Active energy ray-curable composition, suture using the same, and method for producing the same

Abstract

To provide an active energy ray-curable composition that enables improvement of sealing performance of a suture portion formed by joining a plurality of materials, and that ensures rapid curing at a deep region of the suture portion where light hardly reaches.SOLUTION: An active energy ray-curable composition comprises a compound having an ethylenically unsaturated group and a photoradical polymerization initiator, wherein, when the viscosity of the active energy ray-curable composition is measured at 25°C using a cone-plate type rotational viscometer in compliance with JIS K 6833, the viscosity is 1 to 1000 mPa s, and wherein, when the tensile strain of a cured product of the active energy ray-curable composition is measured at 23°C in compliance with JIS K 7161:2014, the tensile strain is 50 to 700%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable composition, and preferably to an active energy ray-curable composition that can be cured by irradiation with active energy rays such as ultraviolet rays, even in areas that are not directly irradiated with active energy rays, and belongs to the technical field. [Background technology]

[0002] In order to improve waterproofing and airtightness in sewn materials that fasten multiple materials together, a sealing process is carried out in which a resin liquid is applied and cured to the area sewn with sewing thread. Examples of this process include waterproofing textile materials that need to prevent water leakage, such as raincoats and tents, and sealing the seams of airbags, which require high airtightness.

[0003] Patent Document 1 describes an airbag in which the edges of a first panel and a second panel are joined together by a joining means, characterized in that the joining means consists of stitching with thread and adhesion with an elastic adhesive such as a silicone adhesive or a urethane adhesive.

[0004] Patent Document 2 describes an airbag in which two sheets of synthetic fiber fabric are bonded together with a room-temperature curing adhesive sealant such as a solventless liquid silicone rubber, wherein the room-temperature curing adhesive sealant has a thixotropy index of 1.5 to 6 at 25°C, and the synthetic fiber fabric has a cover factor of 1500 to 2100.

[0005] Patent Document 3 describes a method for reducing air leakage from a one-piece woven (OPW) airbag, the method including forming an OPW airbag having seams and applying a hot melt sealant material to one or more seams of the OPW airbag.

[0006] However, silicone adhesives and urethane adhesives require moisture for hardening and take about a day to fully harden, resulting in insufficient productivity. Furthermore, the adhesives do not fully harden in the gaps between the wires because moisture is less likely to penetrate into those areas, resulting in insufficient sealing. Furthermore, the high viscosity of hot melt sealant materials makes it difficult to ensure that the resin penetrates sufficiently into the gaps between seams. Furthermore, since it is difficult for an active energy ray-curable composition to cure in areas that are not exposed to active energy rays, when an article that is difficult for active energy rays to transmit, such as sewing thread, is bonded, the active energy ray-curable composition remains uncured in so-called "dark areas" where the active energy rays do not reach, such as the gap between the sewing thread and the base fabric, resulting in a problem of insufficient sealing. The ability to cure even in dark areas is called "dark area curability," which is also known by other names such as "shadow area curability," "shaded area curability," "dark reaction curability," "light-shielded area curability," and "dark cure ability," and these are collectively referred to in this specification as "dark area curability." [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-1854 [Patent Document 2] JP 2007-38694 A [Patent Document 3] Special Publication No. 2020-536003 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention provides an active energy ray-curable composition that can improve the sealing properties of a seam formed by sewing together a plurality of materials and can cure in a short time even the inner part of the seam where light is difficult to reach. [Means for solving the problem]

[0009] As a result of extensive investigations, the present inventors have found that it is possible to provide an active energy ray-curable composition which comprises a compound having an ethylenically unsaturated group and a photoradical polymerization initiator, and which has a specific tensile strain and viscosity, thereby improving the sealing properties of a seam formed by sewing together multiple materials, and which can cure in a short time even at the inner part of a seam where light is difficult to reach.

[0010] The present invention includes the following embodiments. [1] An active energy ray-curable composition comprising a compound having an ethylenically unsaturated group and a photoradical polymerization initiator, wherein the active energy ray-curable composition has a viscosity of 1 to 1000 mPa s when measured at 25°C using a cone-and-plate rotational viscometer in accordance with JIS K 6833, and a cured product of the active energy ray-curable composition has a tensile strain of 50 to 700% when measured at 23°C in accordance with JIS K 7161:2014. [2] The active energy ray-curable composition according to [1], wherein the compound having an ethylenically unsaturated group includes a urethane (meth)acrylate and a monofunctional unsaturated compound. [3] The active energy ray-curable composition according to [2], wherein the urethane (meth)acrylate has a weight average molecular weight Mw of 3,000 to 100,000. [4] [1] The active energy ray-curable composition according to [1], wherein the photoradical polymerization initiator has an absorption coefficient (mL / g·cm) at 405 nm of 100 or more. [5] The active energy ray-curable composition according to [1] or [4], wherein the photoradical polymerization initiator is contained in an amount of 0.01 to 15 parts by mass relative to 100 parts by mass of the total amount of the compounds having an ethylenically unsaturated group. [6] The active energy ray-curable composition according to any one of [1] to [4], which contains a fluorescent agent and / or a reducing agent. [7] The active energy ray-curable composition according to [6], wherein the emission spectrum of the fluorescent agent has a maximum in the range of 380 to 500 nm. [8] The active energy ray-curable composition according to [7], wherein the fluorescent agent is contained in an amount of 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of the compounds having an ethylenically unsaturated group. [9] [6] The active energy ray-curable composition according to [6], wherein the reducing agent has an absorption coefficient (mL / g·cm) at 405 nm of 100 or more.

[10] The active energy ray-curable composition according to [9], wherein the reducing agent comprises at least one selected from the group consisting of thiol compounds, divalent tin compounds, and trivalent phosphorus compounds.

[11] The active energy ray-curable composition according to

[10] , wherein the reducing agent is contained in an amount of 0.1 to 20 parts by mass relative to 100 parts by mass of the total amount of the compounds having an ethylenically unsaturated group.

[12] A sealant for application to sutures, comprising the active energy ray-curable composition according to any one of [1] to [4].

[13] A sewn product obtained by applying a sealant containing an active energy ray-curable composition to a seam formed by sewing together a plurality of materials, and then irradiating the applied area with active energy rays to cure the sealant, wherein the active energy ray-curable composition contains a compound having an ethylenically unsaturated group and a photoradical polymerization initiator, and the viscosity of the active energy ray-curable composition is 1 to 1000 mPa s when measured at 25°C using a cone-and-plate rotational viscometer in accordance with JIS K 6833, and the tensile strain of a cured product of the active energy ray-curable composition is 50 to 700% when measured at 23°C in accordance with JIS K 7161:2014.

[14] A method for producing a sutured product, comprising applying a sealant containing an active energy ray-curable composition to a seam formed by sewing together a plurality of materials, and then irradiating the applied sealant with active energy rays to cure the sealant, wherein the active energy ray-curable composition contains a compound having an ethylenically unsaturated group and a photoradical polymerization initiator, and the viscosity of the active energy ray-curable composition is 1 to 1000 mPa s when measured at 25°C using a cone-and-plate rotational viscometer in accordance with JIS K 6833, and the tensile strain of the cured product of the active energy ray-curable composition is 50 to 700% when measured at 23°C in accordance with JIS K 7161:2014. [Effects of the Invention]

[0011] The composition of the present invention improves the sealing properties of seams formed when multiple materials are sewn together, and can cure in a short time even at the inner part of the seam where light is difficult to reach. Furthermore, by controlling the tensile strain of the cured product to a predetermined value, the sealing properties can be maintained even after bending processing. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to these.

[0013] In this specification, the expression "a to b" representing a numerical range means "not less than a and not more than b," unless otherwise specified.

[0014] In the present specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. In addition, in the present specification, the upper or lower limit of a numerical range may be replaced with a value shown in the examples.

[0015] In this specification, "% by mass" and "% by weight" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0016] Furthermore, in the embodiment of the present invention, a combination of two or more of the preferred embodiments described below is also a preferred embodiment.

[0017] In this specification, acrylate and / or methacrylate will be referred to as (meth)acrylate, acryloyl group and / or methacryloyl group will be referred to as (meth)acryloyl group, and acrylic acid and / or methacrylic acid will be referred to as (meth)acrylic acid.

[0018] <Compounds Having Ethylenically Unsaturated Groups> Examples of the ethylenically unsaturated group include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, and a (meth)allyl group. A (meth)acryloyl group is preferred, and an acryloyl group is more preferred, as this provides excellent curability of the composition.

[0019] The compound having an ethylenically unsaturated group may be a compound having one or more ethylenically unsaturated groups, and specific examples include a compound having one ethylenically unsaturated group (hereinafter referred to as a "monofunctional unsaturated compound") and a compound having two or more ethylenically unsaturated groups (hereinafter referred to as a "polyfunctional unsaturated compound").

[0020] <Monofunctional unsaturated compounds> Among compounds having an ethylenically unsaturated group, specific examples of monofunctional unsaturated compounds include compounds having one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylate"), (meth)acrylamide having one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylamide"), compounds having one vinyl group, and compounds having one allyl group.

