Fiber aggregate
A coating film with controlled Martens hardness on woven, knitted, or non-woven fabrics addresses the issue of peeling and damage by setting the hardness between 200 N/mm² to 230 N/mm², ensuring resistance to rubbing and maintaining functional properties.
Patent Information
- Application Number
- JP2023220349
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-12-27
- Publication Date
- 2025-07-09
AI Technical Summary
Existing methods for applying coating films on woven, knitted, or non-woven fabrics to provide antibacterial and dustproof properties fail to account for the differences in curing conditions and external forces between film substrates and fibers, leading to potential peeling and damage of the coating film.
A coating film with a Martens hardness of 200 N/mm² to 230 N/mm² at a maximum indentation depth of 100 nm is applied to woven, knitted, or non-woven fabrics, using a resin composition that includes a functional agent and specific curable polymers, ensuring the film's resistance to rubbing and peeling.
The coating film effectively prevents peeling and damage from rubbing, maintaining antibacterial and antiviral properties by setting the Martens hardness within a predetermined range, enhancing the film's strength and durability.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to a fibrous aggregate having a coating film.
Background Art
[0002] In order to impart functions such as antibacterial properties and dustproof properties to a mesh substrate such as a filter, a resin composition containing a functional material may be used to form a coating film and fix it on the mesh surface. Since the coating film is not damaged or peeled off by an external force such as rubbing, the coating film requires a certain hardness. In the case of a film substrate or the like, the pencil hardness test is often used as an index of the coating film hardness. However, since the coating width formed on the fiber in a textile product such as a mesh is narrow, it is impossible to evaluate the coating film hardness by the pencil hardness. In order to apply a coating resistant to rubbing, it is necessary to measure the coating film hardness in a minute area. However, directly measuring the coating film hardness on the fiber and performing coating film design has not been conventionally performed, and the resin composition has always been trial and error based on the intuition of the developer. The hardness of a coating film in a minute area can be measured as Martens hardness with a ultra-micro hardness tester, and the measurement standard is defined in ISO14577-1. 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 0.15 GPa or more and 0.35 GPa or less at an indentation depth of 2000 nm.
Prior Art Documents
Patent Documents
[0003]
Patent Document 1
Summary of the Invention
Problems to be Solved by the Invention
[0004] The present invention provides a novel technique capable of making it less likely that a coating film on the surface of a woven fabric, knitted fabric or non-woven fabric is damaged by rubbing. [Means for Solving the Problem]
[0005] Even if a coating film having the same configuration as a coating film with a coating film strength that does not cause peeling or the like on a film substrate is formed on a woven fabric, knitted fabric, or non-woven fabric, the coating film does not necessarily prevent peeling or the like. This is because the curing conditions of the coating film, for example, the irradiation state of active energy rays, are not necessarily the same on the film and on fibers such as woven fabrics, so the cross-linked state of the coating film is different between the film substrate and the fibers, or the way external forces are applied is different between the film and the fibers, making the coating film more likely to be damaged. Therefore, in the case of a substrate that is easily bent or shear-deformed like a woven fabric, applying a resin composition of a coating film effective for a film-like substrate may not achieve the expected effect. As a result of intensive research, the present inventors have found that by setting the coating film hardness on the surface of the fibers constituting a woven fabric or the like within a predetermined range, it is possible to make the coating film less likely to be damaged by rubbing.
[0006] The gist of the present invention is as follows. [1] A fiber aggregate at least a part of the surface of which is coated, a substrate made of a woven fabric, knitted fabric, or non-woven fabric, and a coating film covering at least a part 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 or more and less than 230 N / mm 2 A fiber aggregate characterized by the above. [2] The fiber aggregate according to [1], wherein the coating film contains a functional agent. [3] The fiber aggregate according to [2], wherein the functional agent is an inorganic material. [4] The fiber aggregate according to [2], wherein the functional agent is an antibacterial agent and / or an antiviral agent. [5] The fiber aggregate according to any one of [1] to [4], wherein the coating film contains an acrylic resin. The fibrous aggregate according to any one of [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. [Advantages of the Invention]
[0007] According to the present invention, it is possible to provide a novel technique that can make it less likely for defects due to rubbing of the coating film on the surface of the fabric, knitted fabric or non-woven fabric to occur. [Brief Description of the Drawings]
[0008]
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[0009] Hereinafter, embodiments of the present invention will be described. In the fiber assembly of this embodiment, at least a part of its surface is coated, and it includes a woven fabric, knitted fabric, or non-woven fabric as a base material (hereinafter also referred to as a base material such as a woven fabric) and a coating film formed on the surface of the base material such as a woven fabric. 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 2 230 N / mm 2 or more and less than. In addition, in this specification, the fiber assembly means a structure formed by aggregating a plurality of fibers.
