 0.01 to 2.5 parts by mass per 100 parts by mass of the fibers used as the raw material.
• a surface-modified layer containing a compound having a hydrogen-bonding functional group is provided on at least a part of the fiber surface, a strong mutual affinity is developed between the hydrogen-bonding functional group and the fiber, and between the hydrogen-bonding functional group and concrete or resin, resulting in improved adhesion between the fiber and resin, and between the fiber and concrete.
• a "surface modification layer covering at least a portion of the surface of the fiber” may mean an embodiment in which a surface modification layer is present on at least a portion of the surface of the fiber, for example, as a membrane or layer, or an embodiment in which the raw material of the fiber contains a component corresponding to the surface modification layer, and the component of the surface modification layer is present on a portion of the surface of the fiber itself.
• the surface modified layer in the present invention is a layer containing a compound having a hydrogen-bonding functional group.
• a compound having a hydrogen-bonding functional group in the surface modified layer it is possible to improve the adhesive strength between the surface modified fiber and resin, or between the surface modified fiber and concrete.
• hydrogen bond refers to a bonding interaction formed between a hydrogen atom (donor) that is bonded to an atom with a large electronegativity (O, N, S, etc.) and is electrically positively polarized, and an electronegative atom (acceptor) that has a lone pair of electrons.
• Examples of the hydrogen-bonding functional group include a hydroxyl group, an epoxy group, an ether group, a mercapto group, a carboxyl group, a carbonyl group, an aldehyde group, an amino group, an imino group, an imidazole group, a urethane group, an amide group, a urea group, an isocyanate group, a nitrile group, a silanol group, and derivatives thereof.
• Examples of the carboxyl group include a group derived from a monocarboxylic acid and a group derived from a dicarboxylic acid.
• Examples of the derivatives of the carboxyl group include a salt thereof, an esterified product thereof, an amidated product thereof, and an acid anhydride thereof.
• Examples of the derivatives of the aldehyde group include an acetalized product thereof.
• Examples of the derivatives of the silanol group include an esterified product thereof.
• one or more selected from a hydroxy group, a carboxy group, a salt of a carboxy group, an ester of a carboxy group, an acid anhydride of a carboxy group, a carbonyl group, an aldehyde group, an acetal of an aldehyde group, an amino group, and an amide group are preferred, and one or more selected from a carboxy group, a carbonyl group, an amino group, and an amide group are more preferred.
• the compound having a hydrogen-bonding functional group include compounds having a hydroxy group, such as ethylene glycol, diethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol; Compounds having an amino group, such as polyethyleneimine, polyallylamine, polyvinylamine, polydiallylmethylamine, polydiallylethylamine, and salts thereof; Compounds having an amide group, such as polyvinylpyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and ⁇ -caprolactam; Compounds having a carboxy group, such as maleic acid, fumaric acid, citraconic acid, perpropionic acid, and itaconic acid; Among the compounds having a hydrogen-bonding functional group, polyethyleneimine, polyallylamine, polyvinylpyrrolidone, etc. are preferred
• the amount of the compound having a hydrogen-bonding functional group in the surface modification layer is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably substantially 100% by mass.
• amount of the compound having a hydrogen-bonding functional group in the surface modification layer is within the above range, it is possible to improve the adhesion between the fiber and the resin, and also to obtain a surface-modified fiber with excellent transparency.
• the surface modification layer covers the entire surface of the fiber, but in reality it is sufficient that the surface modification layer covers at least a part of the fiber surface.
• the specific amount of the surface modification layer covering the fiber surface is 0.01 to 2.5 parts by mass relative to 100 parts by mass of the fiber used as the raw material, preferably 0.05 to 2.0 parts by mass, more preferably 0.1 to 1.5 parts by mass, even more preferably 0.15 to 1.2 parts by mass, even more preferably 0.15 to 1.0 parts by mass, and particularly preferably 0.2 to 0.5 parts by mass.
• the surface modification layer may or may not contain other components in addition to those described above, such as a crosslinking agent, an acid, a base, an inorganic salt, an organic salt, a pigment, a dye, an antioxidant, a polymerization initiator, and a plasticizer.
• the content of the other components in the surface modification layer is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of improving the adhesive strength with the resin.
• the hue parameter (YI) of the surface modified layer is preferably 0 to 50.
• the hue parameter (YI) of the surface modified layer is more preferably 0 to 45, even more preferably 0 to 35, even more preferably 0 to 30, and particularly preferably 0 to 25.
• the hue parameter (YI) of the surface modified layer in the present invention is a hue measured in accordance with JIS Z8722:2009, and specifically, can be measured by the method described in the examples.
• the fibers used in the surface-modified fiber of the present invention are not particularly limited, and hydrophilic or hydrophobic fibers can be used.
