Photopolymerizable compositions, cured products, and optical components

Abstract

Provided is a photopolymerizable composition which contains: one or more types of compound selected from a compound represented by formula (1) and a compound represented by formula (2); a polymerizable compound; and a photopolymerization initiator. Further provided are a cured article and optical member which use the same.

Description

[Technical Field]

[0001] This invention relates to a photopolymerizable composition containing an ultraviolet absorber. Furthermore, this invention relates to cured products and optical components using the photopolymerizable composition. [Background technology]

[0002] The effects of various wavelengths of light directly entering the human eye on the retina have attracted attention, and there are concerns that ultraviolet (UV) and blue light, in particular, can damage the retina and cause eye diseases. When using devices equipped with displays, such as liquid crystal displays, electroluminescent displays, smartphones, and tablet devices, users look directly at the screen of the display, which contains a light source. In recent years, the effects of UV light on the retina when using image display devices and small devices for extended periods have attracted attention. For this reason, attempts have been made to reduce the effects of UV light on the user's eyes by equipping these devices with UV-cut filters. UV absorbers are used in such UV-cut filters.

[0003] Furthermore, in recent years, there has been a growing need for UV-cut filters that block ultraviolet light in the long-wavelength region around 400 nm.

[0004] Patent Document 1 describes an invention relating to a photopolymerizable composition comprising an ultraviolet absorber having a specific structure that selectively absorbs light around a wavelength of 400 nm, a polymerizable monomer, a photopolymerization initiator, and a solvent. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2017-119700 [Overview of the project] [Problems that the invention aims to solve]

[0006] UV absorbers can experience a decrease in their UV absorption performance over time due to light exposure. In particular, UV absorbers whose maximum absorption wavelength is located on the longer wavelength side of the ultraviolet region tend to have poor light resistance, and their UV absorption performance is more prone to decline over time. Therefore, in recent years, there has been a growing demand for further improvements in the light resistance of UV absorbers.

[0007] Furthermore, when a UV absorber is included in a photopolymerizable composition, the exposure light is absorbed by the UV absorber when the photopolymerizable composition is cured by irradiation with light. As a result, it is difficult for active species such as radicals to be generated from the photopolymerization initiator by the exposure light, and the degree of curing of the resulting cured product may be insufficient. Consequently, cured products obtained by curing a photopolymerizable composition containing a UV absorber may have insufficient solvent resistance.

[0008] Furthermore, when a UV absorber is included in a photopolymerizable composition, the resulting cured product tends to contain a large amount of decomposition products of the photopolymerization initiator and residues of unreacted photopolymerization initiators. Therefore, when the cured product is irradiated with light for a long period of time, the decomposition products of the photopolymerization initiator and residues of unreacted photopolymerization initiators present in the cured product decompose over time, generating reactive species such as radicals. These reactive species attack the UV absorber, and the UV absorption performance tends to decrease over time.

[0009] Therefore, an object of the present invention is to provide a photopolymerizable composition that can form a cured product with excellent light resistance and solvent resistance. Another object of the present invention is to provide a cured product and an optical component. [Means for solving the problem]

