Photocurable resin composition, cured product, and laminate

Abstract

To provide a photocurable resin composition excellent in quick curability by irradiation with a low integrated quantity of light and capable of giving a cured product having flexibility.SOLUTION: The photocurable resin composition contains the following components (A)-(E): (A) a monofunctional urethane (meth)acrylate having a polyether skeleton; (B) a monofunctional (meth)acrylic monomer having a polyether skeleton and having no urethane skeleton; (C) a photoradical polymerization initiator; (D) a tetrafunctional or higher polyfunctional (meth)acrylic monomer; and (E) a polyether-based plasticizer having no (meth)acryloyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photocurable resin composition, a cured product, and a laminate. [Background technology]

[0002] Conventionally, flexible photocurable resin compositions have been used to bond a liquid crystal display display unit to a protective panel in order to alleviate stress when large-area components are bonded together and to alleviate impact on the bonded laminate. For example, Japanese Patent Application Laid-Open No. 2015-163699 discloses a photocurable adhesive composition containing, as its main components, polyisoprene (meth)acrylate oligomer, polybutadiene (meth)acrylate oligomer, etc. Summary of the Invention

[0003] Photocurable resin compositions used in the assembly of industrial products are required to be rapidly curable by low cumulative light dose irradiation from the viewpoint of productivity, but the photocurable adhesive composition described in JP 2015-163699 A has the problem of being inferior in rapid curing ability by low cumulative light dose irradiation. In the present invention, low cumulative light dose irradiation means 0.5 to 25.0 kJ / m 2 Say the range of.

[0004] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photocurable resin composition that has excellent rapid curing properties when irradiated with a low cumulative light dose, and that can give a flexible cured product.

[0005] The gist of the present invention will now be described. [1] A photocurable resin composition comprising the following components (A) to (E): (A) component: a monofunctional urethane (meth)acrylate having a polyether skeleton; Component (B): a monofunctional (meth)acrylic monomer having a polyether skeleton and not having a urethane skeleton; Component (C): photoradical polymerization initiator; (D) component: a polyfunctional (meth)acrylic monomer having 4 or more functional groups; and Component (E): A polyether-based plasticizer that does not have a (meth)acryloyl group. [2] Fast curing with low cumulative light exposure (G'2 (7.5 kJ / m 2 ) / G'1(15.0kJ / m 2 )) is in the range of 0.90 to 1.50. [3] The photocurable resin composition according to [1] or [2], characterized in that the component (A) is contained in an amount of 20 to 90 parts by mass per 100 parts by mass of the total of the components (A) and (B). [4] The photocurable resin composition according to any one of [1] to [3], characterized in that it contains 0.1 to 15 parts by mass of the component (C), 0.1 to 15 parts by mass of the component (D), and 30 to 200 parts by mass of the component (E), relative to 100 parts by mass in total of the components (A) and (B). [5] The photocurable resin composition according to any one of [1] to [4], wherein the number of repeating alkylene oxide moieties in the component (E) is 3 to 300. [6] The photocurable resin composition according to any one of [1] to [5], characterized in that the viscosity at 25°C is 0.01 to 15 Pa·s. [7] 7.5kJ / m 2 The photocurable resin composition according to any one of [1] to [6], characterized in that the storage modulus (G'2) of the cured product obtained by irradiating the composition with ultraviolet light is 100 to 2000 Pa. [8] The photocurable resin composition according to any one of [1] to [7], which does not contain a bifunctional (meth)acrylate. [9] A cured product obtained by curing the photocurable resin composition according to any one of [1] to [8].

[10] A laminate obtained by laminating materials using the photocurable resin composition according to any one of [1] to [8]. DETAILED DESCRIPTION OF THE INVENTION

[0006] The invention is described in detail below. In this specification, "X to Y" is used to mean "at least X and at most Y," with the numerical values ​​(X and Y) before and after it being included as the lower and upper limits, respectively. In addition, in the present invention, "(meth)acrylate" means both acrylate and methacrylate.

[0007] One aspect of the present invention is a photocurable resin composition containing the following components (A) to (E): (A) component: a monofunctional urethane (meth)acrylate having a polyether skeleton; Component (B): a monofunctional (meth)acrylic monomer having a polyether skeleton and not having a urethane skeleton; Component (C): photoradical polymerization initiator; (D) component: a polyfunctional (meth)acrylic monomer having 4 or more functional groups; and Component (E): A polyether-based plasticizer that does not have a (meth)acryloyl group.