• the term "fiber” includes not only short fibers and long fibers, but also nonwoven fabrics, woven fabrics, knitted fabrics, felts, sponges, and other forms.
• hydrophilic synthetic fibers include synthetic fibers made of a thermoplastic resin having hydrophilic functional groups such as hydroxyl groups, carboxyl groups, sulfonic acid groups, and amino groups, and/or hydrophilic bonds such as amide bonds.
• thermoplastic resins include polyvinyl alcohol-based resins, polyamide-based resins (aliphatic polyamides such as polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, and polyamide 9C (a polyamide composed of nonanediamine and cyclohexanedicarboxylic acid); semi-aromatic polyamides synthesized from aromatic dicarboxylic acids and aliphatic diamines, such as polyamide 9T (a polyamide composed of nonanediamine and terephthalic acid); wholly aromatic polyamides synthesized from aromatic dicarboxylic acids and aromatic diamines, such as polyparaphenylene terephthalamide), and polyacrylamide-based resins).
• hydrophilic synthetic fibers may be used alone or in combination of two or more.
• these hydrophilic synthetic fibers may or may not be subjected to a hydrophilization treatment described below in order to further enhance the hydrophilicity.
• hydrophilic natural fibers include natural cellulose fibers such as wood pulp, e.g., kraft pulp, and non-wood pulp, e.g., cotton pulp and straw pulp.
• Hydrophilic regenerated fibers include regenerated cellulosic fibers such as rayon, lyocell, cupra, and polynosic. These natural fibers and regenerated fibers may be used alone or in combination of two or more kinds. Furthermore, these hydrophilic natural fibers and regenerated fibers may or may not be subjected to a hydrophilization treatment described below in order to further enhance the hydrophilicity.
• Hydrophilic fibers only need to have hydrophilic surfaces, and may be, for example, hydrophobic fibers whose surfaces have been treated to make them hydrophilic, core-sheath composite fibers with a hydrophobic resin as the core and a hydrophilic resin as the sheath, or non-composite fibers with a single structure that does not have a core-sheath structure.
• hydrophilic resins that make up the sheath see the descriptions of hydrophilic synthetic fibers.
• hydrophobic fibers made of hydrophobic resins include the hydrophobic fibers described below.
• the hydrophilization treatment is not particularly limited as long as it is a treatment that chemically or physically imparts hydrophilic functional groups to the fiber surface.
• it can be performed by modifying hydrophobic fibers made of a hydrophobic resin described below with a compound or derivative thereof that contains a hydrophilic functional group such as an isocyanate group, an epoxy group, a hydroxyl group, an amino group, an ether group, an aldehyde group, a carbonyl group, a carboxyl group, or a urethane group, or by modifying the surface by electron beam irradiation.
• hydrophobic fibers that could not be firmly adhered to resin using conventional technology.
• Hydrophobic fibers generally do not have polar functional groups on their fiber surface, and therefore have poor affinity with the adhesive components described below, and cannot be firmly adhered to resin.
• by providing a surface modification layer on the fiber surface as in the present invention even hydrophobic fibers can be firmly adhered to resin.
• Hydrophobic fibers that can be used in the present invention include, for example, polyolefin fibers such as polyethylene and polypropylene, polyester fibers such as polyethylene terephthalate, and wholly aromatic polyester fibers.
• polyester fibers are preferred because of their excellent manufacturing costs, strength, heat resistance, and durability.
• the fibers may be used alone or in combination of two or more kinds.
• the fibers used in the surface-modified fiber of the present invention preferably have a single-filament fineness of 500 to 4,500 dtex. If the single-filament fineness is 500 dtex or more, it is easy to produce industrially.
• the fiber used in the surface modified fiber of the present invention preferably has a single fiber fineness of 500 to 4,000 tex, and even more preferably 1,000 to 3,000 tex.
• the surface-modified fiber of the present invention is preferably produced by a production method having the following steps (1) and (2).
• steps (1) and (2) When produced by the method having the following steps, it is possible to produce a surface-modified fiber while preventing decomposition of the surface-modified layer, so that it is possible to have excellent adhesive strength and suppress coloring.
• Step (1) A step (2) of preparing a solution or dispersion of the compound having a hydrogen-bonding functional group and applying the solution or dispersion to the fiber.
• the solvent or dispersion medium in which the compound having a hydrogen-bonding functional group is dissolved or dispersed is not particularly limited, but from the viewpoints of storage stability and cost, water or a water-soluble organic solvent is preferred.
• the water-soluble organic solvent include organic solvents such as monohydric alcohols having 1 to 8 carbon atoms, such as methanol, ethanol, isopropanol, n-butanol, isopentyl alcohol, and tertiary butanol, polyhydric alcohols such as ethylene glycol, diethylene glycol, and glycerin, ketones having 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone, and carbonate-based organic solvents, such as propylene carbonate.