[0021] Specific examples of monofunctional (meth)acrylates include: alkyl (meth)acrylates having 8 or more carbon atoms, such as octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; mono(meth)acrylates of polyols such as trimethylolpropane mono(meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol mono(meth)acrylate, ditrimethylolpropane mono(meth)acrylate, and dipentaerythritol mono(meth)acrylate; monofunctional (meth)acrylates having an alicyclic group, such as isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, tricyclodecanemethylol (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; monofunctional (meth)acrylates having an aromatic group, such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenol (meth)acrylate, (meth)acrylates of alkylene oxide adducts of phenol, (meth)acrylates of alkylene oxide adducts of alkylphenols, (meth)acrylates of alkylene oxide adducts of p-cumylphenol, and (meth)acrylates of alkylene oxide adducts of o-phenylphenol; Examples include alkyl carbitol (meth)acrylates such as carbitol (meth)acrylates such as ethyl carbitol (meth)acrylate, butyl carbitol (meth)acrylate, and 2-ethylhexyl carbitol (meth)acrylate.

[0022] The monofunctional (meth)acrylate may be a compound having various functional groups, such as a hydroxyl group, a carboxyl group, a cyclic ether group, and a heterocyclic ring. Examples of monofunctional (meth)acrylates having a hydroxyl group include (meth)acrylates having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, as well as 2-hydroxy-3-phenoxypropyl (meth)acrylate. Examples of monofunctional (meth)acrylates having a carboxy group include (meth)acrylic acid, a Michael addition type dimer of (meth)acrylic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, and monohydroxyethyl phthalate (meth)acrylate. Examples of compounds having a cyclic ether group include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)methyl (meth)acrylate, and 3-ethyl-3-oxetanylmethyl (meth)acrylate. Examples of the monofunctional (meth)acrylate having a heterocycle include (meth)acryloylmorpholine, and monofunctional (meth)acrylates having an imide group such as N-(2-(meth)acryloxyethyl)hexahydrophthalimide and N-(2-(meth)acryloxyethyl)tetrahydrophthalimide.

[0023] Examples of monofunctional (meth)acrylamides include N-alkyl(meth)acrylamides such as N,N-dimethyl(meth)acrylamide, (meth)acryloylmorpholine, N-methyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nn-butyl(meth)acrylamide, N-sec-butyl(meth)acrylamide, Nt-butyl(meth)acrylamide, and Nn-hexyl(meth)acrylamide; N-hydroxyalkyl (meth)acrylamides such as N-hydroxyethyl (meth)acrylamide; and Examples of N,N-dialkyl(meth)acrylamides include N,N-dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide, and N,N-dihexyl(meth)acrylamide.

[0024] Examples of vinyl compounds include compounds having one vinyl group.Specific examples include vinyl monomers such as styrene, vinyltoluene, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinylpyridine, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-hydroxyethyl vinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether.

[0025] The allyl compound includes a compound having one allyl group, specifically, allyl alcohol.

[0026] <Polyfunctional unsaturated compounds> Examples of polyfunctional unsaturated compounds include compounds having two (meth)acryloyl groups (hereinafter referred to as "bifunctional (meth)acrylates") and compounds having three or more (meth)acryloyl groups (hereinafter referred to as "trifunctional or higher (meth)acrylates").

[0027] Specific examples of the bifunctional (meth)acrylate include aliphatic diol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, and 2-butyl-2-ethyl-1,3-propanediol diacrylate; di(meth)acrylates of trihydric or higher polyols such as glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, and dipentaerythritol di(meth)acrylate; Di(meth)acrylates of these polyol alkylene oxide adducts; Di(meth)acrylates having an isocyanuric acid skeleton, such as di(meth)acrylates of isocyanuric acid ethylene oxide adducts; and Di(meth)acrylates of alkylene oxide adducts of bisphenols, such as di(meth)acrylates of alkylene oxide adducts of bisphenol A and di(meth)acrylates of alkylene oxide adducts of bisphenol F The following can be mentioned: In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, tetramethylene oxide, and a combination of ethylene oxide and propylene oxide.

[0028] Examples of trifunctional or higher (meth)acrylates include: Polyol poly(meth)acrylates such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethanolamine tri(meth)acrylate, pentaerythritol tri- or tetra(meth)acrylate, ditrimethylolpropane tri- or tetra(meth)acrylate, diglycerin tri- or tetra(meth)acrylate, and dipentaerythritol tri-, tetra-, penta-, or hexa(meth)acrylate; and Tri-, tetra-, penta-, or hexa(meth)acrylates of alkylene oxide adducts of these polyols; and Examples include tri(meth)acrylates having an isocyanuric acid skeleton, such as tri(meth)acrylates of alkylene oxide adducts of isocyanuric acid. Examples of the alkylene oxide adducts include ethylene oxide adducts, propylene oxide adducts, and adducts of ethylene oxide and propylene oxide.

[0029] A bifunctional (meth)acrylate and a trifunctional or higher functional (meth)acrylate may be used in combination, for example, a mixture of di- and triacrylates of an ethylene oxide adduct of isocyanuric acid.

[0030] In addition to the compounds mentioned above, examples of the polyfunctional unsaturated compound include urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate and polyether (meth)acrylate, polyfunctional polymer, polyfunctional vinyl compound, and polyfunctional allyl compound. These compounds will be explained below.

[0031] <Urethane (meth)acrylate> Urethane (meth)acrylate is a (meth)acrylate compound having a urethane bond. Examples of urethane (meth)acrylates include reaction products of polyols, organic polyisocyanates, and hydroxyl group-containing (meth)acrylates (hereinafter referred to as "urethane (meth)acrylate oligomers"), and reaction products of organic polyisocyanates and hydroxyl group-containing (meth)acrylates (hereinafter referred to as "urethane adducts"). The raw material compounds and production method of the urethane (meth)acrylate will be described below.

[0032] In the case of a urethane (meth)acrylate oligomer, a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate are used as raw material compounds for the urethane (meth)acrylate, and in the case of a urethane adduct, an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate are used.

[0033] Specific examples of polyols include polyether polyols, polycarbonate polyols, polyester polyols, and diols having a polyene skeleton. The polyether polyol may be a polyalkylene glycol having two or more oxyalkylene units, and specific examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of polycarbonate polyols include reaction products of carbonates and diols. Specific examples of carbonates include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. Examples of diols include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, nonanediol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol, and hydroxypivalic acid neopentyl glycol ester (hereinafter referred to as "low molecular weight diols"). Examples of polyester polyols include reaction products of at least one selected from the group consisting of the above-mentioned low-molecular-weight diols, polyether polyols, and polycarbonate polyols with an acid component. Specific examples of the acid component include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid, or their anhydrides, and ring-opening reaction products of polycarbonate diols and caprolactone. Examples of diols having a polyene skeleton include diols having a polybutadiene skeleton, diols having a polyisoprene skeleton, diols having a hydrogenated polybutadiene skeleton, and diols having a hydrogenated polyisoprene skeleton. The above polyols may be used alone or in combination of two or more.

[0034] The organic polyisocyanates include diisocyanates and triisocyanates. Specific examples of diisocyanates include aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and naphthalene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylene diisocyanate. Specific examples of triisocyanates include 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate. The organic polyisocyanates may be used alone or in combination of two or more.

[0035] Specific examples of hydroxyl group-containing (meth)acrylates include hydroxyl group-containing monofunctional (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethylol mono(meth)acrylate, pentanediol mono(meth)acrylate, hexanediol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, tripropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-hydroxy-3-butoxypropyl (meth)acrylate; and Examples thereof include mono- or di(meth)acrylates of trimethylolpropane, mono-, di-, or tri(meth)acrylates of pentaerythritol, mono-, di-, or tri(meth)acrylates of ditrimethylolpropane, and mono-, di-, tri-, tetra-, or penta(meth)acrylates of dipentaerythritol, and hydroxyl group-containing polyfunctional (meth)acrylates such as epoxy (meth)acrylates. The above hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more.

[0036] Among urethane (meth)acrylates, urethane (meth)acrylate oligomers can be produced by heating and stirring a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate in the presence of a urethane-forming catalyst, and optionally in the presence of a reaction solvent, to form a urethane. In this case, the polyol, organic polyisocyanate, and hydroxyl group-containing (meth)acrylate can be charged and reacted all at once (hereinafter referred to as a "one-stage reaction"), or the polyol and organic polyisocyanate can be reacted to produce an isocyanate group-containing prepolymer, and then the hydroxyl group-containing (meth)acrylate can be added (hereinafter referred to as a "two-stage reaction"). In the case of a urethane adduct, it can be produced by heating and stirring in the presence of an organic polyisocyanate, a hydroxyl group-containing (meth)acrylate and a urethane-forming catalyst, and if necessary in the presence of a reaction solvent, to form a urethane.

[0037] Examples of the urethanization catalyst include amine compounds and metal catalysts. A specific example of the amine compound is triethylamine. Specific examples of metal catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin diacetylacetonate, bismuth dioctate, iron (III) acetylacetonate, zinc acetylacetonate, and aluminum acetylacetonate. The urethanization catalysts may be used alone or in combination of two or more.