[0010] (Base material such as woven fabric) The base material such as a woven fabric in this embodiment is a woven fabric woven with fibers in a predetermined weaving pattern, a knitted fabric knitted in a predetermined knitting pattern, or a non-woven fabric formed by randomly entangling fibers as a base material, and its material is not particularly limited as long as a coating film can be formed on the surface such as a woven fabric. Examples of such materials for woven fabrics and the like include organic fibers formed from various resins and inorganic fibers formed from inorganic materials such as glass, ceramics, and metals. Organic fibers include synthetic fibers as exemplified below and natural fibers such as cotton, hemp, and silk. The woven fabric and the like may be formed by combining one or more of these, or may be formed of fibers in which the surface layer portion and the central portion of the fiber are made of different materials.
[0011] Examples of resins that can constitute organic fibers include thermoplastic resins such as polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, EVA resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, methyl 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), PTFE, etc.; biodegradable resins such as polylactic acid resin, polyhydroxybutyrate resin, modified starch resin, polycaprolactone resin, polybutylene succinate resin, polybutylene adipate terephthalate resin, polybutylene succinate terephthalate resin, polyethylene succinate resin, etc.; thermosetting resins such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, epoxy acrylate resin, acrylic urethane resin, urethane resin, etc.; elastomers such as polystyrene elastomer, polyethylene elastomer, polypropylene elastomer, polyurethane elastomer, etc., and natural resins such as lacquer. Also, examples of inorganic fiber materials include glass, carbon, metal, etc. As the metal, materials 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 part of the surface of the substrate. The coating film of this embodiment can be formed, for example, from a resin composition. Specifically, on the surface of a substrate such as a fabric, a composition containing at least one selected from the group consisting of thermosetting or active energy ray-curable monomers and polymers is crosslinked and cured by heating, irradiating with active energy rays, or using both heating and irradiation with active energy rays to obtain a coating film. The active energy rays are not particularly limited, and examples include ionizing radiations such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. Hereinafter, a thermosetting or active energy ray-curable monomer may be collectively referred to as a curable monomer, a thermosetting or active energy ray-curable polymer may be collectively referred to as a curable polymer, and further, the curable monomer and the curable polymer may be collectively referred to as a curable resin. The martens hardness of the coating film of the present embodiment, as described above, is 200 N / mm when measured at a maximum indentation depth of 100 nm or less 2 or more and 230 N / mm 2 Although it is less than, the martens hardness of the coating film can be adjusted by controlling the type and blending ratio of the curable resin and the like.
[0013] When the coating film includes a plurality of coating layers, the resin compositions forming each layer may be the same or different.
[0014] 〈Curable Polymer〉 The curable polymer is a polymer containing a curable functional group. The curable polymer also includes a so-called oligomer region, and its weight average molecular weight is 500 or more. From the viewpoint of increasing the coating film hardness, 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 including carbon-carbon bonds, ether bonds, urea bonds, ester bonds, urethane bonds, siloxane bonds, etc. as the main chain, and contains curable functional groups as side chains or end groups. The curable functional group is a functional group that can form a crosslink by a chemical bond with the polymer, and curable functional groups known to those skilled in the art such as vinyl groups, ethynyl groups, epoxy groups, amino groups, hydroxyl groups, carboxyl groups, acid anhydrides, methylol groups, and silanol groups are applicable. The curable polymer may be an organic polymer or an inorganic polymer. From the viewpoint of transparency, a polymer chain containing carbon-carbon bonds is preferable, and from the viewpoint of formability, a polymer chain containing a urethane bond is preferable.
