Fiber assembly

Abstract

[Problem] To provide a new technology that is less likely to cause defects due to rubbing of a coating film on the surface of a woven fabric, a knitted fabric, or a non-woven fabric. [Solution] This fiber assembly has a surface in which at least a portion thereof is coated. The fiber assembly is characterized by having a base material that is formed of a woven fabric, a knitted fabric, or a non-woven fabric, and a coating film that covers at least a portion of the surface of the base material, and is characterized in that the Martens hardness of the coating film measured at a maximum indentation depth of 100 nm or less is not less than 200 N / mm2 but less than 230 N / mm2.

Description

Fiber assembly

[0001] The present invention relates to a fiber assembly having a coating film.

[0002] To impart antibacterial or dust-proof properties to mesh substrates such as filters, coatings are sometimes formed from resin compositions containing functional materials and fixed to the mesh surface. A certain level of hardness is required for the coating to resist damage or peeling due to external forces such as abrasion. Pencil hardness tests are often used as an indicator of coating hardness for film substrates. However, the coating width formed on the fibers of woven products such as mesh is narrow, making it impossible to evaluate coating hardness using pencil hardness. Applying a coating that is resistant to abrasion requires measuring the coating hardness over a small area. However, direct measurement of coating hardness on fibers has not been used to design coatings, and resin compositions have typically been determined by trial and error, relying on the developer's intuition. Coating hardness over a small area can be measured as Martens hardness using an ultra-microhardness tester, and measurement standards are established in ISO 14577-1. Patent Document 1 discloses a laminated film in which the Martens hardness of a coating film formed on a film substrate is 0.300 GPa or more and 0.65 GPa or less at an indentation depth of 100 nm, and the Martens hardness is 0.15 GPa or more and 0.35 GPa or less at an indentation depth of 2000 nm.

[0003] Japanese Patent Application Laid-Open No. 2023-126785

[0004] The present invention provides a novel technique that can make it more difficult for a coating film on the surface of a woven fabric, knitted fabric, or nonwoven fabric to be damaged by rubbing.

[0005] Even if a coating film having the same composition as a coating film having a coating strength that does not cause peeling or the like on a film substrate is formed on a woven fabric, knitted fabric, or nonwoven fabric, the coating film does not necessarily not cause peeling or the like. This is thought to be because the curing conditions of the coating film on the film and on fibers such as woven fabrics, for example, the irradiation state of active energy rays, are not necessarily the same, so the crosslinking state of the coating film is different on the film substrate and on the fibers, or the way external forces are applied is different between films and fibers, resulting in different susceptibility to coating damage or the like. Therefore, in the case of substrates that are easily bent or shear-deformed, such as woven fabrics, the expected effect may not be obtained even if a coating resin composition that is effective on film-like substrates is applied. As a result of extensive research, the present inventors have found that by setting the coating film hardness on the surface of fibers constituting woven fabrics or the like within a predetermined range, the coating film can be made less susceptible to damage due to rubbing.

[0006] The gist of the present invention is as follows: [1] A fiber assembly having at least a portion of its surface coated, comprising a substrate made of woven, knitted or nonwoven fabric, and a coating film covering at least a portion of the substrate surface, wherein the Martens hardness of the coating film measured at a maximum indentation depth of 100 nm or less is 200 N / mm ２ 230N / mm or more ２ [2] The fiber assembly according to [1], wherein the coating film contains a functional agent. [3] The fiber assembly according to [2], wherein the functional agent is an inorganic material. [4] The fiber assembly according to [2], wherein the functional agent is an antibacterial agent and / or an antiviral agent. [5] The fiber assembly according to any one of [1] to [4], wherein the coating film contains an acrylic resin. [6] The fiber assembly according to any one of [1] to [4], wherein the coating film has a thickness of less than 500 nm. [7] The coating film formed on a woven, knitted or nonwoven fabric has a Martens hardness of 200 N / mm, measured at a maximum indentation depth of 100 nm or less. ２ 230N / mm or more ２ The method for increasing the resistance to abrasion of the coating film comprises setting the composition of the resin constituting the coating film so that the resistance to abrasion is less than or equal to 100%.

[0007] According to the present invention, a novel technique can be provided that can make it more difficult for the coating film on the surface of a woven fabric, knitted fabric or nonwoven fabric to be damaged by rubbing.