[0008] This provides a photocurable resin composition that exhibits excellent rapid curing properties when exposed to a low cumulative light dose and that can give a flexible cured product.

[0009] <Component (A)> The photocurable resin composition of the present invention may contain a monofunctional urethane (meth)acrylate having a polyether skeleton as component (A), but by combining it with other components of the present invention, it can be rapidly cured with low cumulative light exposure to obtain a low-elasticity cured product. The urethane (meth)acrylate is a compound having a urethane bond formed by reacting an isocyanate group with a hydroxyl group and a (meth)acryloyl group. The polyether skeleton refers to a skeleton having an alkylene oxide, such as polyethylene oxide, polypropylene oxide, or polybutylene glycol.

[0010] The method for producing the component (A) is not particularly limited, but examples thereof include urethane (meth)acrylates formed from the reaction product of a polyol compound having a hydroxyl group and a (meth)acrylate having an isocyanate group, and urethane (meth)acrylates formed from the reaction product of a polyol compound having a hydroxyl group, a polyisocyanate compound, and a (meth)acrylate having a hydroxyl group. Examples of the polyol compound having a hydroxyl group include polyethylene oxide, polypropylene oxide, and polybutylene glycol. The number of repeating alkylene oxides is not particularly limited, but is, for example, 3 to 500, more preferably 5 to 100, and particularly preferably 10 to 50. Examples of the (meth)acrylate having an isocyanate group include 2-isocyanatoethyl (meth)acrylate and 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate. The polyisocyanate compound is not particularly limited, but examples thereof include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Among these, aliphatic polyisocyanates and alicyclic polyisocyanates are preferred from the viewpoint of obtaining a flexible cured product. These may be used alone or in combination.

[0011] Examples of aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene-1,5-disocyanate, and triphenylmethane triisocyanate. Examples of alicyclic polyisocyanates include isophorone diisocyanate, bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, norbornane diisocyanate, and bicycloheptane triisocyanate. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and 1,6,11-undeca triisocyanate. Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, (poly)ethylene glycol mono(meth)acrylate, (poly)propylene glycol mono(meth)acrylate, and pentaerythritol tri(meth)acrylate. Among these, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxycyclohexyl (meth)acrylate are preferred from the viewpoint of obtaining a cured product with excellent flexibility. These may be used alone or in combination.

[0012] Catalysts used in the synthesis of component (A) include, for example, lead oleate, antimony trichloride, triphenylaluminum, trioctylaluminum, tetrabutyltin, dibutyltin dilaurate, copper naphthenate, zinc naphthenate, zinc octylate, zinc octenate, zirconium naphthenate, cobalt naphthenate, tetra-n-butyl-1,3-diacetyloxydistannoxane, triethylamine, 1,4-diaza[2,2,2]bicyclooctane, and N-ethylmorpholine. Among these, dibutyltin dilaurate, zinc naphthenate, zinc octylate, and zinc octenate are preferred because they cure rapidly with low cumulative light exposure and produce cured products with low elasticity. These catalysts are preferably used in an amount of 0.0001 to 10 parts by weight per 100 parts by weight of the total reactants. The reaction temperature is typically 10 to 100°C, and preferably 30 to 90°C.

[0013] The weight-average molecular weight of component (A) in the present invention is not particularly limited, but in order to obtain a flexible cured product with excellent rapid curing properties when exposed to low cumulative light doses, the weight-average molecular weight is preferably, for example, from 1,000 to 300,000, more preferably from 3,000 to 50,000, and particularly preferably from 5,000 to 40,000.Unless otherwise specified, the weight-average molecular weight is calculated by a standard polystyrene conversion method using size exclusion chromatography (SEC).

[0014] There are no particular limitations on the commercially available product of component (A), and it can be obtained, for example, from Rahn AG or Negami Chemical Industrial Co., Ltd. Specific examples include GENOMER 4188, 4312, 4316, and 4590 manufactured by Rahn AG.