[0038] In the case of a urethane (meth)acrylate oligomer, the ratio of polyol to organic polyisocyanate may be appropriately set depending on the structure of the urethane (meth)acrylate to be finally obtained. Specifically, the total amount of isocyanate groups in the organic polyisocyanate is preferably 1.05 to 2 moles per mole of the total amount of hydroxyl groups in the polyol. The proportion of the hydroxyl group-containing (meth)acrylate is preferably such that no isocyanate group remains in the resulting urethane (meth)acrylate. When the resin is produced by the two-stage reaction described above, the amount of the hydroxyl group-containing (meth)acrylate is preferably 1.0 to 1.5 moles per mole of the total amount of isocyanate groups in the isocyanate group-containing prepolymer. When producing the urethane (meth)acrylate by the one-stage reaction described above, the ratio of the hydroxyl group-containing (meth)acrylate is preferably 1.0 to 1.5 moles per mole of the total amount of isocyanate groups remaining in the isocyanate group-containing prepolymer calculated based on the structure of the urethane (meth)acrylate to be finally obtained. In this case, the total amount of hydroxyl groups in the polyol and the acid group-containing (meth)acrylate is preferably 1.0 to 1.5 moles per mole of the total amount of isocyanate groups in the organic polyisocyanate.

[0039] In the case of a urethane adduct, the proportion of the hydroxyl group-containing (meth)acrylate is preferably such that no isocyanate groups remain in the resulting urethane (meth)acrylate, and the amount of the hydroxyl group-containing (meth)acrylate is preferably 1.0 to 1.5 moles per mole of the total amount of isocyanate groups in the organic polyisocyanate.

[0040] If the molecular weight of the urethane (meth)acrylate produced by this reaction becomes high, the reaction mixture may become highly viscous and difficult to stir, so a reaction solvent may be added to the reaction components. The reaction solvent is preferably one that does not participate in the urethanization reaction, and examples thereof include organic solvents such as aromatic solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. When an organic solvent is used, the amount of the organic solvent may be appropriately determined depending on the viscosity of the urethane (meth)acrylate to be produced, but is preferably set to be 0 to 70% by mass in the reaction solution. Here, the reaction solution means the total amount of raw material compounds when only raw material compounds are used, and means the total amount including a reaction solvent and the like when a reaction solvent and the like are used in addition to the raw material compounds. Specifically, it means a solution of a polyol, an organic polyisocyanate, a hydroxyl group-containing (meth)acrylate, and a reaction solvent and the like used as needed.

[0041] As a reaction solvent, together with or instead of the organic solvent, a (meth)acrylate compound other than the urethane (meth)acrylate used as a component of the composition (hereinafter referred to as "other (meth)acrylate") can be blended. As the other (meth)acrylate, those described below as other components can be used. When the other (meth)acrylate is blended to carry out a urethane reaction and the resulting urethane (meth)acrylate is blended into the composition, unlike when the organic solvent is blended, it is preferable because there is no need to dry the composition after application. When other (meth)acrylates are blended into the reaction components, the blending amount may be appropriately set depending on the proportion of other (meth)acrylates to be blended into the final composition. For example, it is preferable to set the blending amount so that it is 10 to 70 mass %, and more preferably 10 to 50 mass %, in the reaction solution.

[0042] The amount of the urethanization catalyst may be a catalytic amount, and is, for example, preferably 0.01 to 1000 wtppm, more preferably 0.1 to 1000 wtppm, relative to the reaction solution. By setting the amount of the metal compound to 0.01 wtppm or more, the urethanization reaction can be favorably promoted, and by setting the amount to 1000 wtppm or less, coloration of the resulting urethane (meth)acrylate can be suppressed.

[0043] In the case of a urethane (meth)acrylate oligomer, the urethanization catalyst can be added when the polyol, organic polyisocyanate, and hydroxyl group-containing (meth)acrylate are charged if a one-stage reaction is used, or when the polyol and organic polyisocyanate are charged if a two-stage reaction is used. In the case of a urethane adduct, it can be added when the organic polyisocyanate and the hydroxyl group-containing (meth)acrylate are charged.

[0044] In the urethane reaction, a small amount of a chain extender may be added for the purpose of adjusting the molecular weight. As the chain extender, those usually used in urethane reactions can be used, and examples thereof include the same low molecular weight polyols as those mentioned above.

[0045] In the urethanization reaction, it is preferable to use a polymerization inhibitor in order to prevent polymerization of the (meth)acryloyl groups in the raw materials or products, and furthermore, an oxygen-containing gas may be introduced into the reaction liquid. Specific examples of the polymerization inhibitor include organic polymerization inhibitors such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, benzoquinone, and phenothiazine; inorganic polymerization inhibitors such as copper chloride and copper sulfate; organic salt polymerization inhibitors such as copper dibutyldithiocarbamate; and stable radicals such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical and galvinoxyl. The polymerization inhibitor may be used alone or in any combination of two or more. The proportion of the polymerization inhibitor in the reaction liquid is preferably 5 to 20,000 wtppm, more preferably 25 to 3,000 wtppm. Examples of oxygen-containing gases include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. etc.

[0046] The reaction temperature may be appropriately set depending on the raw materials used and the structure and molecular weight of the target urethane (meth)acrylate, but is usually preferably 25 to 150° C., more preferably 30 to 120° C. The reaction time may also be appropriately set depending on the raw materials used and the structure and molecular weight of the target urethane (meth)acrylate, but is usually preferably 1 to 70 hours, more preferably 2 to 30 hours.

[0047] The weight average molecular weight (hereinafter referred to as "Mw") of the urethane (meth)acrylate in the present invention is preferably 3,000 to 100,000 from the viewpoint of improving the elongation percentage and sealing properties of the composition. In the present invention, Mw refers to a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as "GPC") into polystyrene equivalent, and means a value measured under the following conditions. Detector: Differential refractive index system (RI detector) Column type: Cross-linked polystyrene column Column temperature: 40℃ Eluent: tetrahydrofuran Molecular weight standard: Polystyrene

[0048] Other examples of urethane (meth)acrylates include compounds such as those described on pages 70 to 74 of the publication "UV·EB Curable Materials" [CMC Corporation, published in 1992].

[0049] <Epoxy (meth)acrylate> Epoxy (meth)acrylate is a compound obtained by addition reaction of epoxy resin with (meth)acrylic acid, and examples thereof include compounds such as those described on pages 74-75 of the aforementioned document "UV / EB Curable Materials."

[0050] Examples of epoxy resins include aromatic epoxy resins and aliphatic epoxy resins. Specific examples of aromatic epoxy resins include resorcinol diglycidyl ether; di- or polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, or alkylene oxide adducts thereof; novolac epoxy resins such as phenol novolac epoxy resins and cresol novolac epoxy resins; glycidyl phthalimide; and o-phthalic acid diglycidyl ester. Other examples include compounds such as those described in Chapter 2 of the literature "Epoxy Resins - Recent Advances" (Shokodo, 1990) and pages 4-6 and 9-16 of the literature "Polymer Processing," Special Issue 9, Vol. 22, Extra Issue, Epoxy Resins [Polymer Publishing Association, 1973].

[0051] Specific examples of aliphatic epoxy resins include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol; diglycidyl ethers of polyalkylene glycols such as diglycidyl ethers of polyethylene glycol and polypropylene glycol; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol, and alkylene oxide adducts thereof; polyglycidyl ethers of polyhydric alcohols such as di- or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerin, and alkylene oxide adducts thereof, and di-, tri-, or tetraglycidyl ethers of pentaerythritol and alkylene oxide adducts thereof; di- or polyglycidyl ethers of hydrogenated bisphenol A and alkylene oxide adducts thereof; tetrahydrophthalic acid diglycidyl ether; and hydroquinone diglycidyl ether. In addition to these, compounds described on pages 3 to 6 of the aforementioned literature "Polymer Processing," special edition, Epoxy Resin, can also be used.

[0052] In addition to these aromatic epoxy resins and aliphatic epoxy resins, examples include epoxy compounds having a triazine nucleus in the skeleton, such as TEPIC (Nissan Chemical Industries, Ltd.) and Denacol EX-310 (Nagase Chemical Industries, Ltd.), as well as compounds such as those described on pages 289 to 296 of the aforementioned literature "Polymer Processing," special edition, Epoxy Resins. In the above, the alkylene oxide in the alkylene oxide adduct is preferably ethylene oxide, propylene oxide, or the like.

[0053] Other examples include compounds such as those described on pages 53 to 56 of the publication "Latest UV Curing Technology" (Published by Printing Information Association, 1991).

[0054] <Polyether (meth)acrylate oligomer> The polyether (meth)acrylate oligomers include polyalkylene glycol (meth)diacrylates, such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate.

[0055] <Polyfunctional unsaturated compounds other than those mentioned above> Examples of polyfunctional polymers include (meth)acrylic polymers having a (meth)acryloyloxy group, and (meth)acrylic polymers having a functional group with a (meth)acryloyl group introduced into the side chain, such as compounds described on pages 78-79 of the aforementioned document "UV / EB Curable Materials."

[0056] Examples of polyfunctional vinyl compounds include compounds having two or more vinyl groups, such as divinylbenzene, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.

