Fiber assembly

Abstract

The present invention provides a new technique for less likely causing defects of a coating film on the surface of a woven fabric, a knitted fabric or a nonwoven fabric due to rubbing. A fiber aggregate characterized in that at least a part of the surface thereof is coated, the fiber aggregate having a base material composed of a woven fabric, a knitted fabric or a nonwoven fabric, and a coating film covering at least a part of the surface of the base material, the coating film having a Martens hardness of 200 N / mm2 or less when measured at a maximum indentation depth of 100 nm or less 2 and less than 230 N / mm2 2 .

Description

Technical Field

[0001] This invention relates to fiber assemblies with coatings. Background Technology

[0002] To impart antibacterial and dust-proof properties to mesh substrates such as filters, a resin composition containing functional materials is sometimes used to form a coating and fix it to the mesh surface. To prevent the coating from breaking or peeling due to external forces such as friction, the coating needs a certain degree of hardness. For thin film substrates, pencil hardness testing is often used to assess coating hardness. However, because the coating width formed on the fibers of woven fabrics such as mesh is narrow, pencil hardness cannot be used to evaluate coating hardness. To implement abrasion-resistant coatings, it is necessary to measure the coating hardness over a small area. However, previously, there was no direct measurement of coating hardness on the fibers for coating design; resin composition was always based on repeated experimentation and intuition by the developer.

[0003] The hardness of coatings with small areas can be measured using an ultramicrohardness tester as the martensitic hardness, with the measurement standard determined by ISO 14577-1. Patent document 1 discloses a laminated film in which the martensitic hardness of the coating formed on the film substrate is ≥0.300 GPa and ≤0.65 GPa at an indentation depth of 100 nm, and ≥0.15 GPa and ≤0.35 GPa at an indentation depth of 2000 nm.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2023-126785 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] This invention provides a new technology that can reduce friction-induced defects in the coating on the surface of woven, knitted, or nonwoven fabrics.

[0009] Solution for solving the problem

[0010] Even if a coating with the same composition as a coating that does not cause peeling or other defects on a thin-film substrate is formed on woven, knitted, or nonwoven fabrics, it may still cause peeling or other defects. This is believed to be because the curing conditions of the coating, such as the irradiation state of active energy rays, may not be the same on thin films and on fibers such as woven fabrics, resulting in different crosslinking states of the coating on thin-film substrates and fibers. Furthermore, the ease with which the coating may break may differ depending on the method of applying external force to the thin film and the fiber. Therefore, in the case of substrates that are easily bent or sheared, such as woven fabrics, even applying a resin composition with an effective coating to a thin-film substrate may not always yield the desired results.

[0011] The inventors conducted in-depth research and found that by making the hardness of the coating film on the surface of the fibers constituting woven fabrics within a specified range, the coating film is less likely to be damaged by friction.

[0012] That is, the main idea of ​​this invention is as follows.

[0013] [1] A fiber assembly, characterized in that at least a portion of its surface is coated,

[0014] The fiber assembly has a substrate made of woven fabric, knitted fabric, or nonwoven fabric, and

[0015] A coating that covers at least a portion of the substrate surface.

[0016] The martensitic hardness of the coating, measured when the maximum indentation depth is below 100 nm, is 200 N / mm. 2 Above and below 230 N / mm 2 .

[0017] [2] The fiber assembly according to [1] is characterized in that the coating film contains a functional agent.

[0018] [3] The fiber aggregate according to [2] is characterized in that the functional agent is an inorganic material.

[0019] [4] The fiber aggregate according to [2] is characterized in that the functional agent is an antibacterial agent and / or an antiviral agent.

[0020] [5] The fiber assembly according to any one of [1] to [4] is characterized in that the coating comprises an acrylic resin.

[0021] [6] The fiber assembly according to any one of [1] to [4] is characterized in that the thickness of the coating is less than 500 nm.

[0022] [7] A method for improving the friction resistance of a coating film, comprising: measuring a Martens hardness of 200 N / mm when the maximum indentation depth of the coating film formed on a woven fabric, knitted fabric or nonwoven fabric is less than 100 nm. 2 Above and below 230 N / mm 2 The composition of the resin constituting the coating film is set in a certain way.