[0015] The amount of component (A) is preferably in the range of 20 to 90 parts by mass, more preferably 25 to 80 parts by mass, even more preferably 30 to 75 parts by mass, and particularly preferably 40 to 70 parts by mass, per 100 parts by mass of the total of components (A) and (B). Alternatively, the amount of component (A) may be 35 to 65 parts by mass, per 100 parts by mass of the total of components (A) and (B). By being within the above range, a photocurable resin composition can be obtained that exhibits even more rapid curing properties with low cumulative light exposure and that produces a flexible cured product.

[0016] <(B) component> The component (B) contained in the photocurable resin composition of the present invention is not particularly limited as long as it is a monofunctional (meth)acrylic monomer having a polyether skeleton but no urethane skeleton, but by combining it with other components of the present invention, it is possible to obtain a cured product that is fast-curable with low cumulative light exposure and has flexibility. The polyether skeleton refers to a skeleton having an alkylene oxide, such as polyethylene oxide, polypropylene oxide, or polybutylene glycol. The number of repeating alkylene oxide moieties is not particularly limited, but is, for example, 2 to 300.

[0017] The component (B) is not particularly limited, and examples thereof include methoxydiethylene glycol mono(meth)acrylate, methoxytriethylene glycol mono(meth)acrylate, methoxytetraethylene glycol mono(meth)acrylate, methoxypentaethylene glycol mono(meth)acrylate, methoxyhexaethylene glycol mono(meth)acrylate, methoxyheptaethylene glycol mono(meth)acrylate, methoxyhexaethylene glycol mono(meth)acrylate, methoxyoctaethylene glycol mono(meth)acrylate, methoxynonaethylene glycol mono(meth)acrylate, methoxydecaethylene glycol mono(meth)acrylate, methoxytripropylene glycol mono(meth)acrylate, methoxytetrapropylene glycol mono(meth)acrylate, methoxypentapropylene glycol mono(meth)acrylate, methoxyhexapropylene glycol mono(meth)acrylate, methoxyheptapropylene glycol mono(meth)acrylate, and methoxyhectapropylene glycol mono(meth)acrylate. , Methoxyoctapropylene glycol mono(meth)acrylate, Methoxynonapropylene glycol mono(meth)acrylate, Methoxydecapropylene glycol mono(meth)acrylate, Methoxytributylene glycol mono(meth)acrylate, Methoxytetrabutylene glycol mono(meth)acrylate, Methoxypentabtylene glycol mono(meth)acrylate, Methoxyhexabtylene glycol mono(meth)acrylate, Methoxyheptabtylene glycol mono(meth)acrylate, Methoxyhectabtylene Glycol mono(meth)acrylate, methoxyoctabutylene glycol mono(meth)acrylate, methoxynonabtylene glycol mono(meth)acrylate, methoxydecabutylene glycol mono(meth)acrylate, ethoxydiethylene glycol mono(meth)acrylate, ethoxytriethylene glycol mono(meth)acrylate, ethoxytetraethylene glycol mono(meth)acrylate, ethoxypentaethylene glycol mono(meth)acrylate, ethoxyhexaethylene glycol mono(meth)acrylate,Ethoxyheptaethylene glycol mono(meth)acrylate, ethoxyhexaethylene glycol mono(meth)acrylate, ethoxyoctaethylene glycol mono(meth)acrylate, ethoxynonaethylene glycol mono(meth)acrylate, ethoxydecaethylene glycol mono(meth)acrylate, ethoxytripropylene glycol mono(meth)acrylate, ethoxytetrapropylene glycol mono(meth)acrylate, ethoxypentapropylene glycol mono(meth)acrylate, ethoxyhexapropylene glycol mono(meth)acrylate, ethoxyheptapropylene glycol mono(meth)acrylate, ethoxyhexapropylene glycol mono(meth)acrylate, ethoxyoctapropylene glycol butylene glycol mono(meth)acrylate, ethoxynonapropylene glycol mono(meth)acrylate, ethoxydecapropylene glycol mono(meth)acrylate, ethoxytributylene glycol mono(meth)acrylate, ethoxytetrabutylene glycol mono(meth)acrylate, ethoxypentabtylene glycol mono(meth)acrylate, ethoxyhexabtylene glycol mono(meth)acrylate, ethoxyheptabtylene glycol mono(meth)acrylate, ethoxyhexabtylene glycol mono(meth)acrylate, ethoxyoctabtylene glycol mono(meth)acrylate, ethoxynonabtylene glycol mono(meth)acrylate, ethoxydecabutylene glycol mono(meth)acrylate, and the like.

