Active energy ray curable composition, sealant for application to sewing parts, and method for manufacturing sewing products.

Abstract

An active energy ray curing composition is provided that exhibits excellent penetration into fabric and adhesion after curing. [Solution] An active energy ray curable composition comprising an ethylenically unsaturated compound and a photoradical polymerization initiator, having a viscosity of 20 mPa·s or less at 25°C and a contact angle with 6,6-nylon of 20° or less; a sealant for coating sewing parts using the active energy ray curable composition; and a method for manufacturing a sewing product.

Description

[Technical Field]

[0001] This disclosure relates to an active energy ray curable composition, a sealant for application to sewing parts, and a method for manufacturing sewing products. [Background technology]

[0002] In sewn products made by sewing together multiple materials, it is sometimes necessary to improve waterproofing and airtightness. For example, some products undergo a sealing process where a resin liquid is applied to the seams and hardened. Examples of such sewn items include raincoats, tents, airbags, and bags.

[0003] Conventional sewn products are known to be those described in Patent Documents 1 to 3. 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, wherein the joining means consists of suturing with thread and bonding with an elastic adhesive.

[0004] Patent Document 2 describes an airbag in which two fabrics made of synthetic fibers are joined together with a room-temperature curing adhesive sealant, wherein the room-temperature curing adhesive sealant has a thixotropy index of 1.5 to 6 at 25°C, and the fabrics made of synthetic fibers have a cover factor of 1500 to 2100.

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

[0006] [Patent Document 1] Japanese Patent Publication No. 2001-1854 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-38694 [Patent Document 3] Japanese Patent Application Laid-Open No. 2020-536003 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] Since the active energy ray-curable composition cures only by irradiating active energy rays, it has excellent workability. However, conventional active energy ray-curable compositions have had a problem in that, with respect to cloth, the wettability with the active energy ray-curable composition is poor depending on the material. In addition, conventional active energy ray curing has had a problem in that only the surface irradiated with active energy can be cured. Although silicone resin or the like may be used, since it is moisture-curable, it takes time to cure, and there is a risk that it cannot be completely cured to the center if there is insufficient moisture, and there has been a problem that the curability varies depending on the season. Therefore, there is a need for an active energy ray-curable composition that enhances the sealing property of a suture formed by stitching a plurality of materials together, can cure the inside of the suture where light hardly reaches in a short time, has excellent workability because the resin penetrates quickly, and further has excellent adhesion so that the sealant does not peel off even when the cloth is folded.

[0008] This disclosure is made in view of the above circumstances. [[ID=3--0]] The problem to be solved by the embodiment of the present disclosure is to provide an active energy ray-curable composition having excellent permeability to cloth and adhesion after curing. Another problem to be solved by the embodiment of the present disclosure is to provide a sealant for sewing part application using the active energy ray-curable composition and a method for manufacturing a sewn product. [Means for Solving the Problems]

[0009] Specific means for solving the above problems include the following aspects. <1> An active energy ray curable composition comprising an ethylenically unsaturated compound and a photoradical polymerization initiator, having a viscosity of 20 mPa·s or less at 25°C and a contact angle with nylon 6,6-20° or less. <2> The storage modulus at 25°C and 1 Hz is 1.0 × 10⁻⁶. 5 The above 1.0 × 10 7 The following conditions apply, and the storage modulus at -30°C and 1 Hz is 1.0 × 10⁻⁶. 8 The following is <1> The activated energy ray curable composition described above. <3> tanδ max However, it is below 0℃ <1> or <2> The activated energy ray curable composition described above. <4> The ethylenically unsaturated compound has a surface tension of 50 × 10 -3 Contains monofunctional aliphatic ethylenically unsaturated compounds with a density of N / m or less. <1> ~ <3> An active energy ray curable composition as described in any one of the following. <5> The ethylenically unsaturated compound includes an ethylenically unsaturated compound having an acidic group. <1> ~ <4> An active energy ray curable composition as described in any one of the following. <6> Further contains a chain transfer agent <1> ~ <5> An active energy ray curable composition as described in any one of the following. <7> The content of the chain transfer agent is 1 to 20 parts by mass per 100 parts by mass of the ethylenically unsaturated compound. <6> The activated energy ray curable composition described above. <8> The content of the photoradical polymerization initiator is 0.01 to 15 parts by mass per 100 parts by mass of the ethylenically unsaturated compound. <1> ~ <7> An active energy ray curable composition as described in any one of the following. <9> It further comprises at least one selected from the group consisting of fluorescent agents and reducing agents. <1> ~ <8> An active energy ray curable composition as described in any one of the following. <10> The aforementioned fluorescent agent <9> The activated energy ray curable composition described above. <11> The emission spectrum of the aforementioned fluorescent agent shows a maximum between 380 nm and 500 nm. <10> The activated energy ray curable composition described above. <12> The amount of the fluorescent agent is 0.001 parts by mass to 5 parts by mass per 100 parts by mass of the ethylenically unsaturated compound. <10> or <11> The activated energy ray curable composition described above. <13> <1> ~ <12> A sealant for application to sewing parts, comprising an active energy ray curable composition as described in any one of the following. <14> After sewing, or while sewing, <1> ~ <12> A method for manufacturing a sewn product, comprising applying an active energy ray curable composition described in any one of the above to the sewn portion, irradiating it with active energy, and sealing it. [Effects of the Invention]

[0010] This disclosure provides an active energy ray curing composition that exhibits excellent penetration into fabric and adhesion after curing. Furthermore, this disclosure provides a sealant for coating sewing parts using the active energy ray curable composition, and a method for manufacturing sewing products. [Modes for carrying out the invention]

[0011] In this disclosure, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this disclosure, the amount of each component in a composition means the total amount of any multiple substances present in the composition, unless otherwise specified, if there are multiple substances corresponding to each component in the composition. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range described in stages. In numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced by the values ​​shown in the examples. In this disclosure, a preferred combination of embodiments is a more preferred embodiment. In the notation of groups (atomic groups) in this disclosure, the notation that does not specify substitution or unsubstituted includes both those with and without substituents. In this disclosure, "(meth)acrylate" means at least one of acrylate and methacrylate. In this disclosure, "urethane (meth)acrylate" means a (meth)acrylate polymer having a urethane skeleton.