[0023] The effects of the invention

[0024] According to the present invention, a new technology is available that can reduce friction-induced defects in the coating on the surface of woven, knitted, or nonwoven fabrics. Attached Figure Description

[0025] Figure 1 This is a SEM image of the coated mesh from Example 1 before the friction test.

[0026] Figure 2 This is a SEM image of the coated mesh after a friction test in Example 1.

[0027] Figure 3 This is a SEM image of the coated mesh of Comparative Example 1 before the friction test.

[0028] Figure 4 This is a SEM image of the coated mesh from Comparative Example 1 after a friction test.

[0029] Figure 5 This is a SEM image of the coated mesh of Comparative Example 2 before the friction test.

[0030] Figure 6 This is a SEM image of the coated mesh from Comparative Example 2 after a friction test. Detailed Implementation

[0031] Hereinafter, embodiments of the present invention will be described. In this embodiment, at least a portion of the surface of the fiber assembly is coated, comprising a woven fabric, knitted fabric, or nonwoven fabric (hereinafter also referred to as a woven fabric or other substrate) as a base material and a coating film formed on the surface of the woven fabric or other substrate. In the fiber assembly of this embodiment, the martensitic hardness of the coating film measured when the maximum indentation depth is 100 nm or less is 200 N / mm. 2 Above and below 230 N / mm 2 .

[0032] It should be noted that, in this specification, a fiber aggregate refers to a structure formed by the aggregation of multiple fibers.

[0033] (Woven fabrics and other substrates)

[0034] In this embodiment, the woven fabric or other substrate refers to a woven fabric formed by weaving fibers into a prescribed woven fabric structure, a knitted fabric formed by weaving fibers into a prescribed knitted fabric structure, or a nonwoven fabric formed by randomly winding fibers. The material is not particularly limited as long as it is a woven fabric or similar material capable of forming a coating on its surface. Examples of materials for such woven fabrics include organic fibers formed from various resins and inorganic fibers formed from inorganic materials such as glass, ceramics, and metals. Examples of organic fibers include synthetic fibers, cotton, linen, silk, and other natural fibers. The woven fabric or similar material can be formed from one or more of these materials, or it can be formed from fibers whose surface and central portions are made of different materials.

[0035] Examples of resins capable of forming organic fibers include polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, EVA resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polymethyl methacrylate 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), PTFE and other thermoplastic resins, polylactic acid resin, and poly... Biodegradable resins include hydroxybutyrate resins, modified starch resins, polycaprolactone resins, polybutylene succinate resins, polybutylene adipate terephthalate resins, polybutylene terephthalate succinate resins, and polyethylene succinate resins; thermosetting resins include phenolic resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, epoxy resins, epoxy acrylate resins, acrylic urethane resins, and urethane resins; elastomers include polystyrene elastomers, polyethylene elastomers, polypropylene elastomers, and polyurethane elastomers; and natural resins such as paints. Additionally, inorganic fiber materials include glass, carbon, and metals, with metals including stainless steel, iron, nickel, chromium, copper, and various alloys—materials known to those skilled in the art.

[0036] (Coatings, resin compositions)

[0037] The coating of this embodiment covers at least a portion of the substrate surface. The coating of this embodiment may, for example, be formed from a resin composition.

[0038] Specifically, a coating film can be obtained by heating or irradiating a composition comprising at least one monomer and polymer selected from the group consisting of thermosetting or active energy-curable materials with active energy rays, or by a combination of heating and irradiation with active energy rays, on the surface of a substrate such as a woven fabric, thereby crosslinking and curing the composition. Active energy rays are not particularly limited and examples include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. Hereinafter, thermosetting or active energy-curable monomers are sometimes collectively referred to as curable monomers, and thermosetting or active energy-curable polymers are collectively referred to as curable polymers; furthermore, curable monomers and curable polymers are collectively referred to as curable resins.

[0039] The coating of this embodiment, as described above, exhibits a Martens hardness of 200 N / mm when the maximum indentation depth is below 100 nm. 2 Above and below 230 N / mm 2 By controlling the type and mixing ratio of the curing resin, the martensitic hardness of the coating film can be adjusted.

[0040] When a coating film has multiple coating layers, the resin compositions forming each layer can be the same or different.

[0041] <Curing polymers>

[0042] Curable polymers are polymers containing curable functional groups.

[0043] The curable polymer also includes so-called oligomer regions, and its weight-average molecular weight is 500 or more. From the viewpoint of improving 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 forming, the weight-average molecular weight of the curable polymer can be 200,000 or less, preferably 100,000 or less, more preferably 80,000 or less.