[0018] <(C) component> The photoradical polymerization initiator, which is component (C) contained in the photocurable resin composition of the present invention, is not particularly limited as long as it is a compound that generates radical species when exposed to ultraviolet light, etc. Examples of the photoradical polymerization initiator include acetophenone-based photoradical polymerization initiators, benzoin-based photoradical polymerization initiators, benzophenone-based photoradical polymerization initiators, thioxanthone-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, and titanocene-based photoradical polymerization initiators. Among these, acetophenone-based photoradical polymerization initiators and acylphosphine oxide-based photoradical polymerization initiators are preferred because of their superior rapid curing properties with low cumulative light exposure.

[0019] Examples of the acetophenone-based photoradical polymerization initiator include, but are not limited to, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer. Commercially available acetophenone-based photoradical polymerization initiators include IRGACURE184, IRGACUR1173, IRGACURE2959, and IRGACURE127 (manufactured by BASF), and ESACUREKIP-150 (manufactured by Lamberti Spa).

[0020] Examples of the acylphosphine oxide-based photoradical polymerization initiator include, but are not limited to, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products of the acylphosphine oxide-based photoradical polymerization initiator include IRGACURE TPO, IRGACURE 819, and IRGACURE 819DW (manufactured by BASF).

[0021] The amount of component (C) is preferably in the range of 0.1 to 15 parts by mass, more preferably 0.3 to 7 parts by mass, and particularly preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total of components (A) and (B). Furthermore, the amount of component (C) may be in the range of 0.4 to 1.6 parts by mass, per 100 parts by mass of the total of components (A) and (B). By keeping the amount within the above range, a photocurable resin composition can be obtained that exhibits even superior rapid curing properties with low cumulative light exposure and that produces a flexible cured product.

[0022] <(D) component> The component (D) contained in the photocurable resin composition of the present invention is not particularly limited as long as it is a polyfunctional (meth)acrylic monomer having tetrafunctional or more. When combined with the other components of the present invention, the component (D) can be rapidly cured with low cumulative light exposure to obtain a cured product with low elasticity. It is preferable that the component (D) is pentafunctional or more, as this provides superior rapid curing properties with low cumulative light exposure.

[0023] The component (D) is not particularly limited, and examples thereof include ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. These polymerizable monomers can be used alone or in combination of two or more.

[0024] The amount of component (D) is preferably in the range of 0.1 to 15 parts by mass, more preferably 0.2 to 5 parts by mass, and particularly preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). By being within the above range, a photocurable resin composition can be obtained that has even better rapid curing properties with low cumulative light exposure and that can give a flexible cured product.

[0025] <(E) component> There are no particular limitations on the polyether plasticizer that does not have a (meth)acryloyl group, which is component (E) contained in the photocurable resin composition of the present invention, but by combining it with other components of the present invention, a photocurable resin composition can be obtained that has excellent fast curing properties when exposed to low cumulative light doses and that can give a flexible cured product.

[0026] The polyether skeleton refers to a skeleton having an alkylene oxide, such as polyethylene oxide, polypropylene oxide, or polybutylene glycol. The number of repeating alkylene oxide units is not particularly limited, but is, for example, 3 to 300, more preferably 5 to 100, and particularly preferably 10 to 60. The number-average molecular weight of component (E) is not particularly limited, but is, for example, 200 to 30,000, preferably 350 to 10,000, and particularly preferably 500 to 5,000. Unless otherwise specified, the number-average molecular weight is calculated using size exclusion chromatography (SEC) in terms of standard polystyrene. By ensuring that the molecular weight is within the above range, a photocurable resin composition can be obtained that exhibits excellent rapid curing properties with low cumulative light exposure and produces a flexible cured product.

[0027] Commercially available products of component (E) include, but are not limited to, PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#15400, PEG#2000, PEG#4000, PEG#6000, PEG#1100, PEG#2000, Uniol D-700, D-1000, D1200, D2000, D4000, PB-500, PB-700, PB-1000, and PB-2000 (manufactured by NOF Corporation).