[0012] "Number-average molecular weight" and "weight-average molecular weight" refer to the values ​​obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter also referred to as "GPC") to polystyrene equivalents. Gel permeation chromatography (GPC) measurements can be performed under the measurement conditions described below to obtain the number-average molecular weight (Mn) and weight-average molecular weight (Mw) in terms of polystyrene. <Measurement conditions> Equipment: HLC-8320 manufactured by Tosoh Corporation Column: TSKgel-SuperMultipore HZ-M (4.6mm ID x 15cm) x 3 tubes manufactured by Tosoh Corporation (for low molecular weight molecules, exclusion limit molecular weight 2,000,000) Column temperature: 40℃ Eluent: Tetrahydrofuran (0.35 ml / min) Detector: Differential refractometer (RI) Sample concentration: 0.1%

[0013] (Activated energy ray curable composition) The active energy ray curable composition according to this disclosure comprises an ethylenically unsaturated compound and a photoradical polymerization initiator, has a viscosity of 20 mPa·s or less at 25°C, and a contact angle with nylon 6,6-20° or less.

[0014] As mentioned above, conventional active energy ray curing compositions have problems with insufficient penetration into fabric and poor adhesion after curing. The inventors have found that as an active energy ray-curable composition, the viscosity at 25°C is 20 mPa·s or less, and the contact angle with nylon is 20° or less. Due to the viscosity being within the above range, it has excellent permeability to cloth, and due to the contact angle with nylon being within the above range, it has excellent permeability to cloth and adhesion after curing. In addition, since the active energy ray-curable composition according to the present disclosure has excellent permeability to cloth and adhesion after curing, it can improve the waterproofness and airtightness of sewn products.

[0015] <Viscosity> The active energy ray-curable composition according to the present disclosure has a viscosity at 25°C of 20 mPa·s or less, and from the viewpoint of permeability to cloth, it is preferably 15 mPa·s or less, and more preferably 10 mPa·s or less. The method for measuring the viscosity in the present disclosure shall be to measure the viscosity at 25°C using an E-type viscometer.

[0016] <Contact Angle> The active energy ray-curable composition according to the present disclosure has a contact angle with 6,6-nylon of 20° or less, and from the viewpoints of permeability to cloth and adhesion after curing, it is preferably 18° or less, more preferably 16° or less, and particularly preferably 1° or more and 15° or less. The method for measuring the contact angle with 6,6-nylon in the present disclosure shall be to use a contact angle meter, drop 2 μL of the composition onto a 6,6-nylon plate at 25°C ± 2°C, and measure the contact angle.

[0017] <Storage Elastic Modulus> The active energy ray-curable composition according to the present disclosure has a storage elastic modulus at 25°C and 1 Hz of 1.0×10 5 or more and 1.0×10 8 or less, preferably, and 1.0×10 5 or more and 5.0×10 7 or less, more preferably, and 1.0×10 5The above 1.0 × 10 7 The following is even more preferable: Furthermore, the active energy ray curable composition relating to this disclosure has a storage modulus of 1.0 × 10⁻¹⁰ at -30°C and 1 Hz, from the viewpoint of penetration into fabric and adhesion after curing. 10 Preferably, it is 1.0 × 10 9 It is more preferable that the following conditions apply: 1.0 × 10 8 It is even more preferable that the following conditions apply: 1.0 × 10 6 The above 1.0 × 10 8 The following is particularly preferable: The method for measuring the storage modulus in this disclosure shall be to measure the storage modulus of the composition using a dynamic viscoelasticity measuring device (manufactured by TA Instruments) under measurement conditions of 2°C / min, 1 Hz, and -100°C to 150°C.

[0018] <tanδ max > The active energy ray curable composition relating to this disclosure has the following characteristics in terms of penetration into fabric and adhesion after curing: tanδ max However, it is preferable that the temperature be 20°C or lower, more preferably 0°C or lower, and particularly preferable that it be between -80°C and 0°C. tanδ in this disclosure max The measurement method shall be calculated from the storage modulus and loss modulus measured by the same method as the measurement method for the storage modulus described above.

[0019] <Ethylene-unsaturated compounds> Examples of ethylenically unsaturated groups include (meth)acryloyl groups, (meth)acrylamide groups, vinyl groups, and (meth)allyl groups. (meth)acryloyl groups are preferred, and acryloyl groups are more preferred, due to their excellent curability of the composition.

[0020] Ethylene-unsaturated compounds can be any compound having one or more ethylenically unsaturated groups. Specifically, examples include compounds with one ethylenically unsaturated group (hereinafter referred to as "monofunctional unsaturated compounds") and compounds with two or more ethylenically unsaturated groups (hereinafter referred to as "polyfunctional unsaturated compounds").

[0021] -Monofunctional unsaturated compounds- In the context of ethylenically unsaturated compounds, 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.

[0022] Specific examples of monofunctional (meth)acrylates include: Alkyl(meth)acrylates with 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; isobornyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclo Monofunctional (meth)acrylates having alicyclic groups, such as lopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, tricyclodecanemethylol (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; Monofunctional (meth)acrylates having aromatic groups, such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenol (meth)acrylate, (meth)acrylate of alkylene oxide adducts of phenols, (meth)acrylate of alkylene oxide adducts of alkylphenols, (meth)acrylate of alkylene oxide adducts of p-cumylphenol, and (meth)acrylate of alkylene oxide adducts of o-phenylphenol; Examples include alkyl carbitol (meth)acrylates such as ethyl carbitol (meth)acrylate, butyl carbitol (meth)acrylate, and 2-ethylhexyl carbitol (meth)acrylate.

[0023] The monofunctional (meth)acrylate may be a compound having various functional groups. Examples of functional groups include hydroxyl groups, carboxyl groups, cyclic ether groups, and heterocycles. Examples of monofunctional (meth)acrylates having a hydroxyl group include hydroxyl group-containing (meth)acrylates 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 carboxyl group include (meth)acrylic acid, Michael addition dimers of (meth)acrylic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, and monohydroxyethyl (meth)acrylate phthalate. 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 monofunctional (meth)acrylates having heterocyclic rings include (meth)acryloylmorpholine, as well as monofunctional (meth)acrylates having imide groups such as N-(2-(meth)acryloxyethyl)hexahydrophthalimide and N-(2-(meth)acryloxyethyl)tetrahydrophthalimide.

[0024] 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 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, as well as N,N-dialkyl(meth)acrylamide.