[0044] Curable polymers comprise polymer chains containing carbon-carbon bonds, ether bonds, urea bonds, ester bonds, urethane bonds, siloxane bonds, etc., as the main chain, and curable functional groups as side chains or terminal groups. Curable functional groups refer to functional groups capable of forming crosslinks with polymers through chemical bonds, equivalent to curable functional groups known to those skilled in the art such as vinyl, ethynyl, epoxy, amino, hydroxy, carboxyl, acid anhydride, hydroxymethyl, and silanol groups. Curable polymers can be organic or inorganic polymers. From the viewpoint of transparency, polymer chains containing carbon-carbon bonds are preferred; from the viewpoint of excipient properties, polymer chains containing urethane bonds are preferred.

[0045] 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 vinyl groups, especially acryloyl or methacryloyl groups, are preferred from the perspective of ease of polymerization.

[0046] Preferred curable polymers include, specifically, urethane (meth)acrylate polymers and acrylic (meth)acrylate polymers.

[0047] The urethane (meth)acrylate polymer can be prepared, for example, by: (1) an addition reaction of a polyisocyanate compound having a terminal isocyanate group in the molecule with a compound having a hydroxyl group and an acryloyl group (or a methacryloyl group), or (2) a reaction of a polyurethane polyol obtained by reacting a polyisocyanate compound with a polyol with an isocyanate group-containing (meth)acrylate monomer.

[0048] Examples of polyisocyanate compounds include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, phenyl dimethyl diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, terephthalene diisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and 2, 2,4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, or diisocyanate compounds obtained by hydrogenating aromatic isocyanates of these diisocyanate compounds (e.g., hydrogenated phenylenedimethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc.), triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, and other binary or ternary polyisocyanate compounds, as well as biuret adducts and isocyanurate cyclic adducts of these diisocyanates.

[0049] Examples of compounds having hydroxyl and acryloyl (or methacryloyl) groups in method (1) above 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, etc. to them.

[0050] Examples of polyols used in method (2) above include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, polycaprolactone diol, polyester polyol, and polyether polyol.

[0051] As an isocyanate-containing (meth)acrylate monomer in the above method (2), examples include unsaturated compounds formed by adding polyisocyanate compounds such as hexamethylene diisocyanate to polymerizable monomers containing active hydrogen, such as ethyl isocyanate, propyl isocyanate, and hydroxyethyl acrylate.

[0052] The urethane (meth)acrylate polymer can be a urethane urea (meth)acrylate polymer having urea bonds. The urethane urea (meth)acrylate polymer can be prepared, for example, by using a polyol in method (2) above in combination with a polyamine.

[0053] Acrylic (meth)acrylate polymers are acrylic polymers containing acryloyl groups and / or methacryloyl groups. Specifically, examples include compounds obtained by adding (meth)acrylic acid to an acrylic resin copolymerized with glycidyl methacrylate; compounds obtained by adding 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, etc., to an acrylic resin copolymerized with 2-acryloyloxyethyl isocyanate; and resins obtained by adding 2-acryloyloxyethyl isocyanate to an acrylic resin copolymerized with hydroxyl-containing monomers.

[0054] One polymer can be used alone, or two or more can be used in combination.

[0055] Commercially available products can be used as curable polymers. 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 manufactured by Nippon Kayaku Co., Ltd.; UF-8001G and UA-510H manufactured by Kyoeisha Chemical Co., Ltd.; and EBECRYL244 and EBECRYL284 manufactured by DAICL-ALLNEX Co., Ltd. EBECRYL8402, EBECRYL8807, EBECRYL264, EBECRYL265, EBECRYL9260, EBECRYL8701, EBECRYL8405, EBECRYL1290, EBECRYL5129, EBECRYL220, KRM8200, KRM7804, KRM8452; UV-1700B, UV-600B, UV-7600B, UV-7640B, UV-7650B, UV-3520EA, UV-7000B, and Ziguang UV-AF305A manufactured by Mitsubishi Chemical Corporation;Arkema's CN-9001, CN-9004, CN-9005, CN-965, CN-9178, CN-9893, CN-9782, CN-964, CN-9013, CN-9010; Shin-Nakamura Chemical Industry Co., Ltd.'s U-10PA, U-10HA, UA-33A, UA-53H, UA-32P, U-15HA, UA-122P, UA-160TM, UA-31F, UA-7100, UA-4200, UA-4400; Negami Kogyo 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-906, 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 ResinUN-7700, Art Resin UN-9000PEP, Art Resin UN-9200, Art Resin UN-904UREA, Art ResinUN-H7UREA, etc. ;