[0028] The amount of component (E) added is not particularly limited, but is, for example, 30 to 200 parts by mass, more preferably 35 to 150 parts by mass, and particularly preferably 40 to 100 parts by mass, of component (E) relative to 100 parts by mass of the total of components (A) and (B). By keeping the amount within the above range, a photocurable resin composition can be obtained that exhibits even better rapid curing properties with low cumulative light exposure and that can yield a flexible cured product.

[0029] <Optional ingredients> Additives such as various elastomers such as styrene copolymers, organic peroxides, polythiols, silane coupling agents, inorganic fillers, organic fillers, storage stabilizers, antioxidants, light stabilizers, rust inhibitors, solvents, pigments, dyes, flame retardants, tackifiers, and surfactants can be used in the photocurable resin composition of the present invention, as long as they do not impair the object of the present invention.

[0030] The photocurable resin composition of the present invention preferably does not contain a bifunctional (meth)acrylate, from the viewpoint of obtaining a flexible, low-elasticity cured product. Examples of bifunctional (meth)acrylates include 1,9-nonanediol di(meth)acrylate, glycerin di(meth)acrylate, neopentyl glycol di(meth)acrylate, and dicyclopentenyl diacrylate. If a bifunctional (meth)acrylate is contained, it is preferably contained in an amount of less than 30% by weight, more preferably less than 1% by weight, and even more preferably less than 0.1% by weight, based on the total amount of all components of the photocurable resin composition. It is particularly preferred that the photocurable resin composition of the present invention does not contain a bifunctional (meth)acrylate. Note that, in the present invention, a trifunctional (meth)acrylate may be contained within a range that does not impair the object of the present invention. In one embodiment, the photocurable resin composition of the present invention does not contain a trifunctional (meth)acrylate.

[0031] The inorganic filler is not particularly limited, but examples thereof include glass, fumed silica, alumina, talc, mica, ceramics, silicone rubber powder, calcium carbonate, aluminum hydroxide, aluminum nitride, carbon powder, kaolin clay, dried clay minerals, and dried diatomaceous earth, and particularly preferably glass, fumed silica, talc, and mica.

[0032] The fumed silica can be blended to adjust the viscosity of the photocurable resin or to improve the mechanical strength of the cured product. Preferably, silica that has been hydrophobized with organochlorosilanes, polyorganosiloxane, hexamethyldisilazane, or the like can be used. Specific examples of silica include commercially available products manufactured by Nippon Aerosil, such as Aerosil R974, R972, R972V, R972CF, R805, R812, R812S, R816, R8200, RY200, RX200, RY200S, and R202. These may be used alone or in combination.

[0033] Examples of the organic filler include polyethylene, polypropylene, nylon, cross-linked acrylic, cross-linked polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral, and polycarbonate. Also included are organic hollow fillers such as MMA-AN-MAN copolymers.

[0034] The amount of the filler added is not particularly limited, but is, for example, in the range of 0.01 to 500 parts by mass, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.5 to 150 parts by mass, per 100 parts by mass of the total amount of components (A) and (B). These may be used alone or in combination.

[0035] <Manufacturing method> The photocurable resin composition of the present invention can be produced by a conventional method, for example, by blending predetermined amounts of components (A) to (E) and other optional components and mixing them using a mixing means such as a planetary mixer at a temperature of preferably 10 to 70°C, more preferably 20 to 50°C, and particularly preferably room temperature (25°C), for preferably 0.1 to 5 hours, more preferably 30 to 3 hours, and particularly preferably around 60 minutes.

[0036] <Curing method> The photocurable resin composition of the present invention can be cured by irradiation with light such as ultraviolet light, visible light, or active energy rays. The term "light" as used herein refers to light in a broad sense, including various active energy rays such as radiation such as α-rays and β-rays, electromagnetic waves such as γ-rays and X-rays, electron beams (EB), ultraviolet light of about 100 to 400 nm, and visible light of about 400 to 800 nm. The light source used for curing is not particularly limited, and examples include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, halogen lamps, xenon lamps, LEDs, fluorescent lamps, sunlight, and electron beam irradiation devices. From the viewpoint of the properties of the cured product, the low-integral light dose irradiation dose is, for example, 7.5 kJ / m. 2 or more, and at least 10 kJ / m 2 It is preferable that:

[0037] <Cured product> A cured product obtained by irradiating the photocurable resin composition of the present invention with light is also an aspect of the present invention. The cured product more preferably satisfies the following characteristic value (1) or characteristic value (2), and particularly preferably satisfies both characteristic value (1) and characteristic value (2).