[0008] 1 is an SEM photograph of the coated mesh of Example 1 before a rubbing test. 2 is an SEM photograph of the coated mesh of Example 1 after a rubbing test. 3 is an SEM photograph of the coated mesh of Comparative Example 1 before a rubbing test. 4 is an SEM photograph of the coated mesh of Comparative Example 1 after a rubbing test. 5 is an SEM photograph of the coated mesh of Comparative Example 2 before a rubbing test. 6 is an SEM photograph of the coated mesh of Comparative Example 2 after a rubbing test.

[0009] Hereinafter, an embodiment of the present invention will be described. The fiber assembly of this embodiment has at least a portion of its surface coated, and is configured to include a substrate, such as a woven fabric, knitted fabric, or nonwoven fabric (hereinafter also referred to as a woven fabric substrate), and a coating film formed on the surface of the woven fabric substrate. In the fiber assembly of this embodiment, the Martens hardness of the coating film measured at a maximum indentation depth of 100 nm or less is 200 N / mm ２ 230N / mm or more ２ In this specification, the term "fiber aggregate" refers to a structure formed by assembling a plurality of fibers.

[0010] (Woven Fabric Substrate) In this embodiment, the woven fabric substrate is a woven fabric in which fibers are woven in a predetermined weave, a knitted fabric in a predetermined knitting pattern, or a nonwoven fabric in which fibers are randomly entangled. The material is not particularly limited as long as a coating film can be formed on the surface of the woven fabric. Examples of materials for such woven fabrics include organic fibers made from various resins and inorganic fibers made from inorganic materials such as glass, ceramics, and metals. Organic fibers include synthetic fibers such as those exemplified below, and natural fibers such as cotton, linen, and silk. The woven fabric may be formed from one or a combination of two or more of these materials, or may be formed from fibers in which the surface and center portions of the fibers are made of different materials.

[0011] Examples of resins that can be used to form organic fibers include polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, EVA resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polymethyl acrylate resin, polyvinyl acetate resin, polyamide resin, polyimide resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacetal resin, polyarylate resin, polysulfone resin, polyvinylidene fluoride resin, Vectran (registered trademark), thermoplastic resins such as PTFE, polylactic acid resin, polyhydroxybutyrate resin, modified Examples of suitable materials include biodegradable resins such as starch resin, polycaprolactone resin, polybutylene succinate resin, polybutylene adipate terephthalate resin, polybutylene succinate terephthalate resin, and polyethylene succinate resin, thermosetting resins such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, epoxy acrylate resin, acrylic urethane resin, and urethane resin, elastomers such as polystyrene elastomer, polyethylene elastomer, polypropylene elastomer, and polyurethane elastomer, and natural resins such as lacquer, etc. Inorganic fiber materials include glass, carbon, and metals, and metals known to those skilled in the art such as stainless steel, iron, nickel, chromium, copper, and various alloys can be used.

[0012] (Coating Film, Resin Composition) The coating film of this embodiment covers at least a portion of the substrate surface. The coating film of this embodiment can be formed, for example, from a resin composition. Specifically, a composition containing at least one selected from the group consisting of thermosetting or active energy ray-curable monomers and polymers is heated or irradiated with active energy rays, or a combination of heating and active energy ray irradiation, to crosslink and cure, thereby obtaining a coating film. The active energy ray is not particularly limited, and examples include ultraviolet light, electron beams, and ionizing radiation such as α-rays, β-rays, and γ-rays. Hereinafter, thermosetting or active energy ray-curable monomers may be collectively referred to as curable monomers, thermosetting or active energy ray-curable polymers may be collectively referred to as curable polymers, and curable monomers and curable polymers may be collectively referred to as curable resins. As described above, the coating film of this embodiment has a Martens hardness of 200 N / mm when measured at a maximum indentation depth of 100 nm or less. ２ 230N / mm or more ２ However, the Martens hardness of the coating film can be adjusted by controlling the type and blending ratio of the curable resin.

[0013] When the coating film has a plurality of coating layers, the resin compositions forming the layers may be the same or different.

[0014] <Curable Polymer> The curable polymer is a polymer containing a curable functional group. The curable polymer also contains a so-called oligomer region, and its weight-average molecular weight is 500 or more. From the viewpoint of increasing the hardness of the coating film, the weight-average molecular weight of the curable polymer is preferably 5,000 or more, more preferably 10,000 or more. From the viewpoint of ease of coating and molding, the weight-average molecular weight of the curable polymer may be 200,000 or less, preferably 100,000 or less, more preferably 80,000 or less.