[0025] Examples of vinyl compounds include compounds having one vinyl group. Specifically, these 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.

[0026] Examples of allyl compounds include compounds that have one allyl group. Specifically, A Examples include alcohols, etc.

[0027] The ethylenically unsaturated compound has a surface tension of 50 × 10 from the viewpoint of penetration into the fabric. -3 It is preferable that the compound contains a monofunctional aliphatic ethylenically unsaturated compound with a surface tension of 40 × 10⁻¹⁰ or less, and has a surface tension of 40 × 10⁻¹⁰. -3 It is more preferable to include a monofunctional aliphatic ethylenically unsaturated compound with a concentration of N / m or less. The surface tension in this disclosure was measured using a contact angle meter (device: DMo-502, manufactured by Kyowa Interface Science Co., Ltd.) and the suspension drop method.

[0028] -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 more (meth)acrylates").

[0029] Examples of bifunctional (meth)acrylates include aliphatic diol diacrylates 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 trivalent 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; These polyol alkylene oxide adducts are di(meth)acrylates; Di(meth)acrylates having an isocyanuric acid skeleton, such as di(meth)acrylates of ethylene oxide adducts of isocyanurate; and Di(meth)acrylates of bisphenol alkylene oxide adducts, such as di(meth)acrylates of bisphenol A alkylene oxide adducts and di(meth)acrylates of bisphenol F alkylene oxide adducts. Examples include: In this case, examples of alkylene oxides in alkylene oxide adducts include ethylene oxide, propylene oxide, tetramethylene oxide, and ethylene oxide and propylene oxide.

[0030] Examples of 3- or more functional (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 isocyanuric acid alkylene oxide adducts. Examples of the alkylene oxide adducts mentioned above include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts.

[0031] It is also possible to use a combination of difunctional (meth)acrylates and trifunctional or more (meth)acrylates. For example, a mixture of di and triacrylates of ethylene oxide adducts of isocyanurate can be used.

[0032] Examples of polyfunctional unsaturated compounds, in addition to the compounds mentioned above, include urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate and polyether (meth)acrylate, polyfunctional polymers, polyfunctional vinyl compounds, and polyfunctional allyl compounds. The following describes these compounds.

[0033] The weight-average molecular weight (hereinafter referred to as "Mw") of the urethane (meth)acrylate is preferably 3,000 to 100,000, from the viewpoint of improving the elongation and sealing properties of the composition. In this disclosure, Mw refers to the molecular weight measured by gel permeation chromatography (hereinafter referred to as "GPC") converted to polystyrene equivalent, and means the value measured under the following conditions. • Detector: Differential refractive system (RI detector) • Column type: Cross-linked polystyrene column Column temperature: 40°C • Eluent: Tetrahydrofuran • Molecular weight standard material: Polystyrene

[0034] Other examples of urethane (meth)acrylates include compounds described on pages 70-74 of the literature "UV / EB Curing Materials" [CMC Corporation, published in 1992].

[0035] Epoxy (meth)acrylates are compounds obtained by the addition reaction of (meth)acrylic acid to epoxy resin, and examples include compounds described on pages 74-75 of the aforementioned document "UV / EB Curing Materials".

[0036] Examples of epoxy resins include aromatic epoxy resins and aliphatic epoxy resins. Examples of aromatic epoxy resins include resorcinol diglycidyl ether; di or polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, or their alkylene oxide adducts; novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; glycidyl phthalimide; and o-diglycidyl phthalate esters. In addition to these, other compounds can be mentioned, such as those described in Chapter 2 of the document "Epoxy Resins - Recent Advances -" (Shokodo, published in 1990) and on pages 4-6 and 9-16 of the document "Polymer Processing" Special Issue 9, Vol. 22 Supplementary Issue Epoxy Resins [Polymers Publication Association, published in 1973].

[0037] 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 polyethylene glycol and polypropylene glycol; diglycidyl ethers of neopentyl glycol, dibromo-neopentyl glycol, and their alkylene oxide adducts; polyglycidyl ethers of polyhydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, and their alkylene oxide adducts, as well as di, tri, or tetraglycidyl ethers of pentaerythritol and its alkylene oxide adducts; di or polyglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; tetrahydrophthalate diglycidyl ether; hydroquinone diglycidyl ether, etc. In addition to these, other compounds can be listed on pages 3-6 of the supplementary volume "Epoxy Resins" of the aforementioned document "Polymer Processing".

[0038] In addition to these aromatic epoxy resins and aliphatic epoxy resins, other examples include epoxy compounds with a triazine core, such as TEPIC [Nissan Chemical Corporation] and Denacol EX-310 [Nagase Chemicals Corporation], as well as compounds described on pages 289-296 of the aforementioned "Polymer Processing" supplement, Epoxy Resins. In the above, ethylene oxide and propylene oxide are preferred as the alkylene oxide in the alkylene oxide adduct.

[0039] Other examples include compounds such as those described on pages 53-56 of the document "Latest UV Curing Technology" [(Printing Information Association Co., Ltd., published in 1991)].

[0040] Examples of polyether (meth)acrylate oligomers include polyalkylene glycol (meth) diacrylate, such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate.

[0041] Examples of polyfunctional polymers include (meth)acrylic polymers having (meth)acryloyloxy groups, and (meth)acrylic polymers having functional groups to which (meth)acryloyl groups have been introduced as side chains, such as compounds described on pages 78-79 of the aforementioned document "UV / EB Curing Materials".

[0042] Examples of polyfunctional vinyl compounds include compounds having two or more vinyl groups. Specifically, these include divinylbenzene, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.

[0043] Examples of polyfunctional allyl compounds include compounds having two or more allyl groups. Specifically, examples include diallyl phthalate, triallyl isocyanurate, and triallyl cyanurate.

[0044] As for the ethylenically unsaturated compound, it is preferable to include a difunctional ethylenically unsaturated compound, and more preferably a difunctional (meth)acrylate compound, from the viewpoint of curability, penetration into fabric, and adhesion after curing.

[0045] As ethylenically unsaturated compounds, urethane (meth)acrylates and monofunctional unsaturated compounds are preferred because they exhibit high elongation of the cured product and excellent adhesion to fibers.

[0046] Furthermore, it is preferable that the ethylenically unsaturated compound has a Tg of 100°C or less after active energy ray curing. In this disclosure, Tg refers to the value measured using a differential scanning calorimeter (DSC) at a heating rate of 10°C / min, and represents the value at the midpoint of the glass transition temperature (Tmg) in the ΔT-temperature curve.