[0016] The number of curable functional groups preferably includes 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 preferable because polymerization is easy.
[0017] Specific examples of preferable 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) adding a compound having a hydroxyl group and an acryloyl group (or a methacryloyl group) to a polyisocyanate compound having a terminal isocyanate group in the molecule, or (2) reacting a polyurethane polyol obtained by reacting a polyisocyanate compound with a polyol with an isocyanate group-containing (meth)acrylate monomer.
[0019] Examples of the polyisocyanate compound 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-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, or a diisocyanate compound obtained by hydrogenating aromatic isocyanates 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 burette type adducts and isocyanurate ring type adducts of these diisocyanates.
[0020] Examples of the compound having a hydroxyl group and an acryloyl group (or 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, etc. to these.
[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 isocyanate ethyl acrylate, isocyanate propyl acrylate, and unsaturated compounds formed by adding a polyisocyanate compound such as hexamethylene diisocyanate to an active hydrogen - containing polymerizable monomer such as 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 combination with 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. Specifically, 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 a hydroxyl - group - containing monomer are included.
[0025] The polymers can be used alone or in combination of two or more.
[0026] As the curable polymer, commercially available products 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, UXF-4002 manufactured by Nippon Kayaku Co., Ltd.; UF-8001G, UA-510H manufactured by Kyoeisha Chemical Co., Ltd.; EBECRYL244, EBECRYL284, EBECRYL8402, EBECRYL8807, EBECRYL264, EBECRYL265, EBECRYL9260, EBECRYL8701, EBECRYL8405, EBECRYL1290, EBECRYL5129, EBECRYL220, KRM8200, KRM7804, KRM8452 manufactured by Daicel Ornex Co., Ltd.; UV-1700B, UV-600B, UV-7600B, UV-7640B, UV-7650B, UV-3520EA, UV-7000B, Violet UV-AF305A manufactured by Mitsubishi Chemical Corporation; CN-9001, CN-9004, CN-9005, CN-965, CN-9178, CN-9893, CN-9782, CN-964, CN-9013, CN-9010 manufactured by Arkema; 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.;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 Resin UN-7700, Art Resin UN-9000PEP, Art Resin UN-9200, Art Resin UN-904UREA, Art Resin UN-H7UREA, etc. manufactured by Negami Kogyo Co., Ltd. can be used.;
[0027] Examples of commercially available acrylic (meth)acrylate oligomers or polymers include, for example, Unidic V-6840, Unidic V-6841, Unidic V-6850, Unidic EMS-635, Unidic WHV-649 manufactured by DIC Corporation; Hitroid 7975, Hitroid 7977, Hitroid 7988, Hitroid 7975D manufactured by Hitachi Chemical Co., Ltd.; 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, Art Cure RA-4101, Art Cure MAP-4000, Art Cure MAP2801, etc. manufactured by Negami Kogyo Co., Ltd. can be used.
[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 generally be 500 or less. The curable functional group equivalent of the curable monomer may be 50 g / eq. or more and may be 200 g / eq. or less.
[0029] The curable monomer preferably has 2 or more, more preferably 3 or more, and particularly preferably 5 or more curable functional groups. In order to adjust the crosslink density, a resin having only one functional group of the same kind as the curable functional group may be contained in the curable resin composition. Preferred examples of the curable functional group include acryloyl group and 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 of a polyhydric alcohol and (meth)acrylic acid, or a transesterification reaction of a polyhydric alcohol and a (meth)acrylate ester.