[0056] 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 HITALOID7975D manufactured by Hitachi Chemical Co., Ltd.; and ART CURE RA-3969MP, ART CURE RA-3960PG, ART CURE RA-3602MI, ART CURE OAP-5000, ART CURE OAP-2511, ART CURE AHC-9202MI80, ART CURE RA-3704MB, ART CURE RA-3953MP, and ART CURE RA-4101 manufactured by Negami Kogyo Co., Ltd. CURE MAP-4000, ART CURE MAP2801, etc.

[0057] <Curing monomers>

[0058] Curable monomers are monomers containing the aforementioned curable functional groups.

[0059] There is no particular limitation on the molecular weight of the curable monomer, which can be set to approximately 500 or less. The curable functional group equivalent of the curable monomer can be above 50 g / eq. or below 200 g / eq.

[0060] The curable monomer preferably has 2 or more curable functional groups, more preferably 3 or more, and particularly preferably 5 or more. To adjust the crosslinking density, the curable resin composition may contain a resin having only one functional group of the same type as the curable functional group. Examples of curable functional groups are acryloyl and methacryloyl groups. Preferred curable monomers are polyfunctional (meth)acrylate monomers.

[0061] Multifunctional (meth)acrylate monomers can be prepared by dehydration reaction of polyols with (meth)acrylic acid or transesterification reaction of polyols with (meth)acrylates.

[0062] Examples of polyfunctional (meth)acrylate monomers with 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, dioxanediol di(meth)acrylate, ethoxylated (2) bisphenol A di(meth)acrylate, ethoxylated (3) bisphenol A di(meth)acrylate, and ethoxylated (4) bisphenol A (meth)acrylate. Ethoxylated (10) bisphenol A di(meth)acrylate, propoxylated (3) bisphenol A di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene di(meth)acrylate and other difunctional (meth)acrylate monomers; glycerol 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 Propane triacrylate, propoxylated (9) trimethylolpropane triacrylate, pentaerythritol tri(meth)acrylate, ethoxylated (4) pentaerythritol tri(meth)acrylate, ethoxylated (8) pentaerythritol tri(meth)acrylate, tri(2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone-modified (1) tri(2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone-modified (3) tri(2-hydroxyethyl) isocyanurate tri(meth)acrylate and other trifunctional (meth)acrylate monomers; pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate (Meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, ethoxylated (4)pentaerythritol tetra(meth)acrylate, ethoxylated (8)pentaerythritol tetra(meth)acrylate and other 4-functional (meth)acrylate monomers; dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate and other 5-functional (meth)acrylate monomers; dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate and other 6-functional (meth)acrylate monomers; tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate and other 7-functional or higher (meth)acrylate monomers.

[0063] One type of curable monomer can be used alone, or two or more types can be used in combination.

[0064] <Non-curing polymers>

[0065] The resin composition may contain a non-curing polymer. By containing a non-curing polymer, flexibility is improved, and coating defects are less likely to occur when the fiber assembly of this embodiment is bent for use.

[0066] Non-curable polymers are thermoplastic polymers that do not contain curable functional groups and do not undergo cross-linking with other polymers based on chemical bonds.

[0067] The weight-average molecular weight of the non-curable polymer is preferably 5,000 or more, more preferably 10,000 or more. Since it is not soluble in the coating solvent or the viscosity of the coating solution becomes too high to coat, the weight-average molecular weight of the non-curable polymer can be 200,000 or less, more preferably 100,000 or less, and more preferably 80,000 or less.

[0068] Examples of non-curing polymers include urethane resins, acrylic resins, polyester resins, and polyolefin resins. From the viewpoint of affinity with the aforementioned curable resins, acrylic resins are preferred.

[0069] In the resin composition, the content of the curable resin can be set to at least 5% by mass relative to the total amount of 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 is within a specified range, but it is preferable that it contains at least 5% by mass of the curable monomer relative to the total amount of the curable polymer and the curable monomer. Furthermore, the number of curable functional groups in the resin composition is preferably between 0.12 mol and 0.32 mol per 100g 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 curable resin incorporated.