[0010] The present invention provides the following: <1> At least one compound selected from the compounds represented by formula (1) and the compounds represented by formula (2), Polymerizable compounds and Photopolymerization initiator, A photopolymerizable composition containing the following: [Chemical formula] In formulas (1) and (2), R 1 , R 2 , R 11 and R 12 each independently represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or an ethylenically unsaturated bond-containing group, R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, an anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group or an ethylenically unsaturated bond-containing group, Y 1 , Y 2 , Y 11 , Y 12 , Y 13 and Y 14 each independently represents an electron-withdrawing group; Y 1 and Y 2 may be bonded to form a ring; Y 11 and Y 12 may be bonded to form a ring; Y 13 and Y 14 may be bonded to form a ring; R 1 and R 3 may be bonded to form a ring; R 3 and R 4 may be bonded to form a ring; R 2 and R 4 may be bonded to form a ring. <2> The compound represented by the above formula (1) is the compound represented by the following formula (3), The compound represented by the above formula (2) is the compound represented by the following formula (4), The photopolymerizable composition according to <1>; [ka] In equations (3) and (4), R 1 , R 2 , R 11 and R 12 Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an ethylenically unsaturated bond-containing group. R 3 and R 4 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, or an ethylenically unsaturated bond-containing group. R 5 , R 6 , R 13 , R 14 , R 15 and R 16 Each of these independently represents a hydrogen atom or a substituent; R 1 and R 3 They may be joined together to form a ring; R 3 and R 4 They may be joined together to form a ring; R 2 and R 4 They may be joined together to form a ring; R 5 and R 6 They may be joined together to form a ring; R 13 and R 14 They may be joined together to form a ring; R 15 and R 16 They may be joined together to form a ring. <3> R in equation (3) 3 and R 4One of the atoms is a hydrogen atom, and the other is a halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, alkylamino group, anilino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, or an ethylenically unsaturated bond-containing group. <2> The photopolymerizable composition described above. <4> The polymerizable compound described above is a compound having two or more ethylenically unsaturated bond-containing groups. <1> ~ <3> A photopolymerizable composition as described in any one of the following. <5> The above photopolymerization initiator is at least one selected from acetophenone compounds, acylphosphine compounds, and benzophenone compounds. <1> ~ <4> A photopolymerizable composition as described in any one of the following. <6> Furthermore, it contains resin, <1> ~ <5> A photopolymerizable composition as described in any one of the following. <7> The above resin includes an alkali-soluble resin. <6> The photopolymerizable composition described above. <8> The above resin is at least one selected from (meth)acrylic resin, polystyrene resin, polyester resin, polyurethane resin, polythiourethane resin, polyimide resin, epoxy resin, polycarbonate resin, cyclic olefin resin, and cellulose acylate resin. <6> or <7> The photopolymerizable composition described above. <9> It is an adhesive or glue. <1> ~ <8> A photopolymerizable composition as described in any one of the following. <10> <1> ~ <9> A cured product obtained by curing any one of the photopolymerizable compositions described in the following. <11> <10> An optical component containing the cured product described above. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a photopolymerizable composition that can form cured products with excellent light resistance and solvent resistance. Furthermore, the present invention can provide cured products and optical components. [Modes for carrying out the invention]

[0012] The details of the present invention will be described in detail below. In this specification, when groups (atomic groups) are not explicitly labeled as substituted or unsubstituted, the term includes both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, 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 specification, total solids refers to the sum of the components of a composition excluding the solvent. In this specification, "(meth)acrylate" refers to both acrylate and methacrylate, or either of them; "(meth)acrylic" refers to both acrylic and methacrylic, or either of them; "(meth)allyl" refers to both allyl and metharyl, or either of them; and "(meth)acryloyl" refers to both acryloyl and methacryloyl, or either of them. In this specification, the term "process" refers not only to an independent process, but also to any process that achieves its intended function, even if it cannot be clearly distinguished from other processes. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as polystyrene equivalent values ​​measured by gel permeation chromatography (GPC).

[0013] <Photopolymerizable composition> The photopolymerizable composition of the present invention is At least one compound selected from the compounds represented by formula (1) and the compounds represented by formula (2), Polymerizable compounds and Photopolymerization initiator, It is characterized by containing [the specified compound]. Hereinafter, the compound represented by formula (1) and the compound represented by formula (2) will be collectively referred to as the specified compound.

[0014] The photopolymerizable composition of the present invention can form cured products with excellent light resistance and solvent resistance. The specific compound contained in the photopolymerizable composition of the present invention has excellent light resistance, making it difficult for the specific compound to decompose or denature due to light irradiation, and thus enabling the formation of cured products with excellent light resistance. Furthermore, since this specific compound has relatively high transmittance to short-wave ultraviolet light (for example, light with a wavelength of 350 nm or less), when the photopolymerizable composition is cured by irradiating it with light, it does not hinder the generation of active species such as radicals from the photopolymerization initiator by exposure light, and the photopolymerizable composition can be sufficiently cured by light irradiation. Moreover, since the specific compound has excellent absorption performance of light around 400 nm, it is presumed to act as a sensitizer for the photopolymerization initiator, and is presumed to further promote the generation of active species such as radicals from the photopolymerization initiator by exposure light. For this reason, the photopolymerizable composition of the present invention can form cured products with excellent solvent resistance. In addition, since the specific compound has excellent absorption performance of light around 400 nm, by using the photopolymerizable composition of the present invention, it is possible to form cured products with excellent shielding performance of light around 400 nm.

[0015] In the photopolymerizable composition of the present invention, when at least one selected from acetophenone compounds, acylphosphine compounds, and benzophenone compounds is used as the photopolymerization initiator, a cured product with particularly excellent light resistance and solvent resistance can be formed.

[0016] The following describes each component contained in the photopolymerizable composition.