[0015] The curable polymer contains a polymer chain containing a carbon-carbon bond, an ether bond, a urea bond, an ester bond, a urethane bond, a siloxane bond, or the like as the main chain, and contains a curable functional group as a side chain or terminal group. The curable functional group is a functional group that can form a crosslink with a polymer by a chemical bond, and includes curable functional groups known to those skilled in the art, such as a vinyl group, an ethynyl group, an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an acid anhydride, a methylol group, and a silanol group. The curable polymer may be an organic polymer or an inorganic polymer. From the viewpoint of transparency, a polymer chain containing a carbon-carbon bond is preferred, and from the viewpoint of formability, a polymer chain containing a urethane bond is preferred.

[0016] The number of curable functional groups is preferably 2 or more, more preferably 3 or more, and particularly preferably 5 or more. The type of curable functional group is not particularly limited, but a vinyl group, particularly an acryloyl group or a methacryloyl group, is preferred because of ease of polymerization.

[0017] Specific examples of preferred curable polymers include urethane (meth)acrylate polymers and acrylic (meth)acrylate polymers.

[0018] The urethane (meth)acrylate polymer can be prepared, for example, by (1) a method of subjecting a polyisocyanate compound having a terminal isocyanate group in the molecule to an addition reaction with a compound having a hydroxyl group and an acryloyl group (or a methacryloyl group), or by (2) a method of reacting a polyurethane polyol obtained by reacting a polyisocyanate compound with a polyol with an isocyanate group-containing (meth)acrylate monomer.

[0019] Examples of polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethyl ... Examples of the isocyanate compound include diisocyanate compounds obtained by hydrogenating aromatic isocyanates from among these diisocyanate compounds (for example, diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate), divalent or trivalent polyisocyanate compounds such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and biuret-type adducts and isocyanurate ring-type adducts of these diisocyanates.

[0020] Examples of the compound having a hydroxyl group and an acryloyl group (or a methacryloyl group) in the above method (1) include pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-hydroxyethyl(meth)acrylate, glycerol di(meth)acrylate, and alkylene oxide-modified or lactone-modified compounds obtained by adding ethylene oxide, propylene oxide, ε-caprolactone, γ-butyrolactone, or the like to these compounds.

[0021] Examples of the polyol in the above method (2) include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, polycaprolactone diol, polyester polyol, and polyether polyol.

[0022] Examples of the isocyanate group-containing (meth)acrylate monomer in the above method (2) include unsaturated compounds obtained by adding a polyisocyanate compound such as hexamethylene diisocyanate to an active hydrogen-containing polymerizable monomer such as isocyanate ethyl acrylate, isocyanate propyl acrylate, or hydroxyethyl acrylate.

[0023] The urethane (meth)acrylate polymer may be a urethane urea (meth)acrylate polymer having a urea bond. The urethane urea (meth)acrylate polymer can be prepared, for example, by using a polyamine in addition to the polyol in the above method (2).

[0024] The acrylic (meth)acrylate polymer is an acrylic polymer containing an acryloyl group and / or a methacryloyl group. Specific examples include a compound in which (meth)acrylic acid is added to an acrylic resin copolymerized with glycidyl methacrylate, a compound in which 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, or the like is added to an acrylic resin copolymerized with 2-acryloyloxyethyl isocyanate, and a resin in which 2-acryloyloxyethyl isocyanate is added to an acrylic resin copolymerized with a hydroxyl group-containing monomer.

[0025] The polymers can be used alone or in combination of two or more.

[0026] Commercially available curable polymers may be used. Examples of commercially available urethane (meth)acrylate oligomers or polymers include DPHA-40H, UX-5000, UX-5102D20, UX-5103D, UX-5005, UX-3204, UX-4101, UXT-6100, UX-6101, UX-8101, UX-0937, UXF-4001-M3, and UXF- 4002; UF-8001G and UA-510H manufactured by Kyoeisha Chemical Co., Ltd.; EBECRYL244, EBECRYL284, EBECRYL8402, EBECRYL8807, EBECRYL264, EBECRYL265, EBECRYL9260, EBECRYL8701, EBECRYL8405, and EBECRYL12 manufactured by Daicel-Allnex Co., Ltd. 90, EBECRYL5129, EBECRYL220, KRM8200, KRM7804, KRM8452; UV-1700B, UV-600B, UV-7600B, UV-7640B, UV-7650B, UV-3520EA, UV-7000B, Shikou UV-AF305A manufactured by Mitsubishi Chemical Corporation; CN-9001, CN-9004, CN manufactured by Arkema -9005, CN-965, CN-9178, CN-9893, CN-9782, CN-964, CN-9013, CN-9010; U-10PA, U-10HA, UA-33A, UA-53H, UA-32P, U-15HA, UA-122P, UA-160TM, UA-31F, UA-7100, UA-4200, UA-4400 manufactured by Shin-Nakamura Chemical Co., Ltd.;Negami Chemical Industrial Co., Ltd.'s Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin H-7M40, Art Resin UN-904, Art Resin UN-904M, Art Resin UN-901T, Art Resin UN-905, Art Resin UN-951, Art Resin UN-952, Art Resin UN-953, Art Resin UN-954, Art Resin UN-9 06, Art Resin UN-906S, Art Resin UN-907, Art Resin UN-908, Art Resin UN-333, Art Resin UN-5507, Art Resin UN-6300, Art Resin UN-6301, Art Resin UN-7600, Art Resin UN-7700, Art Resin UN-9000PEP, Art Resin UN-9200, Art Resin UN-904UREA, Art Resin UN-H7UREA, etc. can be used.