[0070] <Polymerization initiator>

[0071] The resin composition may contain a polymerization initiator or a curing catalyst corresponding to the type of resin and the polymerization method used. Hereinafter, polymerization initiators and curing catalysts are sometimes collectively referred to as curing initiators. The amount of curing initiator mixed in 100 parts by weight of resin is preferably 0.01 parts by weight or more and 10 parts by weight or less, more preferably 1 part by weight or more and 10 parts by weight or less.

[0072] The curing initiator can be a polymerization initiator or curing catalyst known to those skilled in the art.

[0073] When curing is carried out by free radical polymerization, organic peroxides such as benzoyl peroxide, dicumyl peroxide, diisopropylbenzene peroxide, diisopropyl peroxide, disec-butyl peroxide, tert-butyl peroxide, tert-butyl peroxyisobutyrate, dialkyl peroxides, dialkyl peroxides, dialkyl peroxides, dialkyl peroxides, dialkyl peroxides, dialkyl peroxides, dialkyl peroxides, ditert-butyl peroxide, tert-butyl peroxide, dialkyl peroxides, dialkyl peroxides, and disulfonic acid compounds such as ammonium salts, potassium salts, and sodium salts of persulfate, perboric acid, perchloric acid, superphosphate, and percarbonate can also be used.

[0074] In addition, examples of photopolymerization initiators include alkyl phenyl ketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, titanium hololithi-based photopolymerization initiators, oxime ester-based polymerization initiators, and photocationic polymerization initiators.

[0075] Examples of alkyl phenyl ketone photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone.

[0076] Examples of acylphosphine oxide photopolymerization initiators include monoacylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-triethylbenzoyl-diphenylphosphine oxide, and 2,4,6-triphenylbenzoyl-diphenylphosphine oxide; and diacylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0077] Examples of titanium-based photopolymerization initiators include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)-phenyl)titanium. Examples of oxime ester polymerization initiators include 1-[4-(phenylthio)-2-(O-benzoyl oxime)]1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone, oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy] ethyl ester, and 2-(2-hydroxyethoxy) ethyl ester.

[0078] As photocationic polymerization initiators, for example, sulfonium salt initiators such as UVI-6992 (manufactured by Dow), CPI-100P (manufactured by San-Apro), and SP-150 (manufactured by ADEKA), and iodomonium salt initiators such as IRGACURE250 (manufactured by BASF) can be used, as well as other photocationic polymerization initiators known to those skilled in the art.

[0079] Polymerization initiators can be used alone or in combination of two or more.

[0080] As described below, curing can be performed by heating or irradiation with active energy rays. For heating curing, heating is sufficient at a temperature below which the woven fabric substrate will not deform, and at a temperature known to those skilled in the art that the curable functional groups react. For irradiation with active energy rays, irradiation at an amount known to those skilled in the art that sufficiently induces the reaction of the curable functional groups is sufficient.

[0081] When it is cured by electron beam irradiation, no polymerization initiator or curing catalyst needs to be added, so it is preferred.

[0082] In addition to the resin components mentioned above, functional agents may also be added to the resin composition. There are no particular limitations on the types of functional agents; they can be selected appropriately based on the desired function. Examples of functional agents include pigments, dyes, fluorescent agents, ultraviolet absorbers, antistatic agents, antibacterial agents, antiviral agents, and antifungal agents, and multiple agents can be used in combination.

[0083] Examples of pigments include zinc white, lead white, zinc barium white, titanium dioxide, precipitating barium sulfate, red lead, iron oxide, potassium ferrocyanide, and carbon black. Examples of ultraviolet absorbers include octyl methoxycinnamate, octyl dimethyl PABA, and tert-butylmethoxydibenzoylmethane. Examples of antistatic agents include anionic and cationic surfactants. Examples of antibacterial and antiviral agents include organic or inorganic compounds containing silver and copper, and quaternary ammonium compounds. Monovalent copper compounds such as cuprous oxide and cuprous halides exhibit particularly excellent antibacterial and antiviral properties and are therefore preferred.

[0084] The amount of functional agent added can be set appropriately according to the amount of functional agent added, preferably less than 50% by mass relative to the solid content of the coating film.