[0038] (1) Storage modulus of cured material after low-integrated light irradiation Each photocurable resin composition was placed on the stage of a rheometer capable of UV irradiation (MARS3 manufactured by Thermo Fisher Scientific K.K.), and the curing rate was 7.5 kJ / m 2The elastic modulus (G'2) when irradiated with an integrated light dose of 100 to 2000 Pa is measured under the following conditions. In order to obtain a flexible, low-elasticity cured product in the present invention, the elastic modulus (G'2) is preferably in the range of 100 to 2000 Pa, more preferably 150 to 1700 Pa, and particularly preferably 200 to 1400 Pa.

[0039] <Rheometer measurement conditions> Geometry: P25 Gap: 1.0 mm Frequency: 1Hz Measurement temperature: 25℃.

[0040] (2) Fast curing with low cumulative light exposure Each photocurable resin composition is set on the stage of a rheometer capable of UV irradiation (MARS3 manufactured by Thermo Fisher Scientific K.K.), and the storage modulus is measured at appropriate times under the following conditions when continuously irradiated with ultraviolet light: 7.5 kJ / m 2 The storage modulus at the time of irradiation with an integrated light dose of 15.0 kJ / m is defined as G'2. 2 The storage modulus when irradiated with this low cumulative light dose is defined as G'1, and the value of G'2 / G'1 (rapid curing property with low cumulative light dose irradiation) is calculated. In the present invention, from the viewpoint of excellent rapid curing property with low cumulative light dose irradiation, G'2 / G'1 is preferably in the range of 0.90 to 1.50, more preferably 0.95 to 1.45, and particularly preferably 0.97 to 1.40.

[0041] <Rheometer measurement conditions> Geometry: P25 Gap: 1.0 mm Frequency: 1Hz Measurement temperature: 25℃.

[0042] <Application method> The photocurable resin composition of the present invention can be applied to a substrate by known methods for applying adhesives or coating materials, such as dispensing using an automatic coater, spraying, inkjet printing, screen printing, gravure printing, dipping, spin coating, or the like.

[0043] <(3) Viscosity measurement> The viscosity (Pa·s) of the photocurable resin composition is measured using a cone-plate viscometer (manufactured by Brookfield) under the following measurement conditions: In the present invention, the viscosity is preferably 0.01 to 15 Pa·s, more preferably 0.03 to 10 Pa·s, and particularly preferably 0.05 to 5 Pa·s, from the viewpoint of ease of application.

[0044] [Measurement conditions] Cone type Shear rate: 38S -1 Temperature: 25℃.

[0045] <Application> The photocurable resin composition of the present invention can be used in a variety of fields, including the automotive, electrical and electronic parts, and aerospace industries. Because of its excellent rapid curing properties with low cumulative light exposure and the ability to produce flexible cured products, particularly preferred applications include a resin for bonding liquid crystal display display parts and protective panels; an elastic curable resin for adjusting the surface pressure applied in the lamination direction between stacked cells of fuel cells, sensors, and secondary batteries (see JP 2009-158381 A); and the like. A laminate formed using the photocurable resin composition of the present invention also constitutes one aspect of the present invention. That is, one embodiment of the present invention is a laminate formed by laminating a first adherend, a cured product obtained by curing the photocurable resin composition of the present invention, and a second adherend, in this order. For example, when the photocurable resin composition of the present invention is used as a bonding resin, the first adherend is a liquid crystal display display part, and the second adherend is a protective panel. [Example]

[0046] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to these examples.

[0047] <Preparation of Photocurable Resin Composition> Each component was collected in the parts by mass shown in Table 1 and mixed in a mixer for 60 minutes at room temperature (25°C) in the dark to obtain a photocurable resin composition. The detailed amounts added are shown in Table 1, and all values ​​are expressed in parts by mass.