[0017] <<Specific compounds>> The photopolymerizable composition of the present invention contains at least one compound (specific compound) selected from the compound represented by formula (1) and the compound represented by formula (2). [ka] In equations (1) and (2), R 1 , R 2 , R 11 and R 12Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an ethylenically unsaturated bond-containing group. R 3 and R 4 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, or an ethylenically unsaturated bond-containing group. Y 1 , Y 2 , Y 11 , Y 12 , Y 13 and Y 14 Each of these independently represents an electron-withdrawing group; Y 1 and Y 2 They may be joined together to form a ring; Y 11 and Y 12 They may be joined together to form a ring; Y 13 and Y 14 They may be joined together to form a ring; R 1 and R 3 They may be joined together to form a ring; R 3 and R 4 They may be joined together to form a ring; R 2 and R 4 They may be joined together to form a ring.

[0018] R in equation (1) 1 and R 2 The alkyl group represented by, and R of formula (2) 11 and R 12The alkyl group represented by is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 15 carbon atoms, and particularly preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. The alkyl group may have substituents. Examples of substituents include the groups listed as substituent T later described, with alkoxy groups, aryloxy groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, and aryloxycarbonyl groups being preferred, and alkoxycarbonyl groups being more preferred. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, sec-butyl group, tert-butyl group, n-hexyl group, n-octyl group, n-decyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, 2-ethylbutyl group, 2-ethylhexyl group, 3,5,5-trimethylhexyl group, 2-hexyldecyl group, 2-octyldecyl group, 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctyl group, isostearyl group, isopalmityl group, vinyl group, allyl group, prenyl group, geranyl group, oleyl group, propargyl group, cyclohexyl group, cyclopentyl group, ethoxycarbonylpropyl group, ethoxycarbonylpentyl group, butoxycarbonylpropyl group, and 2-ethylhexyloxycarbonylpropyl group.

[0019] R in equation (1) 1 and R 2 The aryl group represented by, and the R in formula (2) 11 and R 12 The aryl group represented is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may have substituents. Examples of substituents include those listed as substituent T later. Specific examples of aryl groups include phenyl group, p-tolyl group, naphthyl group, metachlorophenyl group, and orthohexadecanoylaminophenyl group. The aryl group is preferably a phenyl group.

[0020] R in formula (1) 1 and R 2 The acyl group represented by, and R in formula (2) 11 and R 12 The acyl group represented by is preferably an acyl group having 2 to 30 carbon atoms. The acyl group may have a substituent. Examples of the substituent include the groups exemplified by substituent T described later. Specific examples of the acyl group include an acetyl group, a pivaloyl group, a 2-ethylhexanoyl group, a stearoyl group, a benzoyl group, a p-methoxyphenylcarbonyl group, and the like.

[0021] R in formula (1) 1 and R 2 The carbamoyl group represented by, and R in formula (2) 11 and R 12 The carbamoyl group represented by is preferably a carbamoyl group having 1 to 30 carbon atoms. The carbamoyl group may have a substituent. Examples of the substituent include the groups exemplified by substituent T described later. Specific examples of the carbamoyl group include an N,N-dimethylcarbamoyl group, an N,N-diethylcarbamoyl group, a morpholinocarbonyl group, an N,N-di-n-octylaminocarbonyl group, an N-n-octylcarbamoyl group, and the like.

[0022] R in formula (1) 1 and R 2 The alkoxycarbonyl group represented by, and R in formula (2) 11 and R 12 The alkoxycarbonyl group represented by includes an alkoxycarbonyl group having 2 to 30 carbon atoms. The alkoxycarbonyl group may have a substituent. Examples of the substituent include the groups exemplified by substituent T described later.

[0023] R in formula (1) 1 and R 2 The aryloxycarbonyl group represented by, and R in formula (2) 11 and R 12The aryloxycarbonyl group represented by includes aryloxycarbonyl groups having 7 to 30 carbon atoms. The aryloxycarbonyl group may have substituents. Examples of substituents include those listed as substituent T later.

[0024] R in equation (1) 1 and R 2 The ethylenically unsaturated bond-containing group represented by, and the R of formula (2) 11 and R 12 Examples of ethylenically unsaturated bond-containing groups represented by include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, (meth)acryloyloxy groups, (meth)acryloylamino groups, vinylphenyl groups, and groups represented by formula (R100).

[0025] *-X R1 -Y R1 -Z R1 ...(R100)

[0026] In formula (R100), X R1 This is a single bond, -C(=O)- *1 , -C(=O)O- *1 Or -C(=O)NRx 1 - *1 Represents Rx 1 represents a hydrogen atom, an alkyl group, or an aryl group. *1 is Y R1 This represents a bonding relationship with, Y R1 represents a single bond or a divalent linking group, Z R1 represents a vinyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamino group, or vinylphenyl group.