[0047] Urethane (meth)acrylates with a Tg of 100℃ or less are commercially available, including "Arronix M-1200" (Tg=35℃), "Arronix M-1600" (Tg=82℃), "Arronix OT-1001" (Tg=-15℃) [all manufactured by Toagosei Co., Ltd.], "Art Resin UN-333" (Tg=4℃), "Art Resin UN-350" (Tg=-57℃), "Art Resin UN-352" (Tg=31℃), "Art Resin UN-353" (Tg=10℃), and "Art Resin UN-1255" (Tg= Examples include "Art Resin UN-2600" (Tg=-1℃), "Art Resin UN-6200" (Tg=-52℃), "Art Resin UN-7600" (Tg=-41℃), "Art Resin UN-7700" (Tg=-41℃), "Art Resin UN-9200A" (Tg=-27℃), "Art Resin UN-333" (Tg=4℃), "Art Resin UN-333" (Tg=4℃)) [all manufactured by Negami Kogyo Co., Ltd.], and "Kayarad UX-3204" (Tg=-14℃) [manufactured by Nippon Kayaku Co., Ltd.].

[0048] Examples of monofunctional unsaturated compounds with 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 alicyclic groups, such as isobornyl acrylate (Tg=94°C), trimethylcyclohexyl acrylate (Tg=52°C), and cyclic trimethylolpropane formal acrylate (Tg=27°C); Monofunctional (meth)acrylates having aromatic groups such as benzyl acrylate (Tg=6℃), phenol ethylene oxide modified (n=2) acrylate (Tg=-8℃), nonylphenol ethylene oxide modified (n=1) acrylate (Tg=17℃), and nonylphenol ethylene oxide modified (n=4) acrylate (Tg=-20℃), and monofunctional (meth)acrylates having heterocyclic groups such as tetrahydrofurfuryl acrylate (Tg=-12℃); Monofunctional (meth)acrylates having a hydroxyl group, such as 2-hydroxy-3-phenoxypropyl acrylate (Tg=17℃); and Examples include monohydroxyethyl acrylate phthalate (Tg=-20℃), ε-caprolactone adduct of hydroxyethyl acrylate [Daicel Corporation, Praxel FA1DDM] (Tg=-40℃), and monofunctional (meth)acrylates having a carboxyl group, such as ω-carboxypolycaprolactone (n=2) monoacrylate (Tg=-40℃). Examples of monofunctional (meth)acrylamides include N-hydroxyethylacrylamide (Tg=98°C). Examples of vinyl compounds include -vinylpyrrolidone (Tg=80°C) and N-vinylcaprolactam (Tg=90°C).

[0049] A preferred combination of components is a bifunctional (meth)acrylate with a Tg of 100°C or less and a monofunctional (meth)acrylate with a Tg of 100°C or less.

[0050] Ethylene-unsaturated compounds may be used individually or in combination of two or more. The content of ethylenically unsaturated compounds is preferably 50% to 95% by mass, and more preferably 65% ​​to 90% by mass, based on the total mass of the composition.

[0051] <Photoradical polymerization initiator> Photoradical polymerization initiators are compounds that generate radicals upon irradiation with active energy rays, thereby initiating the polymerization of compounds containing ethylenically unsaturated groups. Furthermore, some types of photoradical polymerization initiators function as sensitizers that promote the photodegradation of other photoradical polymerization initiators.

[0052] Specific examples of photoradical polymerization initiators include benzyldimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexylphenyl 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, and 2-hydroxy-1-{4-[4 Aromatic ketone compounds such as -(2-hydroxy-2-methylpropionyl)-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-ylphenyl)-butan-1-one, phenylglyoxylic acid methyl esters, ethylanthraquinone, and phenanthrenequinone; Benzophenone 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)phenylphosphinate, 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 and acridone-based compounds such as 10-butyl-2-chloroacridone; Oxime esters such as 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o- 2,4,5-triarylimidazole dimers such as 2-(o-methoxyphenyl)-4,5-phenylimidazole dimer, 2-(p-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 2,4,5-triarylimidazole dimers. Examples 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-pyrrole-1-yl)-phenyl)titanium, and germanium-based photoinitiators such as bis-(4-methoxybenzoyl)diethylgermanium.

[0053] Among these, photopolymerization initiators with an extinction coefficient (mL / g·cm) of 100 or more at 405 nm are preferred for improving dark-area curing performance, and those with an extinction 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-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium (absorption coefficient at 405 nm = 1197), and germanium-based photopolymerization initiators such as ivocerin (absorption coefficient at 405 nm = 1741) are preferred because they exhibit high curability in the dark.

[0054] The photoradical polymerization initiator may be used alone or in combination of two or more types. The content of the photoradical polymerization initiator is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the ethylenically unsaturated compound. When the content of the photoradical polymerization initiator is within the above range, the composition exhibits excellent curability in dark areas and curability at the bottom of the coating film.

[0055] <Fluorescent dye> The active energy ray curable composition according to this disclosure preferably further contains at least one selected from the group consisting of a fluorescent agent and a reducing agent, and more preferably further contains a fluorescent agent, from the viewpoint of curability in dark areas and adhesion after curing. A fluorescent agent is a compound that possesses fluorescent properties (photoluminescence).

[0056] The fluorescent agent is preferably one whose absorption spectrum has a maximum between 300 nm and 450 nm, and more preferably between 350 nm and 400 nm. Note that the absorption spectrum of a fluorescent agent refers to the value obtained by measuring an acetonitrile solution of the fluorescent agent (concentration 0.008% to 1% by mass, adjusted so that the absorbance peak is 1 or less) using a spectrophotometer.

[0057] Furthermore, the fluorescent agent is preferably one whose emission spectrum has a maximum between 380 nm and 500 nm, and more preferably between 400 nm and 470 nm. The emission spectrum of a 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, adjusted so as not to exceed the measurement limit of the instrument).

[0058] By showing maximum values ​​in the absorption and emission spectra within the above ranges, excessive absorption of emitted light by the fluorescent agent and photoradical polymerization initiator can be suppressed, thereby improving dark-area curing performance.