[0031] Examples of polyfunctional (meth)acrylate monomers with a sclerogenic functional group equivalent of 50 g / eq. or more and 200 g / eq. or less include bifunctional (meth)acrylate monomers such as 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 (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, 9,9 - bis[4-(2 - hydroxyethoxy)phenyl]fluorene di(meth)acrylate; trifunctional (meth)acrylate monomers such as 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, 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, caprolactone - modified (3) tris(2 - hydroxyethyl) isocyanurate tri(meth)acrylate;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, ethoxylated (8) pentaerythritol tetra(meth)acrylate; pentafunctional (meth)acrylate monomers such as dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate; hexafunctional (meth)acrylate monomers such as dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate; (meth)acrylate monomers having seven or more functional groups such as tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, etc. can be mentioned.;
[0032] The curable monomer can be used alone or in combination of two or more kinds.;
[0033] 〈Non-curable polymer〉 The resin composition may contain a non-curable polymer. By containing a non-curable polymer, the flexibility is enhanced, and when the fiber aggregate of the present embodiment is bent and used, the coating film is less likely to be damaged.;
[0034] A non-curable polymer is a thermoplastic polymer that does not contain a curable functional group and does not undergo cross-linking 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. Since it does not dissolve in the coating solvent or the viscosity of the coating solution becomes high and coating becomes 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 the non-curable polymer include urethane resin, acrylic resin, polyester resin, polyolefin resin, etc. From the viewpoint of affinity with the above-described curable resin, acrylic resin is preferred.
[0036] In the resin composition, the content of the curable resin can be at least 5% by mass or more based on the total amount of the curable and non-curable polymers. The ratio of the curable polymer to the curable monomer in the curable resin may be freely set as long as the martens hardness after curing is within a predetermined range, but it is preferable that the curable monomer is contained in an amount of 5% by mass or more based on the total amount of the curable polymer and the curable monomer. Also, the number of curable functional groups in the resin composition is desirably 0.12 mol or more and 0.32 mol or less per 100 g of the resin component. The number of curable functional groups in the resin composition can be calculated from the molecular weight, the number of functional groups, and the blending amount of the curable resin.
[0037] <Polymerization initiator> The resin composition can contain a polymerization initiator or a curing catalyst according to the type of resin constituting it 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 blending amount of the curing initiator is preferably 0.01 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, based on 100 parts by mass of the resin component.
[0038] As the curing initiator, a polymerization initiator or a curing catalyst known to those skilled in the art can be used. When curing by radical polymerization, for example, azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, benzoyl peroxide, dicumyl peroxide, dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxy esters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as di-t-butyl peroxide and other organic peroxides, and ammonium salts, potassium salts, sodium salts and other inorganic peracid compounds of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonic acid can also be used. When performing photopolymerization, examples include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, titanocene-based photopolymerization initiators, oxime ester-based polymerization initiators, and photo cationic polymerization initiators.
[0039] Examples of alkylphenone-based photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-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-hydrodoxy-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, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.
[0040] Examples of acylphosphine oxide-based photoinitiators 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-based photoinitiators include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium. Examples of oxime ester-based polymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(0-acetoxime), 2-oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, and 2-(2-hydroxyethoxy)ethyl ester.
[0042] Examples of cationic photoinitiators 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). Known cationic photoinitiators in the art can be used.
[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 may be performed by heating at a temperature known to those skilled in the art at which the curable functional groups react below the temperature at which the textile substrate does not deform. When performing active energy ray irradiation, an irradiation dose known to those skilled in the art at which the curable functional groups sufficiently react may be irradiated.
[0045] Curing by electron beam irradiation is preferable because it eliminates the need to add a polymerization initiator or a curing catalyst.
[0046] A functional agent can be added to the resin composition in addition to the above-described resin components. The type of the functional agent is not particularly limited and may be appropriately selected according to the function to be imparted. Examples of the functional agent include pigments, dyes, fluorescent agents, ultraviolet absorbers, antistatic agents, antibacterial agents, antiviral agents, antifungal agents, etc., and a plurality of them may be used in combination. Examples of the pigment include zinc white, lead white, lithopone, titanium dioxide, precipitated barium sulfate, red lead, iron oxide, potassium ferrocyanide, carbon black, etc. Examples of the ultraviolet absorber include octyl methoxycinnamate, octyl dimethyl PABA, t-butylmethoxydibenzoylmethane, etc. Examples of the antistatic agent include anionic surfactants, cationic surfactants, etc. Examples of the antibacterial agent and the antiviral agent include organic compounds or inorganic compounds containing silver or copper, quaternary ammonium compounds, etc. Monovalent copper compounds such as cuprous oxide and cuprous halide are preferable because they are particularly excellent in antibacterial and antiviral properties. The addition amount of the functional agent may be appropriately set according to the functional agent to be added, but is preferably 50% by mass or less based on the solid content of the coating film. In addition, various additives such as a surface conditioner can be added as necessary. When a surface conditioner is added, the wettability and leveling property when applying the resin composition to the textile substrate are improved, and a coating film with a more uniform surface can be obtained.