[0027] Commercially available acrylic (meth)acrylate oligomers or polymers include, for example, Unidic V-6840, Unidic V-6841, Unidic V-6850, Unidic EMS-635, and Unidic WHV-649 manufactured by DIC Corporation; Hitaloid 7975, Hitaloid 7977, Hitaloid 7988, and Hitaloid 7975D manufactured by Hitachi Chemical Co., Ltd.; and Artopolymer 1000 manufactured by Negami Chemical Industries, Ltd. Examples of materials that can be used include Artcure RA-3969MP, Artcure RA-3960PG, Artcure RA-3602MI, Artcure OAP-5000, Artcure OAP-2511, Artcure AHC-9202MI80, Artcure RA-3704MB, Artcure RA-3953MP, Artcure RA-4101, Artcure MAP-4000, and Artcure MAP2801.

[0028] <Curable Monomer> The curable monomer is a monomer containing the above-mentioned curable functional group. The molecular weight of the curable monomer is not particularly limited, but can be generally 500 or less. The curable functional group equivalent of the curable monomer may be 50 g / eq. or more and 200 g / eq. or less.

[0029] The curable monomer preferably has two or more, more preferably three or more, and particularly preferably five or more curable functional groups. In order to adjust the crosslink density, the curable resin composition may contain a resin having only one functional group of the same type as the curable functional group. Preferred examples of the curable functional group include an acryloyl group and a methacryloyl group. A preferred curable monomer is a polyfunctional (meth)acrylate monomer.

[0030] The polyfunctional (meth)acrylate monomer can be prepared by a dehydration reaction between a polyhydric alcohol and (meth)acrylic acid, or by a transesterification reaction between a polyhydric alcohol and a (meth)acrylic acid ester.

[0031] Examples of polyfunctional (meth)acrylate monomers having a curable functional group equivalent of 50 g / eq. or more and 200 g / eq. or less include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol (200) di(meth)acrylate, allyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dioxane glycol di(meth)acrylate, ethoxylated (2) bisphenol A di(meth)acrylate, ethoxylated ... Bifunctional (meth)acrylate monomers such as ethoxylated (3) bisphenol A di(meth)acrylate, ethoxylated (4) bisphenol A (meth)acrylate, ethoxylated (10) bisphenol A di(meth)acrylate, propoxylated (3) bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene di(meth)acrylate; glycerin tri(meth)acrylate Trimethylolpropane tri(meth)acrylate, ethoxylated (3) trimethylolpropane triacrylate, ethoxylated (6) trimethylolpropane triacrylate, ethoxylated (9) trimethylolpropane triacrylate, propoxylated (3) trimethylolpropane triacrylate, propoxylated (6) trimethylolpropane triacrylate, propoxylated (9) trimethylolpropane triacrylate, pentaerythritol tri(meth)acrylate trifunctional (meth)acrylate monomers such as tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated (4) pentaerythritol tri(meth)acrylate, ethoxylated (8) pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone-modified (1) tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and caprolactone-modified (3) tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate;Examples of such monomers include tetrafunctional (meth)acrylate monomers such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated (4) pentaerythritol tetra(meth)acrylate, and ethoxylated (8) pentaerythritol tetra(meth)acrylate; pentafunctional (meth)acrylate monomers such as dipentaerythritol penta(meth)acrylate and tripentaerythritol penta(meth)acrylate; hexafunctional (meth)acrylate monomers such as dipentaerythritol hexa(meth)acrylate and tripentaerythritol hexa(meth)acrylate; and heptafunctional or higher (meth)acrylate monomers such as tripentaerythritol hepta(meth)acrylate and tripentaerythritol octa(meth)acrylate.