• water and alcohols having 1 to 6 carbon atoms are more preferred, and water is even more preferred.
• the amount of the compound having a hydrogen-bonding functional group when dissolving or dispersing the compound having a hydrogen-bonding functional group in the solvent or dispersion medium is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 20 parts by mass, even more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the solvent or dispersion medium.
• amount of the compound having a hydrogen-bonding functional group per 100 parts by mass of the solvent or dispersion medium is within the above range, it becomes possible to uniformly attach the compound having a hydrogen-bonding functional group to the fibers while suppressing production costs.
• the method for applying the solution or dispersion of the compound having a hydrogen-bonding functional group to the fiber is not particularly limited, and it is preferable to apply the solution or dispersion by one or more methods selected from, for example, immersion, a roll coater, an oiling roller, an oiling guide, nozzle (spray) application, brush application, etc.
• the temperature of the heat treatment in the step (2) is preferably 180 to 280° C., more preferably 190 to 270° C., even more preferably 200 to 260° C., even more preferably 220 to 250° C., and even more preferably 230 to 250° C. If the heat treatment temperature exceeds the upper limit, coloring occurs due to thermal decomposition. On the other hand, if the heat treatment temperature is less than the lower limit, sufficient adhesiveness is not achieved.
• the heat treatment time is preferably 0.1 to 50 seconds, more preferably 1 to 45 seconds, even more preferably 2 to 40 seconds, even more preferably 3 to 35 seconds, even more preferably 3 to 20 seconds, and even more preferably 3 to 10 seconds. If the heat treatment time exceeds the upper limit, coloring occurs due to thermal decomposition. On the other hand, if the time is less than the lower limit, adhesion may decrease. When the heat treatment time is set to a short time of 30 seconds or less, the treatment can be carried out online using a heat treatment furnace in the production process of polyvinyl alcohol-based fibers.
• the heat treatment may be carried out once, or it may be carried out two or more times by changing the treatment temperature and treatment time. However, if heat treatment is carried out multiple times at high temperatures, the surface-modified layer may decompose, which may result in discoloration or reduced adhesive strength.
• the surface-modified fibers can be in various shapes depending on the application. For example, they may be short fibers such as cut fibers, or long fibers. In the case of long fibers, it is also a preferred embodiment that they are multifilaments.
• the strength of the surface-modified fiber is preferably 4 to 30 cN/dtex, and more preferably 5 cN/dtex or more.
• the strength of the surface-modified fiber of the present invention can be measured by the method described in the Examples.
• the surface-modified fiber of the present invention can be used in any shape, but is preferably used in the form of a fiber cord, woven fabric, knitted fabric, etc., which contains at least a portion of the surface-modified fiber, and is more preferably used as a woven fabric or knitted fabric which contains at least a portion of the surface-modified fiber.
• a fiber cord woven fabric, knitted fabric, etc.
• it can also be used as a surface-modified fiber to be embedded in resin, cement, etc.
• the molded article of the present invention is not particularly limited as long as it uses the surface-modified fiber. Since the surface-modified fiber has excellent adhesion to resin, it is preferable to use a molded article having the surface-modified fiber and a resin layer. From the viewpoint of maintaining the shape of the resin, the surface-modified fiber used in the molded article is preferably used as a woven or knitted fabric containing the surface-modified fiber at least in part, and more preferably used as a part of a laminate in which a reinforcing layer made of the woven or knitted fabric and a resin layer are laminated.
• the resin used in the molded article of the present invention is not particularly limited, and examples thereof include polyolefin-based resins such as polyethylene resin, polypropylene resin, and polybutylene resin; methacrylic-based resins such as polymethyl methacrylate resin; polystyrene-based resins such as polystyrene resin, ABS resin, and AS resin; polyester-based resins such as polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate resin, polyethylene naphthalate (PEN) resin, and poly 1,4-cyclohexyldimethylene terephthalate (PCT) resin; polyamide (PA) resins such as 6-nylon resin, 6,6-nylon resin, and PA9T; polyvinyl chloride resin, polyoxymethylene (POM) resin, polycarbonate (PC) resin, polyphenylene sulfide resin, and the like.
• the resins include polyphenylene ether (PPS) resin, modified polyphenylene ether (PPE) resin, polyetherimide (PEI) resin, polysulfone (PSF) resin, polyethersulfone (PES) resin, polyketone resin, polyarylate (PAR) resin, polyethernitrile (PEN) resin, polyetherketone (PEK) resin, polyetheretherketone (PEEK) resin, polyetherketoneketone (PEKK) resin, polyimide (PI) resin, polyamideimide (PAI) resin, and fluorine (F) resin; liquid crystal polymer resins such as liquid crystal polyester resin; thermoplastic elastomers such as polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, and fluorine; and copolymer resins and modified resins thereof. These resins may be used alone or in combination of two or more. Among these, polyvinyl chloride resin is preferred from the
• the molded article of the present invention may be a fiber-reinforced resin obtained by mixing the surface-modified fiber with a resin.