[0059] Fluorescent whitening agents are known as compounds that satisfy the above-mentioned preferred absorbance and emission wavelengths for fluorescent agents. Fluorescent whitening agents are preferred because they are readily available and have good stability. Specific examples of fluorescent whitening agents include, for example, thiophene-based fluorescent whitening agents, coumarin-based fluorescent whitening agents, stilbene-based fluorescent whitening agents, naphthalene-based fluorescent whitening agents, and benzimidazole-based fluorescent whitening agents.

[0060] Examples of thiophene-based fluorescent whitening agents include 2,5-bis(5-t-butyl-2-benzoxazolyl)thiophene, 2,5-bis(benzoxazole-2-yl)thiophene, 2,5-bis(benzoxazole-2-yl)thiophene, and 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole). Thiophene-based fluorescent whitening agents are commercially available and can be used. Examples include Tinopal OB (manufactured by BASF Japan) and NIKKAFLUOR OB (manufactured by Nippon Chemical Industries, Ltd.).

[0061] 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'-idropyrazolyl)coumarin, 4-methyl-3-(4'-cyanophenyl)-7-(3',5'-dimethylpyrazolyl)coumarin, 4-methyl-3-(4'-ethoxycarbonylphenyl)-7-(3',5'-dimethylpyrazolyl)coumarin, 3-( Examples include 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-dithielamino-1,3,5-triazine. Coumarin-based fluorescent whitening agents are commercially available and can be used. Examples include NIKKAFLUOR MC-T (manufactured by Nippon Chemical Industries, Ltd.), Kayalight B (manufactured by Nippon Kayaku Co., Ltd.), Hakkol P, and Hakkol PY-1800 (manufactured by Showa Chemical Industry Co., Ltd.).

[0062] Examples of stilbene-based fluorescent whitening agents include 4,4'-bis(2-benzoxazolyl)stilbene, 4-(2H-naphtho[1,2-d]triazole-2-yl)stilbene-2-sulfonate sodium, 4,4'-bis[(1,4-dihydro-4-oxo-6-phenylamino-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonate disodium, and 2,2'-(1,2- Ethendiyl)bis[5-(3-phenylureido)benzenesulfonate sodium], 2,2'-(1,2-ethendiyl)bis[5-[(4-amino-6-chloro-1,3,5-triazine-2-yl)amino]benzenesulfonate sodium], 4,4'-bis[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazine-2-yl]amino]stilbene-2,2'- Disodium disulfonate, 2,2'-[1,2-ethendiylbis(3-sodiosulfo-4,1-phenylene)]bis(2H-naphtho[1,2-d]triazole-6-sulfonate sodium), 2,2'-(1,2-ethendiyl)bis[5-[(2,4-dimethoxybenzoyl)amino]benzenesulfonate sodium], 2,2'-(1,2-ethendiyl)bis[5-[[4-methoxy-6-[ Examples include sodium phenylamino[-1,3,5-triazine-2-yl]amino]benzenesulfonic acid, sodium 4,4'-bis[(6-amino-1,4-dihydro-oxo-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonate, and sodium 2,2'-([1,1'-biphenyl]-4,4'-diyldivinylene)bis(benzenesulfonate)disodium. Stilbene-based fluorescent whitening agents are commercially available and can be used. Examples include the stilbene-based fluorescent whitening agents NIKKAFLUOR SB, RP, and 2R (manufactured by Nippon Chemical Industries, Ltd.), and KAYAPHOR AS Liquid and Kayaphor SN conc (manufactured by Nippon Kayaku Co., Ltd.).

[0063] Examples of naphthalene-based fluorescent whitening agents include 1,4-bis(2-benzoxazolyl)naphthalene. Naphthalene-based fluorescent whitening agents are commercially available and can be used. For example, NIKKAFLUOR KB (manufactured by Nippon Chemical Industries, Ltd.) is one such product.

[0064] Benzimidazole-based fluorescent whitening agents are commercially available and can be used. For example, HOSTALUX ACK LIQ (manufactured by Clariant Japan) is one such product.

[0065] Other fluorescent agents besides those mentioned above include polycyclic aromatic hydrocarbon compounds. Examples include anthracene compounds and perylene compounds.

[0066] Among these fluorescent agents, thiophene-based fluorescent whitening agents, coumarin-based fluorescent whitening agents, stilbene-based fluorescent whitening agents, naphthalene-based fluorescent whitening agents, benzimidazole-based fluorescent whitening agents, and perylene compounds are preferred due to their excellent dark curability, storage stability, and solubility. Of these, thiophene-based fluorescent whitening agents, coumarin-based fluorescent whitening agents, and stilbene-based fluorescent whitening agents are more preferred. Preferred specific thiophene-based fluorescent whitening agents include 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), preferred specific coumarin-based fluorescent whitening agents include 4-methyl-7-diethylaminocoumarin, and preferred specific stilbene-based fluorescent whitening agents include 4,4'-bis(2-methoxystyryl)biphenyl.

[0067] These compounds can be used individually or in combination of two or more.

[0068] Fluorescent dyes may be used individually or in combination of two or more types. The fluorescent agent content is preferably 0.001 to 5 parts by mass, and more preferably 0.002 to 1 part by mass, per 100 parts by mass of the ethylenically unsaturated compound. When the fluorescent agent content is 0.001 parts by mass or more, the hardening properties in dark areas are excellent, and when it is 5 parts by mass or less, the hardening properties at the bottom of the coating film are excellent.

[0069] <Reducing agent> A reducing agent is an element or molecule that reduces other chemical species in a redox reaction. Specific examples of reducing agents include amine compounds, thiourea derivatives, metal salts, organic acid compounds, aldehyde compounds, phenol compounds, and phosphorus compounds.

[0070] 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-dimeth 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 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.

[0071] Examples of thiourea derivatives include 2-imidazolidinethion, 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.

[0072] Examples of 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, and Examples include nadylacetylacetonate (IV), vanadyl stearate, vanadium naphthenate, vanadium acetylacetonate (III), vanadium benzoylacetonate, bis(acetylacetonate)oxovanadium (IV), bis(benzoylacetonate)oxovanadium (IV), bis(stearoyloxy)oxovanadium (IV), vanadyl oxalate, and vanadyl naphthenate. Furthermore, the vanadium compound may be a pentavalent vanadium compound, such as vanadium(V) pentoxide, metavanadate(V) salt, or tri(alkoxy)oxovanadium(V). A pentavalent vanadium compound can form a tetravalent vanadium compound in the composition in the presence of an acidic compound such as a phosphoric acid compound (e.g., dibutyl phosphate and tributyl phosphate).