[0047] (Thickness of the coating film) The thickness of the coating film of the fiber assembly of the present embodiment is not particularly limited and may be appropriately adjusted according to the purpose of use of the fiber assembly or the like. However, when the fiber assembly of the present embodiment is to be used in a bent state, it is desirable that the thickness does not exceed 500 nm. By setting the coating film thickness to 500 nm or less, when the fiber assembly of the present embodiment is used in a bent state, the coating film is less likely to be damaged compared to the case where it is out of the range.
[0048] (Method for forming coating film) As a method for forming a coating film on the surface of a substrate such as a woven fabric, for example, a known method can be applied. Specifically, for example, it can be produced through a process of manufacturing a resin composition, a process of applying the resin composition to a substrate such as a woven fabric, and a process of curing the applied resin composition.
[0049] (1) Preparation process of resin composition The resin composition is prepared by a known method. For example, using a commonly used mixing device such as a ball mill, each component of the curable resin, and in some cases, a functional agent is further mixed to obtain the resin composition. The resin composition is dissolved or dispersed in a solvent to prepare a varnish used in the coating process. The solvent for dissolving the resin composition is not particularly limited and may be appropriately selected according to the components contained in the resin composition and the type of the fabric substrate to be coated. For example, 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; halogen solvents such as dichloromethane and chloroform can be mentioned. These may be used alone or in combination of two or more. Among the coating processes, ester solvents, ether solvents, alcohol solvents, and ketone solvents are preferred.
[0050] (2) Coating process The varnish prepared in the resin composition preparation step is applied to a base material such as a fabric. A known method may be used for the application method, and it is not particularly limited. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a bar coating method, a die coating method, an inkjet method, etc. may be mentioned. After application, a drying treatment is performed to remove the solvent contained in the varnish. The drying temperature is not particularly limited, and it may be set to conditions known to those skilled in the art according to the coating amount, the type of solvent, and the type of curable functional group of the curable resin. Specifically, the solvent may be volatilized at a temperature that does not exceed the melting point of the fabric or the like as the base material and at which the curing reaction of the curable resin does not start in the drying step. For example, it may be appropriately set between 50°C and 150°C.
[0051] (3) Curing step The fabric or the like coated with the resin composition is cured by heating or irradiating with active energy rays. The heating temperature in the case of heat curing may be determined according to the type of the cured resin in the resin composition as long as it does not exceed the melting point of the fabric or the like as the base material. From the viewpoint of further suppressing changes over time such as coloring, it is better for the coating film curing reaction to proceed as completely as possible. The degree of progress 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 with active energy rays, the type of active energy rays is not particularly limited. The active energy rays are appropriately selected according to the type of the polymerizable monomer or oligomer. The active energy rays are not particularly limited, and examples include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Since it polymerizes easily without adding a polymerization initiator, an electron beam is particularly preferable. The irradiation amount may be an irradiation amount within a range in which the resin composition is cured and the organic substances constituting the coating film are not deteriorated. For example, in the case of ultraviolet irradiation on the resin composition, the integrated light amount is 200 mJ / cm 2 or more and 400 mJ / cm 2 or less, and in the case of electron beam irradiation, an active energy ray of 50 kGry or more and 150 kGry or less may be irradiated.