[0057] The polyfunctional allyl compound may be a compound having two or more allyl groups, such as diallyl phthalate, triallyl isocyanurate, and triallyl cyanurate.

[0058] As the compound having an ethylenically unsaturated group of the present invention, urethane (meth)acrylates and monofunctional unsaturated compounds are preferred because they provide a cured product of the composition with high elongation and excellent adhesion to fibers.

[0059] Furthermore, the compound having an ethylenically unsaturated group preferably has a Tg of 100° C. or less after being cured with active energy rays. In the present invention, Tg is the temperature measured at a temperature rising rate of 10°C / min using a differential scanning calorimeter (DSC). The value measured at 100°C is the value at the midpoint of the glass transition temperature (Tmg) on ​​the △T-temperature curve. It means the value that

[0060] Urethane (meth)acrylates with a Tg of 100°C or less are commercially available, including "Aronix M-1200" (Tg=35°C), "Aronix M-1600" (Tg=82°C), and "Aronix OT-1001" (Tg=-15°C) (all manufactured by Toagosei Co., Ltd.), "Art Resin UN-333" (Tg=4°C), "Art Resin UN-350" (Tg=-57°C), "Art Resin UN-352" (Tg=31°C), "Art Resin UN-353" (Tg=10°C), and "Art Resin UN-1255" (Tg= Examples of resins that can be used include "Art Resin UN-2600" (Tg=-1°C), "Art Resin UN-6200" (Tg=-52°C), "Art Resin UN-7600" (Tg=-41°C), "Art Resin UN-7700" (Tg=-41°C), "Art Resin UN-9200A" (Tg=-27°C), "Art Resin UN-333" (Tg=4°C), and "Art Resin UN-333" (Tg=4°C)) (all manufactured by Negami Chemical Industrial Co., Ltd.), and "Kayarad UX-3204" (Tg=-14°C) (manufactured by Nippon Kayaku Co., Ltd.).

[0061] Examples of the monofunctional unsaturated compound having a Tg of 100° C. or less include monofunctional (meth)acrylates, monofunctional (meth)acrylamides, and vinyl compounds. Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates such as isononyl acrylate (Tg=-58°C) and lauryl acrylate (Tg=-23°C); Monofunctional (meth)acrylates having an alicyclic group, such as isobornyl acrylate (Tg=94°C), trimethylcyclohexyl acrylate (Tg=52°C), and cyclic trimethylolpropane formal acrylate (Tg=27°C); Monofunctional (meth)acrylates with aromatic groups, such as benzyl acrylate (Tg = 6°C), phenol ethylene oxide-modified (n = 2) acrylate (Tg = -8°C), nonylphenol ethylene oxide-modified (n = 1) acrylate (Tg = 17°C), and nonylphenol ethylene oxide-modified (n = 4) acrylate (Tg = -20°C) Monofunctional (meth)acrylates having a heterocycle such as tetrahydrofurfuryl acrylate (Tg=-12°C); Monofunctional (meth)acrylates having a hydroxyl group, such as 2-hydroxy-3-phenoxypropyl acrylate (Tg=17°C); and Examples include monofunctional (meth)acrylates having a carboxy group, such as monohydroxyethyl phthalate acrylate (Tg = -20°C), an ε-caprolactone adduct of hydroxyethyl acrylate (manufactured by Daicel Corporation, Placcel FA1DDM) (Tg = -40°C), and ω-carboxypolycaprolactone (n = 2) monoacrylate (Tg = -40°C). Examples of monofunctional (meth)acrylamides include N-hydroxyethyl acrylamide (Tg=98° C.). Examples of vinyl compounds include N-vinylpyrrolidone (Tg=80° C.) and N-vinylcaprolactam (Tg=90° C.).

[0062] A preferred combination of components is a combination of a bifunctional (meth)acrylate having a Tg of 100°C or less and a monofunctional (meth)acrylate having a Tg of 100°C or less.

[0063] <Photoradical polymerization initiator> A photoradical polymerization initiator is a compound that generates radicals upon irradiation with active energy rays and initiates polymerization of a compound having an ethylenically unsaturated group. Furthermore, some types of photoradical polymerization initiators function as sensitizers that accelerate the photodecomposition of other photoradical polymerization initiators.

[0064] Specific examples of the photoradical polymerization initiator include benzil dimethyl ketal, benzil, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-{4-[4- aromatic ketone compounds such as {(2-hydroxy-2-methyl-propionyl)-benzyl}-phenyl}-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, phenylglyoxylic acid methyl ester, ethyl anthraquinone, and phenanthrenequinone; benzophenone-based compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane, methyl-2-benzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxy-4'-dimethylaminobenzophenone; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphineate, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; Thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl]oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride, and fluorothioxanthone; acridone compounds such as acridone and 10-butyl-2-chloroacridone; Oxime esters such as 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluoro ... 2,4,5-triarylimidazole dimers such as 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer; and Examples of such photoinitiators include acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane, titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, and germanium-based photoinitiators such as bis-(4-methoxybenzoyl)diethylgermanium.

[0065] Among these, photopolymerization initiators with an absorption coefficient (mL / g·cm) at 405 nm of 100 or more are preferred in terms of improving dark curing properties, and those with an absorption coefficient of 500 or more are even more preferred. Specifically, acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (absorption coefficient at 405 nm = 899) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (absorption coefficient at 405 nm = 165), titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium (absorption coefficient at 405 nm = 1197), and germanium-based photopolymerization initiators such as ivoserine (absorption coefficient at 405 nm = 1741) are preferred because of their high dark curability.

[0066] The proportion of the photoradical polymerization initiator is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total of the compounds having an ethylenically unsaturated group. If the amount of the photoradical polymerization initiator is less than 0.01 parts by mass, the dark curability of the composition will be insufficient, and if it exceeds 15 parts by mass, the curability of the bottom part of the coating film will deteriorate.

[0067] <Fluorescent agent> A fluorescent agent means a compound that has fluorescent properties (photoluminescence).

[0068] The fluorescent agent preferably has an absorption spectrum with a maximum between 300 and 450 nm, more preferably between 350 and 400 nm. The absorption spectrum of a fluorescent agent refers to the value obtained by measuring a solution of the fluorescent agent in acetonitrile (concentration 0.008 to 1% by mass, concentration adjusted so that the absorbance peak is 1 or less) using a spectrophotometer.

[0069] The fluorescent agent preferably has an emission spectrum with a maximum between 380 and 500 nm, more preferably between 400 and 470 nm. The emission spectrum of the fluorescent agent refers to the value obtained by measuring the emission spectrum at an excitation light wavelength of 365 nm using a spectrofluorometer with a tetrahydrofuran solution of the fluorescent agent (concentration 0.0001 to 0.01% by mass, the concentration adjusted so as not to exceed the measurement limit of the device).

[0070] When the absorption spectrum and emission spectrum show maxima within the above ranges, excessive absorption of the emitted light by the fluorescent agent and photoradical polymerization initiator can be suppressed, thereby improving dark curability. On the other hand, fluorescent agents that do not show maxima within these ranges have poor dark curability.

[0071] Fluorescent brighteners are known as compounds that satisfy the above-mentioned preferred absorption and emission wavelengths for fluorescent agents, and are preferred for reasons such as their ease of availability and low risk. Specific examples of the fluorescent brightening agent include thiophene-based fluorescent brightening agents, coumarin-based fluorescent brightening agents, stilbene-based fluorescent brightening agents, naphthalene-based fluorescent brightening agents, and benzimidazole-based fluorescent brightening agents.

[0072] Examples of thiophene-based fluorescent brighteners include 2,5-bis(5-t-butyl-2-benzoxazolyl)thiophene, 2,5-bis(benzoxazol-2-yl)thiophene, 2,5-bis(benzoxazol-2-yl)thiophene, and 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole). Thiophene-based fluorescent whitening agents are commercially available, and commercially available products can be used, such as Tinopal OB (manufactured by BASF Japan) and NIKKAFLUOR OB (manufactured by Nippon Chemical Industry Co., Ltd.).

[0073] Examples of coumarin-based fluorescent whitening agents include 4-methyl-7-hydroxycoumarin, 4-methyl-7-diethylaminocoumarin, 4-methyl-7-aminocoumarin, 4-methyl-7-pyrrolinidylcoumarin, 4-methyl-7-(3',5'-diphenyl-4',5'-hydropyrazolyl)coumarin, 4-methyl-3-(4'-cyanophenyl)-7-(3',5'-dimethylpyrazolyl)coumarin, 4-methyl-3-(4'-ethoxycarbonylphenyl)-7-(3',5'-dimethylpyrazolyl)coumarin, 3-( 4'-carbonylphenyl)-4-methyl-7-diethylaminocoumarin, 3-(4'-acetylaminophenyl)-4-methyl-7-diethylaminocoumarin, 3-phenyl-7-(3'-methylpyrazolyl)coumarin, 3-(4'-acetylaminophenyl)-7-acetylaminocoumarin, 7-amino-3,4-benzocoumarin, 7-acetylamino-3,4-benzocoumarin, and 2-(3-phenylcoumarin-7-ylamino)-4-chloro-6-dithielan-1,3,5-triazine. Coumarin-based fluorescent whitening agents are commercially available, and commercially available products can be used, such as NIKKAFLUOR MC-T (manufactured by Nippon Chemical Industry Co., Ltd.), Kayalight B (manufactured by Nippon Kayaku Co., Ltd.), Hakkol P, and Hakkol PY-1800 (manufactured by Showa Chemical Industry Co., Ltd.).