[0085] In addition, various additives such as surface conditioners can be added as needed. Adding surface conditioners improves the wettability and leveling properties of the resin composition when coating a woven fabric substrate, resulting in a more uniform coating.

[0086] (Coating thickness)

[0087] The thickness of the coating film of the fiber assembly in this embodiment is not particularly limited, and can be appropriately adjusted according to the intended use of the fiber assembly. However, in order to enable the fiber assembly of this embodiment to be bent for use, it is desirable that the thickness not exceed 500 nm. By making the coating film thickness 500 nm or less, even when the fiber assembly of this embodiment is bent for use, the coating film is less likely to be damaged compared to cases outside this range.

[0088] (Methods for forming a coating film)

[0089] The method for forming a coating film on the surface of a substrate such as a woven fabric can be, for example, a known method. Specifically, it can be manufactured by a process of manufacturing a resin composition, a process of coating the resin composition onto a substrate such as a woven fabric, and a process of curing the coated resin composition.

[0090] (1) Preparation process of resin composition

[0091] The resin composition is prepared by a known method. For example, the components of a curable resin are mixed using a commonly used mixing device such as a ball mill, and functional agents are further mixed in as needed to obtain the resin composition. The resin composition is then dissolved or dispersed in a solvent to prepare a varnish for use in a coating process. There are no particular limitations on the solvent used to dissolve the resin composition. The appropriate solvent should be selected based on the components in the resin composition and the type of woven fabric substrate to which it is coated. Examples of solvents 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 phenethyl ether; 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, isopropanol, butanol, and isobutanol; and halogen solvents such as dichloromethane and chloroform. Only one solvent or two or more solvents can be used. In the coating process, ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferred.

[0092] (2) Coating process

[0093] The varnish prepared in the resin composition preparation step is applied to a substrate such as woven fabric. Any known method can be used for application, and there are no particular limitations. Examples include dip coating, air knife coating, curtain coating, roller coating, bar coating, mold 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 can be set according to conditions known to those skilled in the art, depending on the coating amount, the type of solvent, and the type of curable functional groups of the curable resin. Specifically, the solvent should evaporate at a temperature not exceeding the melting point of the woven fabric or similar substrate, and at a temperature where the curing reaction of the curable resin does not begin during the drying process; for example, a temperature appropriately set between 50°C and 150°C is acceptable.

[0094] (3) Curing process

[0095] The woven fabric or similar material coated with the resin composition is cured by heating or irradiation with active energy rays. The heating temperature during curing can be determined based on the type of curing resin in the resin composition, as long as it does not exceed the melting point of the substrate such as the woven fabric. From the viewpoint of further suppressing changes in color over time, it is preferable to allow the coating 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 groups or measuring the gel fraction.

[0096] When curing the resin composition by irradiation with active energy rays, the type of active energy ray is not particularly limited. The active energy ray is appropriately selected based on the type of polymerizable monomer or oligomer. Examples of active energy rays include ultraviolet light, electron beams, alpha rays, beta rays, gamma rays, and other ionizing radiation. Since polymerization is readily achieved even without the addition of a polymerization initiator, electron beams are particularly preferred. The irradiation dose is sufficient to ensure that the resin composition cures without deteriorating the organic material constituting the coating film; for example, a cumulative light dose of 200 mJ / cm² when irradiating the resin composition with ultraviolet light is acceptable. 2 Above 400mJ / cm 2 The following are acceptable active energy rays that, when irradiated by an electron beam, are above 50 kGry and below 150 kGry.

[0097] Here, the coating of the fiber assembly of this embodiment has a martensitic hardness of 200 N / mm when the maximum indentation depth is less than 100 nm. 2 Above and below 230 N / mm 2 As mentioned above, the martensitic hardness of the coating film can be adjusted by controlling the type of curing resin, the mixing ratio, etc.

[0098] For example, by setting the composition of the curable resin such that the number of curable functional groups in 100g of the curable resin is more than 0.12 mol and less than 0.32 mol, a Martens hardness of 200 N / mm can be obtained. 2 Above and below 230 N / mm 2 The coating film. It should be noted that the number of curable functional groups in the curable resin can be calculated from the equivalent amount of curable functional groups in the curable resin and its mixing ratio.