[0032] The curable monomers may be used alone or in combination of two or more.

[0033] <Non-curable polymer> The resin composition may contain a non-curable polymer. By containing a non-curable polymer, flexibility is increased, and damage to the coating film is less likely to occur when the fiber assembly of the present embodiment is used while being bent.

[0034] The non-curable polymer is a thermoplastic polymer that does not contain a curable functional group and does not undergo crosslinking by chemical bonding with other polymers. The weight-average molecular weight of the non-curable polymer is preferably 5,000 or more, more preferably 10,000 or more. Because the non-curable polymer is insoluble in a coating solvent or the viscosity of the coating solution increases, making coating difficult, the weight-average molecular weight of the non-curable polymer is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 80,000 or less.

[0035] Examples of non-curable polymers include urethane resins, acrylic resins, polyester resins, polyolefin resins, etc. Acrylic resins are preferred from the viewpoint of affinity with the above-mentioned curable resins.

[0036] In the resin composition, the content of the curable resin can be at least 5% by mass or more relative to the total amount of the curable and non-curable polymers. The ratio of the curable polymer to the curable monomer in the curable resin can be freely set as long as the Martens hardness after curing falls within a predetermined range, but it is preferable that the curable monomer contains 5% by mass or more relative to the total amount of the curable polymer and the curable monomer. In addition, the number of curable functional groups in the resin composition is preferably 0.12 mol or more and 0.32 mol or less per 100 g of resin component. The number of curable functional groups in the resin composition can be calculated from the molecular weight of the curable resin, the number of functional groups, and the amount of the curable resin.

[0037] <Polymerization initiator> The resin composition may contain a polymerization initiator or a curing catalyst depending on the type of resin constituting the resin and the polymerization method to be applied. Hereinafter, the polymerization initiator and the curing catalyst may be collectively referred to as a curing initiator. The amount of the curing initiator to be blended is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less, per 100 parts by mass of the resin component.

[0038] The curing initiator may be a polymerization initiator or curing catalyst known to those skilled in the art. When curing is performed by radical polymerization, for example, azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2-methylpropionamidine) dihydrochloride, organic peroxides such as dialkyl peroxycarbonates such as benzoyl peroxide, dicumyl peroxide, diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide, and inorganic peroxy compounds such as ammonium salts, potassium salts, and sodium salts of persulfuric acid, perborate, perchloric acid, perphosphoric acid, and percarbonate may also be used. In the case of photopolymerization, examples of the photopolymerization initiator include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, titanocene-based photopolymerization initiators, oxime ester-based polymerization initiators, and photocationic polymerization initiators.

[0039] Examples of alkylphenone photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0040] Examples of the acylphosphine oxide photopolymerization initiator include monoacylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4,6-triethylbenzoyldiphenylphosphine oxide, and 2,4,6-triphenylbenzoyldiphenylphosphine oxide; and bisacylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0041] Examples of titanocene photopolymerization initiators include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium. Examples of oxime ester polymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, and 2-(2-hydroxyethoxy)ethyl ester.

[0042] Examples of the cationic photopolymerization initiator that can be used include sulfonium salt-based polymerization initiators such as UVI-6992 (manufactured by Dow), CPI-100P (manufactured by San-Apro), and SP-150 (manufactured by ADEKA), and iodonium salt-based initiators such as IRGACURE250 (manufactured by BASF), all of which are well known to those skilled in the art.

[0043] The polymerization initiator may be used alone or in combination of two or more.

[0044] As described below, curing can be carried out by heating or irradiating with active energy rays. Heat curing can be carried out by heating at a temperature known to those skilled in the art at which the curable functional groups react but not exceeding a temperature at which the textile substrate does not deform. When irradiating with active energy rays, the amount of irradiation known to those skilled in the art at which the curable functional groups react sufficiently can be used.

[0045] Curing by electron beam irradiation is preferred because it does not require the addition of a polymerization initiator or a curing catalyst.