[0074] Examples of stilbene-based fluorescent brighteners include 4,4'-bis(2-benzoxazolyl)stilbene, sodium 4-(2H-naphtho[1,2-d]triazol-2-yl)stilbene-2-sulfonate, and 4,4'-bis[(1,4-dihydro-4-oxo-6-phenylamino-1,3,5-triazin-2-yl)amino]stilbene-2,2'. -disulfonic acid disodium salt, 2,2'-(1,2-ethenediyl)bis[sodium 5-(3-phenylureido)benzenesulfonate], 2,2'-(1,2-ethenediyl)bis[sodium 5-[(4-amino-6-chloro-1,3,5-triazin-2-yl)amino]benzenesulfonate], 4,4'-bis[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]stilbene-2,2'-disulfonic acid disodium salt, 2,2'-[1,2-ethenediylbis(3-sodium sulfo-4,1-phenylene)]bis(2H-naphtho[1,2-d]triazole-6-sulfonate) sodium 2,2'-(1,2-ethenediyl)bis[5-[(2,4-dimethoxybenzoyl)amino]benzenesulfonate], disodium 2,2'-(1,2-ethenediyl)bis[5-[[4-methoxy-6-[phenylamino]-1,3,5-triazin-2-yl]amino]benzenesulfonate], sodium 4,4'-bis[(6-amino-1,4-dihydro-oxo-1,3,5-triazin-2-yl)amino]stilbene-2,2'-disulfonate, and disodium 2,2'-([1,1'-biphenyl]-4,4'-diyldivinylene)bis(benzenesulfonate). Stilbene-based fluorescent brighteners are commercially available, and commercially available products can be used. Examples include stilbene-based fluorescent brighteners NIKKAFLUOR SB, RP, and 2R (manufactured by Nippon Chemical Industry Co., Ltd.), KAYAPHOR AS Liquid, and Kayaphor SN conc (manufactured by Nippon Kayaku Co., Ltd.).

[0075] Examples of naphthalene-based fluorescent whitening agents include 1,4-bis(2-benzoxazolyl)naphthalene. Naphthalene-based fluorescent whitening agents are commercially available, and commercially available products can be used, such as NIKKAFLUOR KB (manufactured by Nippon Chemical Industry Co., Ltd.).

[0076] Benzimidazole-based fluorescent whitening agents are commercially available, and commercially available products can be used, such as HOSTALUX ACK LIQ (manufactured by Clariant Japan).

[0077] Other fluorescent agents include polycyclic aromatic hydrocarbon compounds, such as anthracene compounds and perylene compounds.

[0078] Among these fluorescent agents, thiophene-based fluorescent brightening agents, coumarin-based fluorescent brightening agents, stilbene-based fluorescent brightening agents, naphthalene-based fluorescent brightening agents, benzimidazole-based fluorescent brightening agents, and perylene compounds are preferred because of their excellent dark curability, storage stability, solubility, etc. Among these, thiophene-based fluorescent brightening agents, coumarin-based fluorescent brightening agents, and stilbene-based fluorescent brightening agents are more preferred, and preferred examples of thiophene-based fluorescent brightening agents include 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), preferred examples of coumarin-based fluorescent brightening agents include 4-methyl-7-diethylaminocoumarin, and preferred examples of stilbene-based fluorescent brightening agents include 4,4'-bis(2-methoxystyryl)biphenyl.

[0079] These compounds may be used alone or in combination of two or more.

[0080] The content of the fluorescent agent is 0.001 to 5 parts by mass, and preferably 0.002 to 1 part by mass, relative to 100 parts by mass of the total of the compounds having an ethylenically unsaturated group. If the content of the fluorescent agent is less than 0.001 parts by mass, the dark curability will be insufficient, and if it exceeds 5 parts by mass, the curability at the bottom of the coating film will deteriorate.

[0081] <Reducing agent> A reducing agent refers to an element or molecule that reduces another chemical species in an oxidation-reduction reaction. Specific examples of the reducing agent include amine compounds, thiourea derivatives, metal salts, organic acid compounds, aldehyde compounds, phenol compounds, phosphorus compounds, and thiol compounds.

[0082] Examples of amine compounds include N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-i-propylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, and N,N-bis(2-hydroxyethyl)-p-toluidine. , N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-i-propylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-di(2-hydroxyethyl)-3,5-di-i-propylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, 4-dimethyl Ethyl aminobenzoate, n-butoxyethyl 4-dimethylaminobenzoate, (2-methacryloyloxy)ethyl 4-dimethylaminobenzoate, trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, (2-dimethylamino)ethyl methacrylate, N,N-bis(methacryloyloxyethyl)-N-methylamine, N,N- Examples of the methacryloyloxyethyl amine include bis(methacryloyloxyethyl)-N-ethylamine, N,N-bis(2-hydroxyethyl)-N-methacryloyloxyethylamine, N,N-bis(methacryloyloxyethyl)-N-(2-hydroxyethyl)amine, tris(methacryloyloxyethyl)amine, N,N-dimethylaminoethyl methacrylate, methyl-4-dimethylaminobenzoate, ethyl-4-dimethylaminobenzoate, isoamyl-4-dimethylaminobenzoate, and diethylenetriamine.

[0083] Examples of thiourea derivatives include 2-imidazolidinethione, 2-mercaptobenzimidazole, thiourea, methylthiourea, tetramethylthiourea, ethylenethiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-dipropylthiourea, N,N'-di-n-butylthiourea, N,N'-dilaurylthiourea, N,N'-diphenylthiourea, trimethylthiourea, 1-acetyl-2-thiourea, and 1-benzoyl-2-thiourea.

[0084] Metal salts include iron(II) acetate, copper(I) acetate, iron(II) formate, copper(I) formate, iron(II) oxalate, copper(I) oxalate, iron(II) stearate, copper(I) stearate, iron(II) bis(2-ethylhexanoate), tin(II) (2-ethylhexanoate), copper(I) bis(2-ethylhexanoate), iron(II) naphthenate, copper(I) naphthenate, cobalt naphthenate, cobalt acetylacetonate, vanadium nitr ... Examples of vanadyl acetylacetonate include vanadyl stearate, vanadium naphthenate, vanadium acetylacetonate(III), vanadium benzoylacetonate, bis(acetylacetonato)oxovanadium(IV), bis(benzoylacetonato)oxovanadium(IV), bis(stearoyloxy)oxovanadium(IV), vanadyl oxalate, and vanadyl naphthenate. The vanadium compound may also be a pentavalent vanadium compound, such as vanadium(V) pentoxide, metavanadate(V), tri(alkoxy)oxovanadium(V), etc. The pentavalent vanadium compound can form a tetravalent vanadium compound in the composition in the presence of an acidic compound such as a phosphate compound (e.g., dibutyl phosphate, tributyl phosphate, etc.).

[0085] Examples of acid compounds include ascorbic acid, sodium ascorbate, and ascorbic acid salts such as potassium ascorbate; erythorbic acid, sodium erythorbate, and potassium erythorbate salts; tartaric acid, sodium tartrate, and potassium tartrate salts; phosphites such as phosphorous acid, sodium phosphite, and potassium phosphite; hydrogen phosphites such as sodium hydrogen phosphite and potassium hydrogen phosphite; sulfites such as sodium sulfite and potassium sulfite; hydrogen sulphite salts such as sodium hydrogen sulphite and potassium hydrogen sulphite; thiosulfates such as sodium thiosulfite and potassium thiosulfite; thiosulfites such as sodium thiosulfite and potassium thiosulfite; pyrosulfites such as sodium pyrosulfite and potassium pyrosulfite; and pyrosulfites such as sodium pyrosulfite and potassium pyrosulfite. In addition to the above, examples include sodium hydroxymethanesulfonate (sodium formaldehyde sulfoxylate), sodium sulfinate derivatives, propyl formate, isoamyl formate, pentyl formate, and phenyl formate.

[0086] Examples of the aldehyde compound include aromatic aldehydes such as benzaldehyde, anisaldehyde, and p-methoxyaldehyde, and aliphatic aldehydes such as propionaldehyde, hexylaldehyde, and glyoxal, and it is preferable to use them as aldimine compounds, which are condensates with primary amines.

[0087] Examples of phenolic compounds include catechol, resorcinol, p-hydroquinone, pyrocatechol, and catecholamine.

[0088] The phosphorus compound is preferably a trivalent compound having reducing properties. Specific examples of trivalent phosphorus compounds include phosphine compounds such as triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, tris(3-hydroxypropyl)phosphine, and triphenylphosphine; and Triphenyl phosphite, tris(nonylphenyl) phosphite, tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono(tridecyl) phosphite, trilauryl trithiophosphite, tetrahydrofuran Examples of suitable phosphites include tetraphenyldipropylene glycol diphosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite), bis(decyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, isodecyl diphenyl phosphite, and triisodecyl phosphite.