[0073] Examples of acidic compounds include ascorbic acid and ascorbates such as sodium ascorbate and potassium ascorbate; erythorbic acid and erythorbates such as sodium erythorbate and potassium erythorbate; tartaric acid and tartrates such as sodium tartrate and potassium tartrate; phosphites such as phosphorous acid and sodium phosphite and potassium phosphite; hydrogen phosphites such as sodium hydrogen phosphite and potassium hydrogen phosphite; sulfites such as sodium sulfite and potassium sulfite; thiosulfites 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; and pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate. Other examples include sodium hydroxymethanesulfonate (sodium formaldehyde sulfoxylate), sodium sulfinate derivatives, propyl formate, isoamyl formate, and pentyl formate, phenyl formate, etc.

[0074] Examples of aldehyde compounds include aromatic aldehydes such as benzaldehyde, anisaldehyde, and p-methoxyaldehyde, as well as aliphatic aldehydes such as propionaldehyde, hexylaldehyde, and glyoxal. It is preferable to use them as aldimine compounds, which are condensates with primary amines.

[0075] Examples of phenolic compounds include catechol, resorcinol, p-hydroquinone, pyrocatechol, and catecholamines.

[0076] As the phosphorus compound, a trivalent compound having reducing properties is preferred. Trivalent phosphorus compounds include, specifically, 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, te Examples of phosphies include traphenyldipropylene 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, isodecyldiphenyl phosphite, and triisodecyl phosphite.

[0077] Among these compounds, metal salts, phosphorus compounds, and thiol compounds are preferred as reducing agents because they can improve dark-area curability, and among these, divalent tin compounds, thiol compounds, and trivalent phosphorus compounds are more preferred. These compounds can be used individually or in combination of two or more.

[0078] The reducing agent may be used alone or in combination of two or more types. The reducing agent content is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the ethylenically unsaturated compound. When the reducing agent content is 0.1 parts by mass or more, the dark area curing properties are excellent, and when it is 20 parts by mass or less, the elastic modulus of the cured product is appropriate, making it suitable as a sealant, and furthermore, the storage stability of the composition is excellent.

[0079] <Chain movement agent> The active energy ray curable composition according to this disclosure preferably further comprises a chain transfer agent. As the chain transfer agent, known chain transfer agents can be used, and thiol compounds are preferred.

[0080] Thiol compounds are compounds that contain one or more thiol groups in their molecule, and specific examples include the following:

[0081] Compounds having one thiol group include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan.

[0082] Compounds having two thiol groups include, for example, 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, and 4,4'-thiodithiol. Examples 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.

[0083] 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.

[0084] Examples of compounds having four thiol groups include pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), and pentaerythritol tetrakisthioglycolate.

[0085] 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 hydroxyl group and then esterification with a mercapto organic acid.

[0086] The chain transfer agent may be used alone or in combination of two or more types. The content of the chain transfer agent is preferably 1 to 20 parts by mass, and more preferably 5 to 15 parts by mass, per 100 parts by mass of the ethylenically unsaturated compound.

[0087] The composition can be manufactured by conventional methods, for example, by stirring and mixing an ethylenically unsaturated compound, a photoradical polymerization initiator, and optionally a chain transfer agent, a fluorescent agent, a reducing agent, and other components described below. The stirring speed and temperature during stirring should be set appropriately according to the composition being manufactured and its purpose. During stirring and mixing, heating may be used as needed. In this case, the temperature is preferably 30°C to 100°C, and particularly preferably 40°C to 80°C.

[0088] The Tg of the cured product of the active energy ray curable composition according to this disclosure is preferably -100°C to 80°C, and more preferably -70°C to 30°C.

[0089] The tensile strain of the cured product of the active energy ray curable composition according to this disclosure is preferably 50% to 700% at 23°C, and more preferably 100% to 500%. When the tensile strain is 50% or more, the sealing performance of the seam is excellent when the composition is applied to the seam between multiple materials and then bent after curing. When the tensile strain is 700% or less, the cured product does not deform excessively and exhibits excellent sealing performance. In this disclosure, tensile strain refers to the nominal strain measured in a tensile test of a hardened sample measuring 5 mm wide x 1 mm thick x 50 mm long, under the conditions of a temperature of 23°C, an initial grip distance of 20 mm, and a test speed of 300 mm / min, in accordance with JIS K7161-1:2014. The curing conditions at this time were a metal halide lamp with an ultraviolet (UV-A) intensity centered at 365 nm at 700 mW / cm². 2 , cumulative light intensity 2000 mJ / cm 2 Adjust the settings to achieve the desired level of UV irradiation, repeat this process twice, and the total accumulated light intensity will reach 4000 mJ / cm². 2 I made it so that it would be like that.

[0090] <Other ingredients> The active energy ray curable composition relating to this disclosure may contain other components depending on the purpose. Other components include, specifically, antioxidants, UV absorbers, leveling agents, silane coupling agents, surface modifiers, and polymerization inhibitors. The following explains these ingredients. Furthermore, the other components listed below may be one of the exemplified compounds used, or two or more may be used in combination.

[0091] -Antioxidant- Antioxidants can be added to improve the durability of the cured product, such as its heat resistance and weather resistance. Examples of antioxidants include phenolic antioxidants and sulfur-based antioxidants. Examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. Commercially available examples 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 compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA Corporation. These can be used individually or in combination of two or more types. A preferred combination of these antioxidants is the combined use of a phenolic antioxidant and a sulfur-based antioxidant. The antioxidant content can be set appropriately depending on the purpose, but preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of the ethylenically unsaturated compound. By setting the content to 0.1 parts by mass or more, the durability of the composition can be improved, while by setting it to 5 parts by mass or less, good curability and adhesion can be achieved.

[0092] - UV absorber - UV absorbers can be added to improve the light resistance of the cured product. Examples of UV absorbers include triazine-based UV absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole-based UV absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130. The content ratio of the ultraviolet absorber can be set appropriately depending on the purpose, but preferably it is 0.01 to 5 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of the ethylenically unsaturated compound. By setting the content ratio to 0.01 parts 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 composition It can be made to have excellent hardening properties.

[0093] -Silane coupling agent- Silane coupling agents can be added to improve the interfacial adhesion strength between the cured product and the substrate. The silane coupling agent is not particularly limited as long as it can contribute to improving adhesion to the substrate.