[0046] In addition to the resin components described above, functional agents can be added to the resin composition. The type of functional agent is not particularly limited and can be selected appropriately depending on the desired function. Examples of functional agents include pigments, dyes, fluorescent agents, UV absorbers, antistatic agents, antibacterial agents, antiviral agents, and antifungal agents, and multiple functional agents can be used in combination. Examples of pigments include zinc oxide, white lead, lithopone, titanium dioxide, precipitated barium sulfate, red lead, iron oxide, potassium iron ferrocyanide, and carbon black. Examples of UV absorbers include octyl methoxycinnamate, octyl dimethyl PABA, and t-butyl methoxydibenzoylmethane. Examples of antistatic agents include anionic surfactants and cationic surfactants. Examples of antibacterial and antiviral agents include organic or inorganic compounds containing silver or copper, and quaternary ammonium compounds. Monovalent copper compounds such as cuprous oxide and cuprous halide are preferred due to their particularly excellent antibacterial and antiviral properties. The amount of functional agent added may be appropriately determined depending on the functional agent to be added, but is preferably 50 mass % or less based on the solid content of the coating film. Furthermore, various additives such as a surface conditioner can be added as needed. Addition of a surface conditioner improves the wettability and leveling properties when the resin composition is applied to a textile substrate, resulting in a coating film with a more uniform surface.

[0047] (Coating Film Thickness) The thickness of the coating film on the fiber assembly of this embodiment is not particularly limited and may be adjusted as appropriate depending on the intended use of the fiber assembly, but if the fiber assembly of this embodiment is to be bent for use, it is desirable that the thickness not exceed 500 nm. By making the coating film 500 nm or less in thickness, the coating film is less likely to break even when the fiber assembly of this embodiment is bent for use, compared to thicknesses outside this range.

[0048] (Method for forming coating film) A coating film can be formed on the surface of a substrate such as a textile by, for example, a known method. Specifically, for example, the coating film can be produced by a process of producing a resin composition, a process of applying the resin composition to a substrate such as a textile, and a process of curing the applied resin composition.

[0049] (1) Resin Composition Preparation Process The resin composition is prepared by a known method. For example, the resin composition is obtained by mixing the components of the curable resin, and optionally a functional agent, using a commonly used mixing device such as a ball mill. The resin composition is dissolved or dispersed in a solvent to prepare a varnish to be used in the coating process. The solvent for dissolving the resin composition is not particularly limited and may be selected appropriately depending on the components contained in the resin composition and the type of textile substrate to be applied. Examples include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutyl alcohol; and halogenated solvents such as dichloromethane and chloroform. These may be used alone or in combination of two or more. In the coating step, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are particularly preferred.

[0050] (2) Coating Step: The varnish prepared in the resin composition preparation step is applied to a substrate such as a textile. The coating method may be any known method and is not particularly limited. Examples include dip coating, air knife coating, curtain coating, roller coating, bar coating, die coating, and inkjet coating. After coating, a drying process is performed to remove the solvent contained in the varnish. The drying temperature is not particularly limited and may be set to conditions known to those skilled in the art depending on the amount applied, the type of solvent, and the type of curable functional group of the curable resin. Specifically, the temperature should not exceed the melting point of the substrate, such as the textile, and should volatilize the solvent at a temperature at which the curable resin's curing reaction does not begin during the drying step; for example, the temperature may be set appropriately between 50°C and 150°C.

[0051] (3) Curing Step: The textile or other material coated with the resin composition is cured by heating or irradiating it with active energy rays. The heating temperature for heat curing may be determined depending on the type of curable resin in the resin composition, as long as it does not exceed the melting point of the substrate, such as the textile. To further suppress changes over time, such as coloration, it is preferable to allow the coating film curing reaction to proceed as completely as possible. The degree of curing can be confirmed by methods known to those skilled in the art, such as measuring the spectral intensity of the curable functional group or measuring the gel fraction. When curing by irradiating active energy rays, the type of active energy rays is not particularly limited. The active energy rays are appropriately selected depending on the type of polymerizable monomer or oligomer. The active energy rays are not particularly limited, and examples include ultraviolet rays, electron beams, and ionizing radiation such as α-rays, β-rays, and γ-rays. Electron beams are preferred because they easily polymerize without the addition of a polymerization initiator. The irradiation dose should be within a range that cures the resin composition and does not deteriorate the organic material that constitutes the coating film. For example, if the resin composition is irradiated with ultraviolet rays, the cumulative light dose should be 200 mJ / cm. ２ More than 400mJ / cm ２ In the case of electron beam irradiation, active energy rays of 50 kGry or more and 150 kGry or less may be irradiated.