[0027] Rx 1 The alkyl group represented by is preferably an alkyl group having 1 to 30 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc. 1The aryl group represented by is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Specific examples include the phenyl group, p-tolyl group, and naphthyl group. 1 It is preferable that it is a hydrogen atom.

[0028] X R1 is -C(=O)NH- *1 It is preferable that this be the case.

[0029] Y R1 Examples of divalent linking groups represented by include hydrocarbon groups, -NH-, -S(=O)2-, -O-, -C(=O)-, -OC(=O)-, -C(=O)O-, -NHC(=O)-, -C(=O)NH-, and groups formed by combining two or more of these. Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups, with aliphatic hydrocarbon groups being preferred. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Furthermore, the cyclic aliphatic hydrocarbon group may be monocyclic or fused. Also, the cyclic aliphatic hydrocarbon group may have a crosslinking structure. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have substituents. Examples of substituents include substituent T, which will be described later. For example, a hydroxyl group is an example of a substituent. Y R1 The divalent linking group represented by is preferably a hydrocarbon group, or a group formed by linking two or more hydrocarbon groups by a single bond or a divalent linking group. Examples of linking groups that link two or more hydrocarbon groups include -NH-, -S(=O)2-, -O-, -C(=O)-, -OC(=O)-, -C(=O)O-, -NHC(=O)-, and -C(=O)NH-, and is preferably -O-, -C(=O)-, -OC(=O)-, -C(=O)O-, -NHC(=O)-, or -C(=O)NH-.

[0030] Z R1The group is preferably a (meth)acryloyloxy group or a vinylphenyl group, and more preferably a (meth)acryloyloxy group.

[0031] R in equation (1) 1 and R 2 , and also R in equation (2) 11 and R 12 Preferably, each of these is independently an alkyl group, an acyl group, a carbamoyl group, or an ethylenically unsaturated bond-containing group.

[0032] R in equation (1) 3 and R 4 Examples of halogen atoms represented by this include fluorine, chlorine, and bromine atoms.

[0033] R in equation (1) 3 and R 4 The alkyl group represented by is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms. The alkyl group is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. The alkyl group may have substituents. Examples of substituents include the groups listed as substituent T later described. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-cyanoethyl group, benzyl group, 2-ethylhexyl group, vinyl group, allyl group, prenyl group, geranyl group, oleyl group, propargyl group, cyclohexyl group, cyclopentyl group, 2-hydroxyethyl group, and 2-hydroxypropyl group, with methyl group and tert-butyl group being preferred, and methyl group being more preferred from the viewpoint of ease of synthesis.

[0034] R in equation (1) 3 and R 4The aryl group represented by is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may have substituents. Examples of substituents include those listed as substituent T later. Specific examples of aryl groups include the phenyl group, the paratolyl group, and the naphthyl group.

[0035] R in equation (1) 3 and R 4 The alkoxy group represented by is preferably an alkoxy group having 1 to 30 carbon atoms. The alkoxy group may have substituents. Examples of substituents include those listed as substituent T later. Specific examples of alkoxy groups include methoxy groups and ethoxy groups.

[0036] R in equation (1) 3 and R 4 The aryloxy group represented is preferably an aryloxy group having 6 to 30 carbon atoms. The aryloxy group may have substituents. Examples of substituents include those listed as substituent T later. Specific examples of aryloxy groups include phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, and 2-tetradecanoylaminophenoxy.

[0037] R in equation (1) 3 and R 4 The acyloxy group represented by is preferably an acyloxy group having 2 to 30 carbon atoms. The acyloxy group may have substituents. Examples of substituents include those listed as substituent T later.

[0038] R in equation (1) 3 and R 4 The alkylamino group represented by is preferably an alkylamino group having 1 to 30 carbon atoms. The alkylamino group may have substituents. Examples of substituents include those listed as substituent T later.

[0039] R in equation (1) 3 and R 4The anilino group represented by is preferably an anilino group having 6 to 40 carbon atoms, more preferably an anilino group having 6 to 30 carbon atoms, even more preferably an anilino group having 6 to 20 carbon atoms, particularly preferably an anilino group having 6 to 15 carbon atoms, and most preferably an anilino group having 6 to 12 carbon atoms. The anilino group may have substituents. Examples of substituents include the group described in substituent T below.