[0052] Here, the coating film of the fiber aggregate of the present embodiment has a Martens hardness measured at a maximum indentation depth of 100 nm or less of 200 N / mm 2 or more and less than 230 N / mm 2 Although it is less, the Martens hardness of the coating film can be adjusted by controlling the type and blending ratio of the curable resin as described above. 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, a coating film with a Martens hardness of 200 N / mm 2 or more and less than 230 N / mm 2 can be obtained. The number of curable functional groups in the curable resin can be calculated from the curable functional group equivalent and its blending ratio of the constituent curable resins. By setting the Martens hardness of the coating film on a substrate such as a fabric to 200 N / mm 2 or more and less than 230 N / mm 2 it is possible to suppress the peeling of the coating film 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 fabric, the peeling of the functionalizing agent due to rubbing is suppressed, and it is possible to suppress the decrease in desired functions such as antibacterial and antiviral properties due to rubbing.
[0053] (Measurement of Coating Film Hardness) The coating film hardness of the fiber aggregate of the present embodiment can be calculated in accordance with ISO14577-1 by measuring the force and indentation depth applied to the coating film on the fiber such as a fabric using a ultra-micro hardness tester, for example, a dynamic ultra-micro hardness tester DUH-211 (manufactured by Shimadzu Corporation) with a Vickers indenter.
[0054] (Abrasion Resistance Test) The resistance of the fiber aggregate of the present invention to damage and peeling of the coating film due to rubbing can be confirmed, for example, by rubbing the fiber aggregate a predetermined number of times with a brush or the like and observing the change in the appearance of the coating film. Specifically, it can be confirmed, for example, by conducting the rubbing test described in the examples of this specification.
[0055] As described above, according to this embodiment, in the woven or non-woven fabric, it is possible to make it less likely to cause defects due to rubbing of the coating film on the surface, and it is possible to increase the strength of the coating film against rubbing.
Example
[0056] [Example 1] The fiber assembly of the example was produced through the following steps of coating agent preparation, coating, and electron beam irradiation.
[0057] (Coating agent preparation) 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 Ornex Co., Ltd.) were measured and uniformly stirred in a beaker to obtain a coating agent sample. Next, it was mixed at a ratio of 40 parts by mass of ethanol and 60 parts by mass of propylene glycol ether to obtain a diluent.
[0058] (Coating method) Using a PET substrate mesh TESP70SS (manufactured by NBC Mesh Tech Co., Ltd.) as the substrate, coating was performed by the dipping method. 100 mL of a solution obtained by diluting the coating agent sample 50-fold with the diluent was placed in a stainless steel square pot. After immersion in this diluent, the excess liquid was wiped off at the edge of the pot, and drying was performed using a multi-safety dryer MSO-60TPS (manufactured by FUTABA SCIENCE CO., LTD.). The temperature of the drying furnace was 120 °C and the drying time was 2 minutes. The number of curable functional groups in 100 g of the curable resin of the obtained coated mesh of Example 1, which is a fiber assembly, is 0.24 mol.
[0059] (Electron beam irradiation) Electron beam irradiation was performed using an electron beam irradiation device ERECTOROBEAM-L EC250 / 15 / 180L (manufactured by Iwasaki Electric Co., Ltd.). The irradiation conditions were an acceleration voltage of 150 kV, an electron current of 5 mA, and a dose of 110 kGy.
[0060] [Example 2] The same operations as in Example 1 were carried out except that 31 parts by mass of the Unidic V-6850 (manufactured by DIC Corporation, weight-average molecular weight: 26,000) in Example 1 were changed to 15 parts by mass of Unidic V-6850 and 13 parts by mass of Art Resin UN-954 (manufactured by Negami Kogyo Co., Ltd., weight-average molecular weight: 4,000), and the coating mesh of Example 2 which is a fiber aggregate was obtained. The number of curable functional groups in 100 g of the curable resin of the obtained coating mesh is 0.31 mol.
[0061] [Example 3] The same operations as in Example 1 were carried out except that 31 parts by mass of the Unidic V-6850 in Example 1 were changed to 26 parts by mass of Art Resin UN-952 (manufactured by Negami Kogyo Co., Ltd., weight-average molecular weight: 8,000), and 4 parts by mass of trimethylolpropane triacrylate (TMPTA, manufactured by Daicel Ornex Co., Ltd.) were changed to 4 parts by mass of phenoxy diethylene glycol acrylate (EBECRYL 110, manufactured by Daicel Ornex Co., Ltd.), and the coating mesh of Example 3 which is a fiber aggregate was obtained. The number of curable functional groups in 100 g of the curable resin of the obtained coating mesh is 0.18 mol.