[0052] Here, the coating film of the fiber assembly of this embodiment has a Martens hardness of 200 N / mm when measured at a maximum indentation depth of 100 nm or less. ２ 230N / mm or more２ However, as described above, the Martens hardness of the coating film can be adjusted by controlling the type and blending ratio of the curable resin. For example, by setting the curable resin composition so that the number of curable functional groups in 100 g of the curable resin is 0.12 mol or more and 0.32 mol or less, the Martens hardness can be adjusted to 200 N / mm ２ 230N / mm or more ２ The number of curable functional groups in the curable resin can be calculated from the curable functional group equivalent of the constituent curable resins and their blending ratios. ２ 230N / mm or more ２ By setting the above value to less than 1 / 2, it is possible to prevent the coating film from falling off due to rubbing. Therefore, for example, when a functionalizing agent such as an antibacterial or antiviral agent is contained in the coating film and applied to a substrate such as a textile, the functionalizing agent is prevented from falling off due to rubbing, and it is possible to prevent a decrease in desired functions such as antibacterial or antiviral properties due to rubbing.

[0053] (Coating Hardness Measurement) The coating hardness of the fiber aggregate of this embodiment can be calculated in accordance with ISO 14577-1 by measuring the load and indentation depth applied to the coating on the fibers of a woven fabric or the like using a Vickers indenter using an ultra-microhardness tester, for example, a dynamic ultra-microhardness tester DUH-211 (manufactured by Shimadzu Corporation).

[0054] (Abrasion Resistance Test) The resistance of the fiber assembly of the present invention to damage or peeling of the coating film due to abrasion can be confirmed by, for example, rubbing the fiber assembly with a brush or the like a predetermined number of times and observing the change in appearance of the coating film. Specifically, it can be confirmed, for example, by carrying out the abrasion test described in the Examples of this specification.

[0055] As described above, according to this embodiment, in a woven fabric or nonwoven fabric, the coating film on the surface thereof can be made less susceptible to damage due to rubbing, and the resistance of the coating film to rubbing can be increased.

[0056] Example 1 A fiber assembly of this example was produced through the following steps of preparing a coating agent, applying the coating, and irradiating with an electron beam.

[0057] (Preparation of coating agent) 65 parts by mass of butyl acetate, 31 parts by mass of Unidic V-6850 (manufactured by DIC Corporation, weight average molecular weight: 26,000), and 4 parts by mass of trimethylolpropane triacrylate (TMPTA, manufactured by Daicel Allnex Co., Ltd.) were weighed and uniformly stirred in a beaker to prepare a coating agent sample. Next, 40 parts by mass of ethanol and 60 parts by mass of propylene glycol ether were mixed to prepare a diluent.

[0058] (Coating Method) A PET-based mesh TESP70SS (manufactured by NBC Meshtec Co., Ltd.) was used as the substrate, and coating was performed by the dipping method. 100 mL of a solution prepared by diluting a coating agent sample 50 times with a diluent was placed in a stainless steel square pad. After immersion in this diluted solution, excess liquid was scraped off with the edge of the pad, and the mesh was dried in a multi-safety dryer MSO-60TPS (manufactured by Futaba Scientific Co., Ltd.). The drying oven temperature was 120°C, and the drying time was 2 minutes. The number of curable functional groups per 100 g of curable resin in the resulting coated mesh of Example 1, which is a fiber assembly, was 0.24 mol.

[0059] (Electron Beam Irradiation) Electron beam irradiation was carried out using an electron beam irradiation apparatus ERECTOROBEAM-L EC250 / 15 / 180L (manufactured by Iwasaki Electric Co., Ltd.) under the conditions of an acceleration voltage of 150 kV, an electron current of 5 mA, and a dose of 110 kGy.

[0060] Example 2 A coated mesh of Example 2, a fiber assembly, was obtained by the same procedure as in Example 1, except that the 31 parts by mass of Unidic V-6850 (manufactured by DIC Corporation, weight average molecular weight: 26,000) used in Example 1 was replaced with 15 parts by mass of Unidic V-6850 and 13 parts by mass of Art Resin UN-954 (manufactured by Negami Chemical Industrial Co., Ltd., weight average molecular weight: 4,000). The number of curable functional groups in 100 g of the curable resin of the resulting coated mesh was 0.31 mol.

[0061] Example 3 A fiber assembly, a coated mesh of Example 3, was obtained by the same procedure as in Example 1, except that the 31 parts by mass of Unidic V-6850 in Example 1 was replaced with 26 parts by mass of Artresin UN-952 (manufactured by Negami Chemical Industrial Co., Ltd., weight average molecular weight: 8,000) and the 4 parts by mass of trimethylolpropane triacrylate (TMPTA, manufactured by Daicel Allnex Corporation) was replaced with 4 parts by mass of phenoxydiethylene glycol acrylate (EBECRYL 110, manufactured by Daicel Allnex Corporation). The number of curable functional groups per 100 g of the curable resin in the resulting coated mesh was 0.18 mol.