[0094] Examples of silane coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, and N-2-(aminoethyl) Examples include -3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. The silane coupling agent can be one of the aforementioned compounds or two or more compounds can be used in combination.

[0095] The proportion of the silane coupling agent can be set appropriately depending on the purpose, but is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the ethylenically unsaturated compound. By increasing the blending ratio to 0.1 parts by mass or more, the adhesive strength of the composition can be improved, while by keeping it at 10 parts by mass or less, changes in adhesive strength over time can be prevented.

[0096] -Surface modifier- The active energy ray curable composition relating to this disclosure may contain a surface modifier for purposes such as improving leveling properties during application or enhancing scratch resistance by increasing the slipperiness of the cured product. Examples of surface modifiers include surface modifiers, surfactants, leveling agents, defoaming agents, lubricity-imparting agents, and antifouling agents, and these known surface modifiers can be used. Among these, silicone-based surface modifiers and fluorine-based surface modifiers are particularly preferred. Specific examples include silicone-based polymers and oligomers having silicone chains and polyalkylene oxide chains, silicone-based polymers and oligomers having silicone chains and polyester chains, fluorine-based polymers and oligomers having perfluoroalkyl groups and polyalkylene oxide chains, and fluorine-based polymers and oligomers having perfluoroalkyl ether chains and polyalkylene oxide chains. Furthermore, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in its molecule may be used for purposes such as improving the durability of the lubricity.

[0097] The surface modifier content is preferably 0.01 to 1.0 parts by mass per 100 parts by mass of the ethylenically unsaturated compound. Within this range, the surface smoothness of the cured film is excellent.

[0098] -Polymerization inhibitor- The active energy ray curable composition relating to this disclosure may contain polymerization inhibitors for purposes such as improving storage stability. Polymerization inhibitors 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 garbinoxyl, 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.

[0099] Among these, stable radicals and nitroso compounds are preferred because they cause minimal discoloration of the composition, prevent thickening and gelation of the composition, and enhance storage stability. The content ratio of the polymerization inhibitor can be set appropriately depending on the purpose, but preferably it is 0.0005 parts by mass to 1 part by mass, and more preferably 0.001 parts by mass to 0.5 parts by mass, per 100 parts by mass of the ethylenically unsaturated compound. If the content ratio is 0.0005 parts by mass or more, the thermal stability and photostability of the composition can be improved, and if it is 1 part by mass or less, the photocurability of the composition can be improved.

[0100] <How to use> The active energy ray curable composition according to this disclosure is used to seal the seams of sewn parts in sewn materials that require waterproofing and airtightness, which are made by sewing together multiple materials. For example, it can be used in various sewn materials such as waterproofing fibrous materials that need to be prevented from leaking water, such as raincoats and tents, and sealing the seams of airbags that require high airtightness.

[0101] Various application methods can be used. For example, knife coating, die coating, roll coating (National, Reverse), brush coating, spray coating, kiss roll coating, flow coating (shower coating, curtain coating), inkjet, jet dispenser, nozzle dispenser, etc.

[0102] As a curing method for the active energy ray curable composition relating to this disclosure, methods used for conventional active energy ray curable compositions can be applied. Examples include ultraviolet light, visible light, and electron beams, but ultraviolet light is preferred among them. 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 should be set appropriately according to the type and composition of the active energy rays. For example, when using a high-pressure mercury lamp, the irradiation intensity should be 50 mW / cm². 2 ~5000mW / cm 2 Preferably, 100 mW / cm² 2 ~3000mW / cm 2 This is more preferable. Irradiation energy of 10 mJ / cm 2 ~50,000 mJ / cm 2 Preferably, 50 mJ / cm 2 ~10000 mJ / cm 2 This is more preferable. Also, when using LEDs, the irradiation intensity should be 50 mW / cm². 2 ~20,000 mW / cm² 2 Preferably, 200 mW / cm² 2 ~10000mW / cm 2 This is more preferable. Irradiation energy of 500 mJ / cm 2 ~100,000 mJ / cm 2 Preferably, 2000 mJ / cm² 2 ~50,000 mJ / cm 2 This is more preferable. In the case of LEDs, a short wavelength is preferred as the emission wavelength, and 365nm, 385nm, or 405nm is preferred.

[0103] Examples of the sewn material include fibrous materials. There are no particular restrictions on the type of fiber used in the fibrous material, and known materials can be used. Examples include aliphatic polyamides such as 6,6-nylon (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 rayons.

[0104] Suitable examples of sewn products relating to this disclosure include waterproofing of textile components that need to be prevented from leaking water, such as raincoats and tents, and airbags that require high airtightness.

[0105] Furthermore, the active energy ray curable composition according to this disclosure can be suitably used as a sealant for application to seams. In other words, the sealing agent for sewing parts according to this disclosure includes the active energy ray curable composition according to this disclosure.

[0106] Furthermore, a preferred method for manufacturing a sewn product according to this disclosure is to apply the active energy ray curable composition according to this disclosure to the sewn portion after sewing or while sewing, irradiate it with active energy, and seal it. [Examples]

[0107] The present disclosure will be further described below with reference to examples, but the present disclosure is not limited to the following examples unless it exceeds the spirit of the disclosure.

[0108] The following details the materials used in the examples and comparative examples.

[0109] <Difunctional ethylenically unsaturated compounds> • UN-6200: Polyether-based urethane acrylate, manufactured by Negami Kogyo Co., Ltd. • M-240: Tetraethylene glycol diacrylate, manufactured by Toagosei Co., Ltd. as "Arronix M-240" • ADE-400A: Polyethylene glycol (n=9) diacrylate, manufactured by NOF Corporation, "Bremmer ADE-400A" • M-270: Polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd. as "Arronix M-270" HX-220: 3-[2,2-dimethyl-3-[[1-oxo-6-(propenoyloxy)hexyl]oxy]propoxy]-2,2-dimethyl-3-oxopropyl 6-(propenoyloxy)hexanoate, manufactured by Nippon Kayaku Co., Ltd. as "KAYARAD HX-220" • SR9003NS: Propoxylated 2-neopentyl glycol, manufactured by Sartomer, "SR9003NS" • NDDA: 1,9-nonanediol diacrylate, manufactured by Kyoeisha Chemical Co., Ltd. as "Light Acrylate 1,9ND-A" • A-PTMG65: Polytetramethylene glycol (n≒9) acrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "NK Ester A-PTMG65"