[0099] By setting the martensitic hardness of the coating on substrates such as woven fabrics to 200 N / mm 2 Above and below 230 N / mm 2 It can suppress the peeling of the coating film caused by friction. Therefore, for example, when the coating film contains functional agents such as antibacterial and antiviral agents and is applied to a substrate such as woven fabric, it can suppress the peeling of functional agents caused by friction and suppress the reduction of desired functions such as antibacterial and antiviral properties caused by friction.

[0100] (Coating hardness test)

[0101] The coating hardness of the fiber assembly in this embodiment can be measured using an ultra-microhardness tester, such as the DUH-211 dynamic ultra-microhardness tester (manufactured by Shimadzu Corporation), by measuring the force and indentation depth of the coating applied to the fiber such as woven fabric using a Vickers indenter, and calculated according to ISO14577-1.

[0102] (Abrasion resistance test)

[0103] The resistance of the fiber assembly of the present invention to damage and peeling of the coating film caused by friction can be confirmed, for example, by rubbing the fiber assembly with a brush or the like a predetermined number of times and observing the change in the appearance of the coating film. Specifically, it can be confirmed, for example, by performing the friction test described in the examples of this specification.

[0104] According to this embodiment, in woven or nonwoven fabrics, it is less likely to produce friction-induced defects in the coating film on its surface, thereby improving the friction resistance of the coating film.

[0105] Example

[0106] [Example 1]

[0107] The fiber assembly of the embodiment is produced through the following processes of coating agent preparation, coating, and electron beam irradiation.

[0108] (Preparation of coating agent)

[0109] Measure 65 parts by weight of butyl acetate, 31 parts by weight of UNIDIC V-6850 (manufactured by DIC Corporation, weight average molecular weight: 26,000), and 4 parts by weight of trimethylolpropane triacrylate (manufactured by TMPTA Daicel-Allnex), and stir them evenly in a beaker to prepare a coating sample.

[0110] Next, a diluent is prepared by mixing 40 parts by weight of ethanol and 60 parts by weight of propylene glycol ether.

[0111] (Coating method)

[0112] As the substrate, TESP70SS (manufactured by NBC Meshtec Co., Ltd.) based on PET substrate is coated by impregnation.

[0113] 100 mL of a liquid prepared by diluting the coating sample 50 times with a diluent was placed in a stainless steel square tray. After immersion in the diluted solution, any remaining liquid on the edge of the tray was wiped off, and the sample was dried using a multi-safety dryer MSO-60TPS (manufactured by Futaba Scientific Co., Ltd.). It should be noted that the drying oven temperature was 120°C and the drying time was 2 minutes. The number of curable functional groups in 100 g of the curable resin of Example 1, obtained as a fiber aggregate, was 0.24 mol.

[0114] (Electron beam irradiation)

[0115] Electron beam irradiation was performed using an ERECTROBEAM-L EC250 / 15 / 180L electron beam irradiation device (manufactured by Iwasaki Electric Co., Ltd.). The irradiation conditions were: accelerating voltage 150 kV, electron current 5 mA, and dose 110 kGy.

[0116] [Example 2]

[0117] The 31 parts by weight of UNIDIC V-6850 (manufactured by DIC Corporation, weight average molecular weight: 26,000) in Example 1 were replaced with 15 parts by weight of UNIDIC V-6850 and 13 parts by weight of Art Resin UN-954 (manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 4,000). All other operations were performed in the same manner as in Example 1 to obtain the coated web of Example 2, which is a fiber aggregate. The number of curable functional groups in 100g of the curable resin of the obtained coated web was 0.31 mol.

[0118] [Example 3]

[0119] The 31 parts by weight of UNIDIC V-6850 in Example 1 were replaced with 26 parts by weight of Art Resin UN-952 (manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 8,000), and the 4 parts by weight of trimethylolpropane triacrylate (manufactured by TMPTA Daicel-Allnex) were replaced with 4 parts by weight of phenoxy diethylene glycol acrylate (manufactured by EBECRYL 110 Daicel-Allnex). All other operations were performed in the same manner as in Example 1 to obtain the coated mesh of Example 3, which is a fiber assembly. The number of curable functional groups in 100g of the curable resin of the obtained coated mesh was 0.18 mol.