[0062] Comparative Example 1 A coated mesh of Comparative Example 1, which is a fiber assembly, was obtained by the same procedure as in Example 1, except that 4 parts by mass of trimethylolpropane triacrylate (TMPTA, manufactured by Daicel Allnex Corporation) in Example 1 was replaced with 4 parts by mass of phenoxydiethylene glycol acrylate (EBECRYL 110, manufactured by Daicel Allnex Corporation). The number of curable functional groups in 100 g of the curable resin in the obtained coated mesh was 0.11 mol.

[0063] Comparative Example 2 A coated mesh of Comparative Example 2, a fiber assembly, was obtained by the same procedure as in Example 1, except that the 65 parts by mass of butyl acetate used in Example 1 was replaced with 70 parts by mass, 31 parts by mass of Unidic V-6850 (manufactured by DIC Corporation, weight-average molecular weight: 26,000) was replaced with 26 parts by mass of Art Resin UN-954 (manufactured by Negami Chemical Industrial Co., Ltd., weight-average molecular weight: 4,000), and 4 parts by mass of trimethylolpropane triacrylate (TMPTA, manufactured by Daicel Allnex Co., Ltd.) was replaced with 4 parts by mass of M-305 (manufactured by Toagosei Co., Ltd., molecular weight: 319.6). The number of curable functional groups per 100 g of the curable resin in the resulting coated mesh was 0.33 mol.

[0064] The coated meshes of the Examples and Comparative Examples were subjected to the following Martens hardness test and abrasion test.

[0065] (Martens Hardness Test) A dynamic ultra-microhardness tester DUH-211 (Shimadzu Corporation) was used to measure Martens hardness within the ISO standard for instrumented indentation hardness (ISO14577-1). The sample was pretreated by gluing it onto a glass plate, and the test was carried out under the measurement conditions listed in Table 1. The results were the average of five measurements.

[0066]

[0067] (Rubbing test) A rubbing test was performed on the coated meshes of Examples 1 to 3 and Comparative Examples 1 and 2 under the following conditions. A BA665 air purifier / air conditioner brush (manufactured by Azuma Kogyo Co., Ltd.) was attached to a shaker. The coated mesh sample was fixed to a glass plate with tape on the top and bottom, and the mesh was positioned so that it would come into contact with the brush, and the test was performed. The shaker was operated at 120 rpm for 8 minutes and 30 seconds. After the rubbing test, the appearance of the coating on the coated mesh was observed using an SEM to confirm the presence or absence of damage to the coating.

[0068] The compositions of the coated meshes of the Examples and Comparative Examples are summarized in Table 2. The results of the Martens hardness test and the rubbing test are shown in Table 3. For the coated mesh of Example 1, a photograph before the rubbing test is shown in Figure 1, and a photograph after the rubbing test is shown in Figure 2. Similarly, photographs of the coated meshes of Comparative Examples 1 and 2 before and after the rubbing test are also shown (Comparative Example 1, before test: Figure 3, after test: Figure 4; Comparative Example 2, before test: Figure 5, after test: Figure 6).

[0069]

[0070]

[0071] As can be seen from Table 3, damage to the coating film due to rubbing was suppressed in the coated meshes of Examples 1 to 3.

Claims

1. A fibrous aggregate having at least a part of its surface coated, comprising a base material made of a woven fabric, a knitted fabric or a non-woven fabric, and a coating film covering at least a part of the surface of the base material, wherein the Martens hardness of the coating film measured at a maximum indentation depth of 100 nm or less is ２ 200 N / mm or more and less than 230 N / mm ２ A fibrous aggregate characterized by being less than that.

2. The fibrous aggregate according to claim 1, wherein the coating film contains a functional agent.

3. The fibrous aggregate according to claim 2, wherein the functional agent is an inorganic material.

4. The fibrous aggregate according to claim 2, wherein the functional agent is an antibacterial agent and / or an antiviral agent.

5. The fibrous aggregate according to any one of claims 1 to 4, wherein the coating film contains an acrylic resin.

6. The fibrous aggregate according to any one of claims 1 to 4, wherein the thickness of the coating film is less than 500 nm.

7. The Martens hardness measured at a maximum indentation depth of 100 nm or less of the coating film formed on the fabric, knitted fabric or non-woven fabric is 200 N / mm ２ or more and less than 230 N / mm ２ A method for enhancing the strength of the coating film against rubbing, which includes setting the composition of the resin constituting the coating film.

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