[0048] <Component (A)> a1: One-terminated polyether-based urethane acrylate with a weight-average molecular weight of 20,000 (manufactured by Negami Chemical Industrial Co., Ltd.) <Comparative ingredient for ingredient (A)> a'1: a double-ended polyether-based urethane acrylate with a weight-average molecular weight of 41,000 (Mitsubishi Chemical Corporation, Shiko UV-3700B) <(B) component> b1: Ethoxydiethylene glycol monoacrylate (Miramer M170 manufactured by Toyo Chemicals Co., Ltd.) b2: Methoxynonaethylene glycol monoacrylate (AM-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.) <Comparative component of (B) ingredient> b'1: Isobornyl acrylate (IBXA manufactured by Osaka Organic Chemical Industry Ltd.) b'2: 2-Hydroxyethyl methacrylate (Acryester HO manufactured by Mitsubishi Rayon Co., Ltd.) <(C) component> c1: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Double Cure 173 manufactured by Double Bond Chemical Ind. Co., Ltd.) <(D) component> d1: Dipentaerythritol hexaacrylate (DPHA manufactured by Daicel Allnex Co., Ltd.) d2: Ditrimethylolpropane tetraacrylate (AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.) <Comparative ingredients for component (D)> d'1: Isocyanuric acid EO-modified di- and triacrylate (M-313 manufactured by Toagosei Co., Ltd.) <(E) component> e1: Polypropylene glycol having a number average molecular weight of 2000 and a repeating number of alkylene oxides of 34 (UNIOL D2000 manufactured by NOF Corporation) <Comparative ingredient for (E) ingredient> e'1: Polyether-based bifunctional acrylate (14EGA manufactured by Kyoeisha Chemical Co., Ltd.) e'2: Acrylic polymer plasticizer (UP1000 manufactured by Toagosei).

[0049] <Preparation of Comparative Example 10> 13 parts by mass of polyisoprene (UC203M) having methacryloyl groups, 57 parts by mass of polyisoprene-based plasticizer, 30 parts by mass of phenoxyethyl acrylate, and 3 parts by mass of Double Cure 173 were added and mixed in a mixer for 60 minutes at room temperature (25°C) in the dark to obtain Comparative Example 10, a photocurable resin composition.

[0050] The test methods (1) to (3) used in the examples and comparative examples in Table 1 are as follows.

[0051] (1) Storage modulus of cured material after low-integrated light irradiation Each photocurable resin composition was placed on the stage of a rheometer capable of UV irradiation (MARS3 manufactured by Thermo Fisher Scientific K.K.), and the curing rate was 7.5 kJ / m 2 The storage modulus (G'2) when irradiated with an integrated light dose of 100 to 2000 Pa was measured under the following conditions. The results are shown in Table 1. In order to obtain a flexible, low-elasticity cured product in the present invention, the storage modulus (G'2) is preferably in the range of 100 to 2000 Pa, more preferably 150 to 1700 Pa, and particularly preferably 200 to 1400 Pa.

[0052] <Rheometer measurement conditions> Geometry: P25 Gap: 1.0 mm Frequency: 1Hz Measurement temperature: 25℃.

[0053] (2) Fast curing with low cumulative light exposure Each photocurable resin composition was set on the stage of a rheometer capable of UV irradiation (MARS3 manufactured by Thermo Fisher Scientific K.K.), and the storage modulus was measured at appropriate times under the following conditions when continuously irradiated with ultraviolet light: 7.5 kJ / m 2 The storage modulus at the time of irradiation with an integrated light dose of 15.0 kJ / m is defined as G'2. 2 The storage modulus when irradiated with this low cumulative light dose is defined as G'1, and the value of G'2 / G'1 (rapid curing property with low cumulative light dose irradiation) is calculated. In the present invention, from the viewpoint of excellent rapid curing property with low cumulative light dose irradiation, G'2 / G'1 is preferably in the range of 0.90 to 1.50, more preferably 0.95 to 1.45, and particularly preferably 0.97 to 1.40.

[0054] <Rheometer measurement conditions> Geometry: P25 Gap: 1.0 mm Frequency: 1Hz Measurement temperature: 25℃.

[0055] <(3) Viscosity measurement> The viscosity (Pa s) of the photocurable resin composition was measured using a cone-plate viscometer (manufactured by Brookfield) under the following measurement conditions. The results are shown in Table 1. In the present invention, the viscosity is preferably 0.01 to 15 Pa s, more preferably 0.03 to 10 Pa s, and particularly preferably 0.05 to 5 Pa s, from the viewpoint of ease of application.

[0056] [Measurement conditions] Cone type Shear rate: 38S -1 Temperature: 25℃.