[0089] A thiol compound is a compound containing one or more thiol groups in the molecule, and specific examples include the following.

[0090] Examples of compounds having one thiol group include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan.

[0091] Examples of compounds having two thiol groups include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2,3-dimercapto-1-propanol, dithioerythritol, 2,3-dimercaptosuccinic acid, 1,2-benzenedithiol, 1,2-benzenedimethanethiol, 1,3-benzenedithiol, 1,3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 3,4-dimercaptotoluene, 4-chloro-1,3-benzenedithiol, 2,4,6-trimethyl-1,3-benzenedimethanethiol, 4,4'-thiodi Examples of suitable mercaptosilanes include phenol, 2-hexylamino-4,6-dimercapto-1,3,5-triazine, 2-diethylamino-4,6-dimercapto-1,3,5-triazine, 2-cyclohexylamino-4,6-dimercapto-1,3,5-triazine, 2-di-n-butylamino-4,6-dimercapto-1,3,5-triazine, ethylene glycol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bisthioglycolate, 2,5-dimercapto-1,3,4-thiadiazole, 2,2'-(ethylenedithio)diethanethiol, 2,2-bis(2-hydroxy-3-mercaptopropoxyphenylpropane), and 1,4-bis(3-mercaptobutyryloxy)butane.

[0092] Examples of compounds having three thiol groups include 1,2,6-hexanetriol trithioglycolate, 1,3,5-trithiocyanuric acid, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tristhioglycolate, and tris[(3-mercaptopropionyloxy)-ethyl]isocyanurate.

[0093] Examples of compounds having four thiol groups include pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), and pentaerythritol tetrakisthioglycolate.

[0094] Examples of compounds having five or more thiol groups include dipentaerythritol hexakis(3-mercaptopropionate) and compounds obtained by radical polymerization of a (meth)acrylate monomer having a hydroxy group with another (meth)acrylate monomer, followed by esterification with a mercapto organic acid.

[0095] Of these compounds, metal salts, phosphorus compounds, and thiol compounds are preferred as reducing agents because they can improve dark curability, and of these, divalent tin compounds, thiol compounds, and trivalent phosphorus compounds are more preferred. These compounds may be used alone or in combination of two or more.

[0096] The content of the reducing agent is 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total of the compounds having an ethylenically unsaturated group. If the content of the reducing agent is less than 0.1 part by mass, the dark curability will be insufficient, while if it exceeds 20 parts by mass, the elastic modulus of the cured product will decrease, making it unsuitable as a sealant, and further the storage stability of the composition will decrease.

[0097] <Active energy ray-curable composition> The present invention relates to an active energy ray-curable composition comprising a compound having an ethylenically unsaturated group, a photoradical polymerization initiator, and further comprising a fluorescent agent and / or a reducing agent, the composition containing the photoradical polymerization initiator in a ratio of 0.01 to 15 parts by mass per 100 parts by mass of the total of the compounds having an ethylenically unsaturated group. The composition of the present invention contains a fluorescent agent or a reducing agent in addition to a compound having an ethylenically unsaturated group and a photoradical polymerization initiator, and has higher dark curing properties than a composition that does not contain a fluorescent agent or a reducing agent.It can also cure an active energy ray-curable composition that has penetrated into the gap between the sewing thread and the base fabric, resulting in good sealing properties.

[0098] The composition of the present invention preferably contains a compound having an ethylenically unsaturated group, a photoradical polymerization initiator, and a fluorescent agent, and contains 0.01 to 15 parts by mass of the photoradical polymerization initiator and 0.001 to 5 parts by mass of the fluorescent agent relative to a total of 100 parts by mass of the compound having an ethylenically unsaturated group. Furthermore, the composition of the present invention preferably contains a compound having an ethylenically unsaturated group, a photoradical polymerization initiator, and a reducing agent, and contains 0.01 to 15 parts by mass of the photoradical polymerization initiator and 0.1 to 20 parts by mass of the reducing agent relative to a total of 100 parts by mass of the compound having an ethylenically unsaturated group. Furthermore, the composition of the present invention preferably contains a compound having an ethylenically unsaturated group, a photoradical polymerization initiator, a fluorescent agent, and a reducing agent, and contains 0.01 to 15 parts by mass of the photoradical polymerization initiator, 0.001 to 5 parts by mass of the fluorescent agent, and 0.1 to 20 parts by mass of the reducing agent relative to a total of 100 parts by mass of the compound having an ethylenically unsaturated group. Among these, a composition containing a fluorescent agent and a reducing agent in addition to a compound having an ethylenically unsaturated group and a photoradical polymerization initiator has extremely high dark curability and therefore better sealing properties.

[0099] The composition may be produced by a conventional method, for example, by stirring and mixing a compound having an ethylenically unsaturated group, a photoradical polymerization initiator, a fluorescent agent, and a reducing agent, and, if necessary, other components described below. The stirring speed, the temperature during stirring, and the like may be appropriately set depending on the composition to be produced and the purpose. During stirring and mixing, heating may be carried out as necessary, preferably at a temperature of 30 to 100°C, and particularly preferably at a temperature of 40 to 80°C.

[0100] The Tg of the cured product of the composition of the present invention is preferably from -100 to 80°C, more preferably from -50 to 60°C.

[0101] The tensile strain of the cured product of the composition of the present invention at 23° C. is preferably 50 to 700%, more preferably 100 to 500%. If the tensile strain is less than 50%, the sealability of the seam cannot be maintained when the composition is applied to a seam between multiple materials and then bent after curing. If the tensile strain exceeds 700%, the cured product will deform excessively, resulting in poor sealability. In the present invention, the tensile strain refers to the nominal strain measured in a tensile test using a hardened sample of 5 mm width × 1 mm thickness × 50 mm length, at a temperature of 23°C, with an initial gripping distance of 20 mm, and at a test speed of 300 mm / min, in accordance with JIS K7161-1:2014. The curing conditions are a metal halide lamp with an ultraviolet (UV-A) intensity of 200 mW / cm2 centered at 365 nm. 2 , cumulative light intensity 1000mJ / cm 2 This process was repeated five times to achieve a total cumulative light dose of 5000 mJ / cm 2 I made it so that it would be like this.

[0102] The composition of the present invention may contain other ingredients depending on the purpose. Specific examples of other components include antioxidants, ultraviolet absorbers, leveling agents, silane coupling agents, surface modifiers, and polymerization inhibitors. These components will be described below. As for the other components described below, only one of the exemplified compounds may be used, or two or more of them may be used in combination.

[0103] <Antioxidants> The antioxidant can be added for the purpose of improving durability such as heat resistance and weather resistance of the cured product. Examples of the antioxidant include phenol-based antioxidants and sulfur-based antioxidants. Examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene, etc. Commercially available antioxidants include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA Corporation. Examples of sulfur-based antioxidants include thioether-based compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA Corporation. These antioxidants may be used alone or in combination of two or more. A preferred combination of these antioxidants is the combined use of a phenol-based antioxidant and a sulfur-based antioxidant. The content of the antioxidant may be appropriately set depending on the purpose, and is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the total amount of the compound having an ethylenically unsaturated group. By making the content ratio 0.1 parts by mass or more, the durability of the composition can be improved, while by making it 5 parts by mass or less, the curability and adhesion can be improved.

[0104] <UV absorber> The ultraviolet absorber can be added for the purpose of improving the light resistance of the cured product. Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers such as TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479, and benzotriazole-based ultraviolet absorbers such as TINUVIN 900, TINUVIN 928, and TINUVIN 1130, all of which are manufactured by BASF. The content of the ultraviolet absorber may be appropriately set depending on the purpose, and is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the total amount of the compound having an ethylenically unsaturated group. By setting the content to 0.01 part by mass or more, the light resistance of the cured product can be improved, while by setting it to 5 parts by mass or less, the curability of the composition can be improved.

[0105] <Silane coupling agent> A silane coupling agent can be added for the purpose of improving the interfacial adhesive strength between the cured product and the substrate. The silane coupling agent is not particularly limited as long as it can contribute to improving the adhesion to the substrate.

[0106] Examples of silane coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, and N-2-(aminoethyl)-3- Examples thereof include aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. The silane coupling agent may be one of the above compounds or a combination of two or more of them.

[0107] The blending ratio of the silane coupling agent may be appropriately set depending on the purpose, and is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the total amount of the compounds having an ethylenically unsaturated group. By making the blending ratio 0.1 parts by mass or more, the adhesive strength of the composition can be improved, while by making it 10 parts by mass or less, it is possible to prevent the adhesive strength from changing over time.

[0108] <Surface modifier> A surface modifier may be added to the composition of the present invention for the purposes of improving leveling properties during application, increasing the slipperiness of the cured product, and improving scratch resistance. Examples of the surface modifier include a surface conditioner, a surfactant, a leveling agent, an antifoaming agent, an agent for imparting smoothness, and an agent for imparting antifouling properties, and these known surface modifiers can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, and fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain. Furthermore, for the purpose of increasing the durability of the lubricity, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in the molecule may be used.