• the resin used for the fiber-reinforced resin may be the resin described above.
• the content of the surface-modified fiber relative to 100 parts by mass of the resin is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass.
• the amount of the surface-modified fiber relative to the resin is within the above range, the dispersibility of the surface-modified fiber in the resin is improved, and an excellent reinforcing effect is exhibited.
• the resin used in the molded article of the present invention may contain additives such as an impact resistance improver, an inorganic filler, etc.
• additives include flame retardants, electrical conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping materials, antibacterial agents, insect repellents, deodorants, coloring inhibitors, heat stabilizers, release agents, antistatic agents, lubricants, colorants, and foaming agents.
• the content thereof is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of the resin.
• the effect of the additive can be obtained while maintaining the reinforcing effect of the surface-modified fiber.
• Polyethyleneimine Polyethyleneimine (1) "Epomin P-3000” manufactured by Nippon Shokubai Co., Ltd.
• Polyvinylpyrrolidone (PVP) Polyvinylpyrrolidone K-85 manufactured by Nippon Shokubai Co., Ltd.
• Polyallylamine "PAA-15” manufactured by Nittobo Medical Co., Ltd.
• Example 1 ⁇ Method for preparing a solution containing a compound having a hydrogen-bonding functional group> The solution used in Example 1 was prepared by mixing 14.3 g of polyethyleneimine (1) and 985.7 g of water. In other Examples and Comparative Examples, aqueous solutions constituting the surface modification layer were prepared in the same manner using the compounds listed in Table 1.
• Example 1 Polyvinyl alcohol-based fibers (PVA-based fibers) were immersed in an aqueous solution containing a compound having a hydrogen-bonding functional group, and then squeezed with a roller. The resulting fiber cord was dried at 140°C for 30 seconds. Then, the fiber cord was heat-treated at 240°C for 5 seconds and wound up to produce a surface-modified fiber.
• PVA-based fibers Polyvinyl alcohol-based fibers
• Examples 2 to 7 Comparative Examples 1 and 2> A surface-modified fiber was prepared in the same manner as in Example 1, except that the production conditions and heat treatment conditions were changed to those shown in Table 1.
• the fibers obtained in the examples and comparative examples were evaluated according to the following methods. The results are shown in Table 1.
• ⁇ Evaluation method> [Hue parameter (YI)]
• the hue parameter (YI) of the obtained surface-modified fiber was measured in accordance with JIS Z8722:2009 using a haze meter SH7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). The values of three points of the surface-modified fiber were measured, and the arithmetic average value was adopted as the hue parameter (YI).
• Table 1 The results are shown in Table 1.
• a resin for evaluation was prepared by adding 1% by mass of a curing agent to an unsaturated polyester resin (manufactured by Nippon Tokushu Toryo Co., Ltd.) and stirring the mixture.
• the resin for evaluation was attached in the form of beads so as to surround the surface-modified fiber obtained, and the fiber was left at room temperature (20°C) for 2 hours.
• the fiber was then heat-treated at 70°C for 2 hours.
• the fiber diameter and axial length (resin diameter) of the obtained sample were measured, and then the sample was fixed to a mount and the adhesive strength was measured using a testing machine (INSTRON's "Universal Material Testing Machine 3365"), and the interface shear stress was calculated using the following formula.
• Interfacial shear stress (N/mm 2 ) maximum detectable load (N)/( ⁇ fiber diameter (mm) ⁇ axial length (mm))
• Examples 8 and 9 Surface-modified fibers were prepared in the same manner as in Example 1, except that the compounds having hydrogen-bonding functional groups shown in Table 2 were used. The obtained surface-modified fibers were then twisted at 120 times/m and aligned to 36 fibers/inch to prepare a curtain-like sample. The sample and a soft polyvinyl chloride resin sheet were overlapped and heated at 1 MPa pressure and 160°C for 10 minutes to obtain a test piece. The obtained test piece was adjusted to a width of 1 inch and the peel strength (N/inch) was measured using a measuring machine (INSTRON's "Universal Material Tester 3365"). The results are shown in Table 2. The measurement results indicate that the larger the numerical value, the greater the adhesive strength between the surface-modified fiber and the polyvinyl chloride resin.
• the present invention makes it possible to obtain surface-modified fibers that have excellent adhesion and can suppress discoloration.

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• 2023
  • 2023-12-20 JP JP2024560360A patent/JP7670938B2/ja active Active
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