[0110] <Monofunctional ethylenically unsaturated compounds> • EEEA: Ethoxyethoxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., "Viscoat #190", surface tension 20-25 × 10 at 25°C -3 N / m • INAA: Isononyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., surface tension 27.5 × 10⁻⁶ at 25°C. -3 N / m • IAA: Isoamyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. ("Light Acrylate IAA") • AIB: Isobutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., "AIB", surface tension 24.7 × 10⁻⁶ at 25°C -3 N / m • TBA: t-butyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., "TBA", surface tension 20-25 × 10 at 25°C -3 N / m IBXA: Isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., surface tension 33 × 10 at 25°C. -3 N / m • TMCHA: 3,3,5-trimethylcyclohexyacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., "Viscoat #196", surface tension 29 × 10 at 25°C -3 N / m

[0111] <Ethylene-unsaturated compounds containing functional groups> • M-5300: ω-carboxy-polycaprolactone monoacrylate, manufactured by Toagosei Co., Ltd. as "Arronix M-5300" • 4-HBA: 4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0112] <Photoradical polymerization initiator> • 184D: 1-Hydroxycyclohexyl phenyl ketone, manufactured by IGM Resins, "Omnirad 184D" • 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, manufactured by IGM Resins, "Omnirad 819" • ONE: Oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone), manufactured by IGM Resins, "ESACURE ONE"

[0113] <Chain movement agent> • PEMP: Pentaerythritol tetrakis(3-mercaptopropionate), manufactured by Sakai Chemical Industry Co., Ltd.

[0114] <Fluorescent dye> PY-1800: 2-(3-phenylcoumarin-7-ylamino)-4-chloro-6-diethylamino-1,3,5-triazine, manufactured by Showa Chemical Industry Co., Ltd. as "HAKKOL PY-1800 (2% tetrahydrofurfuryl acrylate (THFA) solution)", maximum emission wavelength between 380nm and 500nm = 438nm

[0115] <Other ingredients> • 8526: Polyether-modified silicone, leveling agent, manufactured by Dow-Toray Industries, Inc. ("DOWSIL 8526")

[0116] (Examples 1-8 and Comparative Examples 1-4) 1. Preparation of photocurable resin composition The compounds shown in Table 1 below were stirred and mixed at 50°C in the proportions shown in Table 1 to produce an active energy ray curable composition.

[0117] The obtained compositions were used for the following evaluations. The results are shown in Table 2.

[0118] <Viscosity> The viscosity of the obtained composition was measured at 25°C using an E-type viscometer.

[0119] <Contact angle> Using a contact angle meter, 2 μL of the obtained composition was dropped onto a 6,6-nylon plate at 25°C, and the contact angle was measured.

[0120] <Storage modulus> The storage modulus of the obtained composition was measured using a dynamic viscoelasticity analyzer (manufactured by TA Instruments) under measurement conditions of 2°C / min, 1 Hz, and -100°C to 150°C.

[0121] <Adhesion confirmation test (grid pattern peeling)> The composition obtained was applied to a 6,6-nylon plate using a bar coater #20, and then UV cured (4,000 mJ / cm²). 2 700mW / cm² 2 )did. The area percentage of the material that did not peel off in a grid pattern was evaluated as follows: A if 80% or more was peeled off, B if 50% or more but less than 80%, and C if less than 50%.

[0122] <Permeability Evaluation> A 2.0 μL droplet of the obtained composition was dropped onto the seam of a 6,6-nylon fabric, and the time it took for it to completely penetrate was evaluated. The penetration time until complete penetration was classified as A if it was 5 seconds or less, B if it was between 5 seconds and 10 seconds, and C if it was more than 10 seconds.

[0123] [Table 1]

[0124] As shown in Table 1, the active energy ray curable compositions of Examples 1 to 8 exhibited superior penetration into fabric and adhesion after curing compared to the active energy ray curable compositions of Comparative Examples 1 to 4.

Claims

1. It comprises an ethylenically unsaturated compound and a photoradical polymerization initiator. The viscosity at 25°C is 20 mPa·s or less. The contact angle with respect to 6,6-nylon is 20° or less. Active energy ray curable composition.

2. The storage modulus at 25°C and 1 Hz is 1.0 × 10⁻⁶. ５ The above 1.0 x 10 ７ The following conditions apply, and the storage modulus at -30°C and 1 Hz is 1.0 × 10⁻⁶. ８ The activated energy ray curable composition according to claim 1, which is as follows:

3. tanδ ｍａｘ The activated energy ray curable composition according to claim 1, wherein the temperature is 0°C or lower.

4. The ethylenically unsaturated compound has a surface tension of 50 × 10 －３ The active energy ray curable composition according to claim 1, comprising a monofunctional aliphatic ethylenically unsaturated compound with a concentration of N / m or less.

5. The active energy ray curable composition according to claim 1, wherein the ethylenically unsaturated compound comprises an ethylenically unsaturated compound having an acid group.

6. The active energy ray curable composition according to claim 1, further comprising a chain transfer agent.

7. The active energy ray curable composition according to claim 6, wherein the content of the chain transfer agent is 1 to 20 parts by mass per 100 parts by mass of the ethylenically unsaturated compound.

8. The active energy ray curable composition according to claim 1, wherein the content of the photoradical polymerization initiator is 0.01 to 15 parts by mass per 100 parts by mass of the ethylenically unsaturated compound.

9. The active energy ray curable composition according to claim 1, further comprising at least one selected from the group consisting of fluorescent agents and reducing agents.

10. The active energy ray curable composition according to claim 9, comprising the fluorescent agent.

11. The activated energy ray curable composition according to claim 10, wherein the emission spectrum of the fluorescent agent exhibits a maximum in the range of 380 nm to 500 nm.

12. The active energy ray curable composition according to claim 10, wherein the amount of the fluorescent agent is 0.001 parts by mass to 5 parts by mass per 100 parts by mass of the ethylenically unsaturated compound.

13. A sealant for coating seams, comprising the active energy ray curable composition according to any one of claims 1 to 12.

14. A method for manufacturing a sewn product, comprising applying an active energy ray-curable composition according to any one of claims 1 to 12 to the sewn portion after sewing, or while sewing, irradiating it with active energy, and sealing it.

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