[0057] [Table 1]

[0058] [Table 2]

[0059] As can be seen from Examples 1 to 7 in Table 1, it was confirmed that the present invention is a photocurable resin composition that exhibits excellent rapid curing properties when irradiated with a low cumulative light dose and that can give a flexible cured product.

[0060] Comparative Example 1 in Table 1 is a photocurable resin composition that does not contain the component (E) of the present invention, but it produces a hard cured product and exhibits poor rapid curing properties with low cumulative light dose irradiation. Comparative Example 2 is a photocurable resin composition that uses e'1, which is not the component (E) of the present invention, but it produces a hard cured product and exhibits poor rapid curing properties with low cumulative light dose irradiation. Comparative Example 3 is a photocurable resin composition that uses e'2, which is not the component (E) of the present invention, but it produces a liquid with low cumulative light dose irradiation. Comparative Example 4 is a photocurable resin composition that uses a'1, which is not the component (A) of the present invention, but it produces a hard cured product. Comparative Example 5 is a photocurable resin composition that uses b'1, which is not the component (B) of the present invention, but it produces a hard cured product. Comparative Example 6 is a photocurable resin composition that uses b'2, which is not the component (B) of the present invention, but it produces a liquid with low cumulative light dose irradiation. Comparative Example 7 is a composition that does not contain the component (B) of the present invention, but it produces a hard cured product. Comparative Example 8 is a photocurable resin composition using d'1, which is not the component (D) of the present invention, and shows poor rapid curing properties when exposed to low cumulative light doses. Comparative Example 9 is a composition that does not contain the component (D) of the present invention, but is liquid when exposed to low cumulative light doses. Comparative Example 10 in Table 2 is a composition corresponding to the prior art, but shows poor rapid curing properties when exposed to low cumulative light doses. [Industrial Applicability]

[0061] The present invention relates to a photocurable resin composition that has excellent rapid curing properties when irradiated with a low cumulative light dose and that gives a flexible cured product, and therefore can be used in a variety of fields and is therefore industrially useful.

Claims

1. A photocurable resin composition comprising the following components (A) to (E), wherein the component (A) is contained in an amount of 30 to 70 parts by mass, the component (C) is contained in an amount of 0.1 to 15 parts by mass, the component (D) is contained in an amount of 0.1 to 15 parts by mass, and the component (E) is contained in an amount of 30 to 200 parts by mass, relative to 100 parts by mass of the total of the components (A) and (B): Component (A): a monofunctional urethane (meth)acrylate having a polyether skeleton; Component (B): a monofunctional (meth)acrylic monomer having a polyether skeleton and not having a urethane skeleton; Component (C): photoradical polymerization initiator; Component (D): a polyfunctional (meth)acrylic monomer having tetrafunctional or higher functionality; and Component (E): A polyether-based plasticizer having no (meth)acryloyl group.

2. Fast curing with low cumulative light exposure (G'2 (7.5 kJ / m ２ ) / G'1 (15.0 kJ / m ２ 2. The photocurable resin composition according to claim 1, wherein the ratio of the saturation coefficient to the viscosity coefficient is in the range of 0.90 to 1.

50.

3. 3. The photocurable resin composition according to claim 1, wherein the component (A) is contained in an amount of 35 to 65 parts by mass per 100 parts by mass of the total of the components (A) and (B).

4. The photocurable resin composition according to any one of claims 1 to 3, characterized in that the photocurable resin composition contains 0.2 to 5 parts by mass of the component (D) relative to 100 parts by mass of the total of the components (A) and (B).

5. 5. The photocurable resin composition according to claim 1, wherein the number of repeating alkylene oxide moieties in the component (E) is 3 to 300.

6. 6. The photocurable resin composition according to claim 1, wherein the viscosity at 25° C. is 0.01 to 15 Pa·s.

7. 7.5 kJ / m ２ 7. The photocurable resin composition according to claim 1, wherein the cured product obtained by irradiating the composition with ultraviolet light has a storage modulus (G′2) of 100 to 2000 Pa.

8. 8. The photocurable resin composition according to claim 1, which does not contain a bifunctional (meth)acrylate.

9. A cured product obtained by curing the photocurable resin composition according to any one of claims 1 to 8.

10. A laminate obtained by laminating materials using the photocurable resin composition according to any one of claims 1 to 8.

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