[0062] [Comparative Example 1] The same operations as in Example 1 were carried out except that 4 parts by mass of trimethylolpropane triacrylate (TMPTA, manufactured by Daicel Ornex Co., Ltd.) in Example 1 were changed to 4 parts by mass of phenoxy diethylene glycol acrylate (EBECRYL 110, manufactured by Daicel Ornex Co., Ltd.), and the coating mesh of Comparative Example 1 which is a fiber aggregate was obtained. The number of curable functional groups in 100 g of the curable resin of the obtained coating mesh is 0.11 mol.
[0063] [Comparative Example 2] 65 parts by mass of butyl acetate in Example 1 was changed to 70 parts by mass, 31 parts by mass of Unidic V-6850 (manufactured by DIC Corporation, weight average molecular weight: 26,000) was changed to 26 parts by mass of Art Resin UN-954 (manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 4,000), and 4 parts by mass of trimethylolpropane triacrylate (TMPTA, manufactured by Daicel Ornex Co., Ltd.) was changed to 4 parts by mass of M-305 (manufactured by Toagosei Co., Ltd., molecular weight: 319.6). The same operations as in Example 1 were performed except for the above changes to obtain a coated mesh of Comparative Example 2, which is a fiber aggregate. The number of curable functional groups in 100 g of the curable resin of the obtained coated mesh is 0.33 mol.
[0064] The following Martens hardness test and rubbing test were performed on the coated meshes of the examples and comparative examples.
[0065] (Martens hardness test) Using a dynamic ultra-micro hardness tester DUH-211 (manufactured by Shimadzu Corporation), the test was conducted based on the Martens hardness within the instrumented indentation hardness (ISO14577-1) of the ISO standard. As a pretreatment, the sample was adhesively fixed on a glass plate, and the test was conducted under the measurement conditions described in Table 1. The results were taken as the average value of 5 measurements.
[0066]
Table 1
[0067] (Rubbing test) The rubbing test was conducted on the coated meshes of Examples 1 to 3 and Comparative Examples 1 and 2 under the following conditions. BA665 air purifier·air conditioner brush (manufactured by Azuma Kogyo Co., Ltd.) was attached to a shaker. The coated mesh used as the sample was fixed to a glass plate with tape on the top and bottom, set at the position where it contacts the brush, and the test was conducted. The operating conditions of the shaker were 120 rpm for 8 minutes and 30 seconds. The appearance of the coating film of the coated mesh after the rubbing test was observed by SEM to confirm the presence or absence of coating film defects.
[0068] The compositions of the coating meshes of the examples and comparative examples are summarized in Table 2. Also, the results of the Martens hardness test and the abrasion test are shown in Table 3. Also, for the coating mesh of Example 1, a photograph before the abrasion test is shown in Fig. 1, and a photograph after the abrasion test is shown in Fig. 2. Similarly, photographs before and after the abrasion test are also shown for the coating meshes of Comparative Examples 1 and 2 (Comparative Example 1 before test: Fig. 3, after test: Fig. 4, Comparative Example 2 before test: Fig. 5, after test: Fig. 6).
[0069]
Table 2
[0070]
Table 3
[0071] As can be understood from Table 3, the loss of the coating film due to abrasion was suppressed in the coating meshes of Examples 1 to 3.
Claims
1. A fibrous aggregate, at least a part of the surface of which is coated, comprising: a base material made of a woven fabric, knitted fabric or non-woven fabric; and a coating film covering at least a part of the surface of the base material. The Martens hardness of the coating film measured at a maximum indentation depth of 100 nm or less is 200 N / mm ２ or more and less than 230 N / mm ２ The fibrous aggregate is characterized by this.
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 so as to be less than the above.
Citation Information
Patent Citations
Laminated film, molded body and method for producing the same
JP2023126785A