[0120] [Comparative Example 1]

[0121] The 4 parts by weight of trimethylolpropane triacrylate (TMPTA, manufactured by Daicel-Allnex) in Example 1 were replaced with 4 parts by weight of phenoxydiethylene glycol acrylate (EBECRYL 110, manufactured by Daicel-Allnex). Otherwise, the same procedures as in Example 1 were performed to obtain the coated mesh of Comparative Example 1, which is a fiber assembly. The number of curable functional groups in 100g of the curable resin of the obtained coated mesh was 0.11 mol.

[0122] [Comparative Example 2]

[0123] The 65 parts by weight of butyl acetate in Example 1 were changed to 70 parts by weight; the 31 parts by weight of UNIDIC V-6850 (manufactured by DIC Corporation, weight average molecular weight: 26,000) were changed to 26 parts by weight of Art Resin UN-954 (manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 4,000); and the 4 parts by weight of trimethylolpropane triacrylate (manufactured by TMPTA Daicel-Allnex) were changed to 4 parts by weight of M-305 (manufactured by Toa Synthetic Co., Ltd., molecular weight: 319.6). All other operations were performed in the same manner as in Example 1 to obtain the coated mesh of Comparative Example 2, which is a fiber aggregate. The number of curable functional groups in 100g of the curable resin of the obtained coated mesh was 0.33 mol.

[0124] The following martensitic hardness test and friction test were performed on the coated screens of the examples and comparative examples.

[0125] (Martens hardness test)

[0126] The martensitic hardness was measured using the DUH-211 dynamic ultramicrohardness tester (manufactured by Shimadzu Corporation) based on the instrumented indentation hardness (ISO14577-1) standard of ISO.

[0127] As a pretreatment, the sample was bonded and fixed onto a glass plate, and the test was carried out under the test conditions recorded in Table 1.

[0128] The result is the average of 5 measurements.

[0129] [Table 1]

[0130]

[0131] (Friction test)

[0132] Friction tests were conducted on the coated screens of Examples 1-3 and Comparative Examples 1 and 2 under the following conditions.

[0133] The BA665 air purifier / air conditioner brush (manufactured by Azuma Kogyo Co., Ltd.) was mounted on the vibrator. The coated mesh, serving as the test sample, was fixed to the top and bottom of a glass plate with tape and placed at the contact point with the brush for testing. The vibrator was operated at 120 rpm for 8 minutes and 30 seconds.

[0134] Use SEM to observe the appearance of the coating on the coated mesh after the friction test to confirm whether there are any defects in the coating.

[0135] The composition of the coated screens of the examples and comparative examples is summarized in Table 2. Additionally, the results of the martensitic hardness test and friction test are shown in Table 3.

[0136] In addition, for the coated screen of Example 1, a photograph before the friction test is shown. Figure 1 The photos after the friction test are shown. Figure 2 Similarly, photographs of the coated screens of Comparative Examples 1 and 2 before and after the friction test are also shown (Comparative Example 1 before the test: Figure 3 After the experiment: Figure 4 Comparative Example 2: Before the experiment: Figure 5 After the experiment: Figure 6 ).

[0137] [Table 2]

[0138]

[0139] [Table 3]

[0140]

[0141] As shown in Table 3, in the coating meshes of Examples 1-3, defects in the coating film caused by friction were suppressed.

Claims

1. A fiber aggregate, characterized in that, At least a portion of its surface is coated. The fiber assembly has a substrate made of woven fabric, knitted fabric, or nonwoven fabric, and A coating that covers at least a portion of the substrate surface. The martensitic hardness of the coating, measured when the maximum indentation depth is below 100 nm, is 200 N / mm. 2 Above and below 230 N / mm 2 .

2. The fiber assembly according to claim 1, characterized in that, The coating contains functional agents.

3. The fiber assembly according to claim 2, characterized in that, The functional agent is an inorganic material.

4. The fiber assembly according to claim 2, characterized in that, The functional agent is an antibacterial agent and / or an antiviral agent.

5. The fiber assembly according to any one of claims 1 to 4, characterized in that, The coating contains an acrylic resin.

6. The fiber assembly according to any one of claims 1 to 4, characterized in that, The thickness of the coating is less than 500 nm.

7. A method for improving the friction resistance of a coating film, comprising: The Martens hardness measured when the maximum indentation depth of the coating formed on woven, knitted, or nonwoven fabrics is less than 100 nm is 200 N / mm. 2 Above and below 230 N / mm 2 The composition of the resin constituting the coating film is set in a certain way.

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