[0109] The content of the surface modifier is preferably 0.01 to 1.0 part by mass per 100 parts by mass of the total amount of the compounds having an ethylenically unsaturated group. Within this range, the surface smoothness of the cured film is excellent.

[0110] <Polymerization inhibitor> A polymerization inhibitor may be added to the composition of the present invention for the purpose of improving storage stability. Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of organic polymerization inhibitors include phenol compounds such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, and 4-tert-butylcatechol; quinone compounds such as benzoquinone; stable radicals such as galvinoxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl; phenothiazine; and N-nitroso-N-phenylhydroxylamine ammonium. Specific examples of inorganic polymerization inhibitors include copper chloride, copper sulfate, and iron sulfate. Specific examples of organic salt polymerization inhibitors include nitroso compounds such as N-nitroso-N-phenylhydroxylamine aluminum salt and ammonium N-nitrosophenylhydroxylamine, and copper dibutyldithiocarbamate.

[0111] Among these, stable radicals and nitroso compounds are preferred because they cause little coloring of the composition and can prevent thickening or gelling of the composition, thereby increasing storage stability. The content of the polymerization inhibitor may be appropriately set depending on the purpose, and is preferably 0.0005 to 1 part by mass, and more preferably 0.001 to 0.5 parts by mass, relative to 100 parts by mass of the total amount of the compound having an ethylenically unsaturated group. When the content is 0.0005 part by mass or more, the thermal stability and light stability of the composition can be improved, and when it is 1 part by mass or less, the photocurability of the composition can be improved.

[0112] The active energy ray-curable composition of the present invention preferably has a viscosity of 1 to 1000 mPa·s as measured at 25°C using a cone-and-plate rotational viscometer in accordance with JIS K 6833. If the viscosity is less than 1 mPa·s, the composition will penetrate the fibers too much, causing the applied resin liquid to spread more than necessary, reducing the amount of resin adhering to the seam and resulting in poor sealing performance. If the viscosity exceeds 1000 mPa·s, the composition will significantly reduce its penetration into the fibers, resulting in poor sealing performance.

[0113] <How to use> The active energy ray-curable composition of the present invention is used for sealing the seams sewn with sewing thread in sewn articles that require waterproofing and airtightness and are made by sewing together multiple materials. For example, the composition can be used in various sewn articles, such as waterproofing of fibrous materials that need to prevent water leakage, such as raincoats and tents, and sealing of seams in airbags that require high airtightness.

[0114] Various coating methods can be used, including knife coating, die coating, roll coating (National, reverse), brush coating, spray coating, kiss roll coating, flow coating (shower coating, curtain coating), inkjet, jet dispenser, and nozzle dispenser.

[0115] The composition of the present invention can be cured by any method that is commonly used for active energy ray-curable compositions, such as ultraviolet light, visible light, and electron beams, with ultraviolet light being preferred. Examples of ultraviolet irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, and light-emitting diodes (LEDs). The irradiation energy may be appropriately set depending on the type of active energy ray and the compounding composition. For example, when a high-pressure mercury lamp is used, the irradiation intensity is 50 to 5000 mW / cm. 2 is preferred, and 100 to 3000 mW / cm 2 More preferably, the irradiation energy is 10 to 50,000 mJ / cm.2 is preferred, and 50 to 10,000 mJ / cm 2 When an LED is used, the irradiation intensity is preferably 50 to 20,000 mW / cm. 2 is preferred, and 200 to 10,000 mW / cm 2 More preferably, the irradiation energy is 500 to 100,000 mJ / cm. 2 is preferred, and 2000 to 50,000 mJ / cm 2 In the case of LEDs, the emission wavelength is preferably short, and preferably 365, 385, or 405 nm.

[0116] The suture may be a fiber material. The type of fiber in the fiber material is not particularly limited, and known materials may be used. Examples include aliphatic polyamides such as nylon 66, nylon 6, nylon 46, and nylon 12; aromatic polyamides such as aramid; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; acrylics; polyurethanes; and rayon.

[0117] Suitable examples of the sewn material of the present invention include waterproofing of fabric members that need to be protected from water leakage, such as raincoats and tents, and airbags that require high airtightness. [Example]

[0118] The present invention will be described in more detail below with reference to examples and comparative examples. In the following description, "parts" means parts by mass.

[0119] Examples 1 to 13, Comparative Examples 1 to 2 The compounds shown in Table 1 below were mixed and stirred at 50° C. in the proportions shown in Table 1 to prepare active energy ray-curable compositions.

[0120] [Table 1]

[0121] The numbers in Table 1 indicate the number of copies, and the abbreviations have the following meanings. Compounds containing ethylenically unsaturated groups UN-6200: Polyether-based urethane acrylate, weight-average molecular weight: approximately 6500, cured product Tg: -52°C, "Art Resin UN-6200" manufactured by Negami Chemical Industries, Ltd. UN-1255: Polyester-based urethane acrylate, weight-average molecular weight approximately 8000, cured product Tg = -14°C, "Art Resin UN-1255" manufactured by Negami Chemical Industries, Ltd. M-1200: Polyester-based urethane acrylate, weight-average molecular weight = approximately 3000, cured product Tg = 35°C, "Aronix M-1200" manufactured by Toagosei Co., Ltd. M-313: A mixture of di- and triacrylates of ethylene oxide adduct of isocyanuric acid, cured product Tg = 250°C or higher, "Aronix M-313" manufactured by Toagosei Co., Ltd. NDDA: 1,9-nonanediol diacrylate, cured product Tg = 68°C, "Light Acrylate 1,9ND-A" manufactured by Kyoeisha Chemical Co., Ltd. EEEA: Ethoxyethoxyethyl acrylate, cured product Tg = -67°C, "Viscoat #190" manufactured by Osaka Organic Chemical Industry Co., Ltd. TMCHA: 3,3,5-trimethylcyclohexyl acrylate, cured product Tg = 52°C, "Viscoat #196" manufactured by Osaka Organic Chemical Industry Ltd. IBXA: Isobornyl acrylate, cured product Tg = 97°C, "IBXA" manufactured by Osaka Organic Chemical Industry Ltd. M-106: o-phenylphenol ethylene oxide adduct acrylate, cured product Tg = 30°C, "Aronix M-106" manufactured by Toagosei Co., Ltd. ACMO: Acryloylmorpholine, cured product Tg = 145°C, "ACMO" manufactured by KJ Chemicals Co., Ltd. M-101A: Phenol ethylene oxide modified (n=2) acrylate, cured product Tg=-8°C, "Aronix M-101A" manufactured by Toagosei Co., Ltd. FA1DDM: ε-caprolactone 1 mol modified 2-hydroxyethyl acrylate, "Placcel FA1DDM" manufactured by Daicel Corporation M-5300: ω-carboxy-polycaprolactone (n=2) monoacrylate, "Aronix M-5300" manufactured by Toagosei Co., Ltd. 4-HBA: 4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. "4-HBA"

[0122] <Photoradical polymerization initiator> BAPO: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, "Omnirad 819" manufactured by IGM Resins Omn-184: 1-hydroxycyclohexyl phenyl ketone, manufactured by IGM Resins. Omnirad-184

[0123] <Fluorescent agent> PY-1800: 2-(3-phenylcoumarin-7-ylamino)-4-chloro-6-diethylamino-1,3,5-triazine, "HAKKOL PY-1800" manufactured by Showa Chemical Industry Co., Ltd., maximum emission wavelength between 380 and 500 nm = 438 nm OB: 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), "Tinopal OB" manufactured by BASF Japan, maximum emission wavelength between 380 and 500 nm: 407 and 429 nm K-AS: Stilbene-based fluorescent whitening agent, "KAYAPHOR AS LIQUID" manufactured by Nippon Kayaku Co., Ltd., maximum emission wavelength between 380 and 500 nm = 404 nm EM-016: Pyran-based fluorescent agent, Yamada Chemical Industry Co., Ltd. "EM-016", maximum emission wavelength between 380 and 500 nm = 436 nm The emission wavelength of the fluorescent agent was determined by preparing a tetrahydrofuran solution (concentration: 0.0001 to 0.01 g / L) and measuring the emission spectrum of each compound at an excitation wavelength of 365 nm using a spectrofluorometer FP-750 (manufactured by JASCO Corporation). The concentration was adjusted so that the emission peak did not exceed the measurement limit of the instrument.

[0124] <Reducing agent> TEH: tin(II) 2-ethylhexanoate, "Nikka Octix Tin" manufactured by Nippon Chemical Industry Co., Ltd. TPP: Triphenylphosphine, "Hokuko TPP" manufactured by Hokko Chemical Industry Co., Ltd. TIDP: Triisodecyl phosphite, ADEKA Corporation "ADEKA STAB 3010" PE1: Pentaerythritol tetrakis(3-mercaptobutyrate), "KarenzMT PE1" manufactured by Resonac Co., Ltd.

[0125] <Other ingredients> Q-1301: N-nitrosophenylhydroxylamine aluminum salt, Fujifilm Wako Pure Chemical Industries, Ltd. "Cupferron Q-1301" SH-28: Silicone leveling agent, "DOWSIL SH-28" manufactured by Dow Toray Industries, Inc. RS-76-NS: Fluorine-based surface modifier, "Megafac RS-76-NS" manufactured by DIC Corporation

[0126] The resulting compositions were evaluated as follows, and the results are shown in Table 2.

[0127] <Viscosity> The viscosity of the resulting composition was measured at 25°C using an E-type viscometer.

[0128] <Dark hardening> A 0.5 mm thick black NBR (acrylonitrile butadiene rubber) (20 mm wide x 100 mm long) [1 in Figure 1] was punched out using a rectangular die 5 mm wide x 50 mm long [Figure 1(a)]. This rubber [1 in Figure 2] was then attached to an easily adhesive PET (polyethylene terephthalate) film [Cosmoshine A-4360, manufactured by Toyobo Co., Ltd., 50 μm thick] [2 in Figure 2] using double-sided tape to create a concave rubber sample. The obtained active energy ray-curable composition was poured into this concave portion, and an aluminum-deposited PET (polyethylene terephthalate) film (manufactured by AS ONE Corporation, product name: aluminum-deposited PET film, film thickness 12 μm) [3 in Figure 2] was laminated onto it, leaving 10 mm from the edge, taking care to prevent bubbles from forming. Next, 0.1 mm thick aluminum plates were placed under the easy-adhesion PET film and on top of the aluminum-deposited PET film of this test specimen, to create a dark-curable test specimen. Next, a metal halide lamp manufactured by Eye Graphics Co., Ltd. was used, and the intensity of the ultraviolet region (UV-A) centered at 365 nm was 200 mW / cm 2 , cumulative light intensity 1000mJ / cm 2 This process was repeated five times, with a total cumulative light dose of 5000 mJ / cm 2 The cured product was prepared so that The resulting cured product was immediately washed with methanol to remove any uncured material, and the length of the cured portion extending from the UV-irradiated portion to the unirradiated portion was then measured to provide an index of dark curability.

[0129] <Storage stability> The obtained active energy ray-curable composition was stored in a refrigerator at 4°C in a completely light-shielded state, and the number of days until the composition gelled was measured and used as an index of storage stability.

[0130] <Tensile strain> A cured sample of the obtained active energy ray-curable composition was prepared, measuring 5 mm in width, 1 mm in thickness, and 50 mm in length. The curing conditions were a metal halide lamp with an intensity of 200 mW / cm of ultraviolet light (UV-A) centered at 365 nm. 2 , cumulative light intensity 1000mJ / cm 2 This process was repeated five times to achieve a total cumulative light dose of 5000 mJ / cm 2 The nominal strain of this cured product was measured in a tensile test in accordance with JIS K7161-1:2014 under conditions of a temperature of 23°C, an initial gripping distance of 20 mm, and a test speed of 300 mm / min.

[0131] <Sealability test (initial and bending test)> The obtained active energy ray-curable composition was brushed onto the seam of a commercially available packable parka made of 100% nylon (Dickies D-396, manufactured by Kokos Shinoka Co., Ltd.), and the composition was exposed to ultraviolet light (UV-A) with a metal halide lamp at a wavelength of 365 nm and an intensity of 200 mW / cm. 2 , cumulative light intensity 1000mJ / cm 2 This process was repeated five times to achieve a total cumulative light dose of 5000 mJ / cm 2 I made it so that it would be like this. Next, this sewn portion was cut into a 50 mm diameter circle, and the end of a 20 mm diameter hard polyvinyl chloride pipe was covered with the cut piece of fabric and wrapped with a rubber band, sealing it so that a 20 mm long sealed sewn portion was exposed. The cloth-covered polyvinyl chloride pipe was then submerged in water, and compressed air of a specified pressure was introduced into the other polyvinyl chloride pipe to check for air leakage. The higher the pressure at which air leakage occurred, the better the sealing performance. Furthermore, the sewn portion cut to a 50 mm diameter was bent once 180 degrees and subjected to a sealing test similar to that described above (bending test).

[0132] [Table 2]

[0133] As is clear from the results of Examples 1 to 13, the compositions of the present invention had excellent sealing properties. Example 13 was a composition that did not contain the optional fluorescent agent and reducing agent, and did not have dark curing properties, but had superior sealing properties compared to the compositions of Comparative Examples 1 and 2. The compositions of Examples 1 to 12 contained a fluorescent agent and had dark curing properties, and thus had superior sealing properties compared to Example 13. Furthermore, the compositions of Examples 6 to 12, which contained a photoradical polymerization initiator in addition to a reducing agent, were particularly excellent in sealing properties. On the other hand, Comparative Example 1 had high viscosity and was unable to fully penetrate the seam, resulting in poor initial sealing properties. Furthermore, Comparative Example 2 had low tensile strain at 23°C, so although the initial sealing properties were high, the sealing properties after bending were poor. [Industrial Applicability]

[0134] The composition of the present invention can improve the sealing properties of seams formed by sewing together multiple materials. Furthermore, the composition of the present invention can cure in a short time even the inner part of a seam, which is difficult for irradiated active energy rays to reach, thereby further improving the sealing properties. Furthermore, by controlling the tensile strain value of the cured product within a specific range, the sealing properties can be maintained even after bending. Furthermore, the sealing process of the seam can be completed in a short time by irradiating active energy rays, thereby significantly improving productivity. Because the composition of the present invention has good sealing properties, it can be widely used for waterproofing fiber materials that need to prevent water leakage, such as raincoats and tents, and for sealing the seams of airbags, which require high airtightness. [Brief explanation of the drawings]

[0135] [Figure 1] 1 is a schematic top view of a test specimen used in a dark curing test. [Figure 2] 1 is a schematic side view of a test specimen used in a dark curing test.

Claims

1. An active energy ray-curable composition comprising a compound having an ethylenically unsaturated group and a photoradical polymerization initiator, wherein the active energy ray-curable composition has a viscosity of 1 to 1000 mPa s when measured at 25°C using a cone-and-plate rotational viscometer in accordance with JIS K 6833, and a cured product of the active energy ray-curable composition has a tensile strain of 50 to 700% when measured at 23°C in accordance with JIS K 7161:2014.

2. The active energy ray-curable composition according to claim 1 , wherein the compound having an ethylenically unsaturated group comprises a urethane (meth)acrylate and a monofunctional unsaturated compound.

3. 3. The active energy ray-curable composition according to claim 2, wherein the urethane (meth)acrylate has a weight average molecular weight Mw of 3,000 to 100,000.

4. 2. The active energy ray-curable composition according to claim 1, wherein the photoradical polymerization initiator has an absorption coefficient (mL / g·cm) at 405 nm of 100 or more.

5. 5. The active energy ray-curable composition according to claim 1, wherein the photoradical polymerization initiator is contained in an amount of 0.01 to 15 parts by mass relative to 100 parts by mass of a total amount of the compound having an ethylenically unsaturated group.

6. The active energy ray-curable composition according to any one of claims 1 to 4, further comprising a fluorescent agent and / or a reducing agent.

7. 7. The active energy ray-curable composition according to claim 6, wherein the emission spectrum of the fluorescent agent exhibits a maximum in the range of 380 to 500 nm.

8. 8. The active energy ray-curable composition according to claim 7, wherein the fluorescent agent is contained in an amount of 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of the compound having an ethylenically unsaturated group.

9. 7. The active energy ray-curable composition according to claim 6, wherein the reducing agent has an absorption coefficient (mL / g·cm) at 405 nm of 100 or more.

10. 10. The active energy ray-curable composition according to claim 9, wherein the reducing agent comprises at least one selected from the group consisting of a divalent tin compound, a trivalent phosphorus compound, and a thiol compound.

11. The active energy ray-curable composition according to claim 10, wherein the reducing agent is contained in an amount of 0.1 to 20 parts by mass relative to 100 parts by mass of the total amount of the compound having an ethylenically unsaturated group.

12. A sealant for application to a suture, comprising the active energy ray-curable composition according to any one of claims 1 to 4.

13. A sewn product obtained by applying a sealant containing an active energy ray-curable composition to a seam formed by sewing together a plurality of materials, and then irradiating the applied portion with active energy rays to cure the sealant, wherein the active energy ray-curable composition contains a compound having an ethylenically unsaturated group and a photoradical polymerization initiator, and the viscosity of the active energy ray-curable composition is 1 to 1000 mPa s when measured at 25°C using a cone-plate rotational viscometer in accordance with JIS K 6833, and the tensile strain of a cured product of the active energy ray-curable composition is 50 to 700% when measured at 23°C in accordance with JIS K 7161:2014.

14. A method for producing a sutured product, comprising applying a sealant containing an active energy ray-curable composition to a seam formed by sewing together a plurality of materials, and then irradiating the applied sealant with active energy rays to cure the sealant, wherein the active energy ray-curable composition contains a compound having an ethylenically unsaturated group and a photoradical polymerization initiator, and the viscosity of the active energy ray-curable composition is 1 to 1000 mPa s when measured at 25°C using a cone-plate rotational viscometer in accordance with JIS K 6833, and the tensile strain of a cured product of the active energy ray-curable composition is 50 to 700% when measured at 23°C in accordance with JIS K 7161:2014.

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