[0040] R in equation (1) 3 and R 4 The acylamino group represented by is preferably an acylamino group having 2 to 30 carbon atoms, more preferably an acylamino group having 2 to 20 carbon atoms, even more preferably an acylamino group having 2 to 15 carbon atoms, and particularly preferably an acylamino group having 2 to 10 carbon atoms. The acylamino group may have substituents. Examples of substituents include the group described in substituent T below.

[0041] R in equation (1) 3 and R 4 The alkylsulfonylamino group represented by is preferably an alkylsulfonylamino group having 2 to 30 carbon atoms, more preferably an alkylsulfonylamino group having 2 to 20 carbon atoms, even more preferably an alkylsulfonylamino group having 2 to 15 carbon atoms, and particularly preferably an alkylsulfonylamino group having 2 to 10 carbon atoms. The alkylsulfonylamino group may have substituents. Examples of substituents include the group described in substituent T below.

[0042] R in equation (1) 3 and R 4The arylsulfonylamino group represented by is preferably an arylsulfonylamino group having 6 to 40 carbon atoms, more preferably an arylsulfonylamino group having 6 to 30 carbon atoms, even more preferably an arylsulfonylamino group having 6 to 20 carbon atoms, particularly preferably an arylsulfonylamino group having 6 to 15 carbon atoms, and most preferably an arylsulfonylamino group having 6 to 12 carbon atoms. The arylsulfonylamino group may have substituents. Examples of substituents include the group described in substituent T below.

[0043] R in equation (1) 3 and R 4 The alkylthio group represented by is preferably an alkylthio group having 1 to 30 carbon atoms, more preferably an alkylthio group having 1 to 20 carbon atoms, even more preferably an alkylthio group having 1 to 15 carbon atoms, particularly preferably an alkylthio group having 1 to 10 carbon atoms, and most preferably an alkylthio group having 1 to 8 carbon atoms. The alkylthio group may be linear or branched. The alkylthio group may have substituents. Examples of substituents include those described in substituent T below.

[0044] R in equation (1) 3 and R 4 The arylthio group represented by is preferably an arylthio group having 6 to 40 carbon atoms, more preferably an arylthio group having 6 to 30 carbon atoms, even more preferably an arylthio group having 6 to 20 carbon atoms, particularly preferably an arylthio group having 6 to 15 carbon atoms, and most preferably an arylthio group having 6 to 12 carbon atoms. The arylthio group may have substituents. Examples of substituents include the group described in substituent T below.

[0045] R in equation (1) 3 and R 4 The ethylenically unsaturated bond-containing group represented by is R in formula (1). 1 and R 2 The ethylenically unsaturated bond-containing group represented by, and the R of formula (2) 11 and R 12The groups described above are examples of ethylenically unsaturated bond-containing groups represented by [the symbol].

[0046] R in equation (1) 3 and R 4 Each of these is preferably independently a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group.

[0047] Furthermore, from the viewpoint of extending the maximum absorption wavelength, in equation (1), R 3 and R 4 Preferably, one of the atoms is a hydrogen atom, and the other is a halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, alkylamino group, anilino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, or an ethylenically unsaturated bond-containing group. 3 and R 4 It is more preferable that one of them is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an aryloxy group, R 3 and R 4 It is even more preferable that one of the atoms is a hydrogen atom and the other is an alkyl group.

[0048] R in equation (1) 1 and R 3 They may be bonded together to form a ring, R 3 and R 4 They may be bonded together to form a ring, R 2 and R 4 These groups may be bonded together to form a ring. The ring formed by the bonding of these groups is preferably a 5-membered or 6-membered ring. The formed ring may have substituents. Examples of substituents include the group described in substituent T below.

[0049] Y in equation (1) 1 and Y 2 , and Y in equation (2) 11 , Y 12 , Y 13 and Y 14Each of these groups independently represents an electron-withdrawing group. The electron-withdrawing groups represented by these groups are preferably substituents with a positive Hammett substituent constant σp value. Examples of electron-withdrawing groups include cyano groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfonyl groups, sulfinyl groups, and sulfamoyl groups. Preferred acyl groups are acetyl groups, propionyl groups, pivaloyl groups, benzoyl groups, and 4-methoxybenzoyl groups. Preferred alkoxycarbonyl groups are methoxycarbonyl groups, ethoxycarbonyl groups, 2-hydroxyethoxycarbonyl groups, 2-(3-trimethoxysilylpropylaminocarbonyloxy)ethoxycarbonyl groups, 2-(3-triethoxysilylpropylaminocarbonyloxy)ethoxycarbonyl groups, and 2-ethylhexylcarbonyloxy groups. The ally-oxycarbonyl group is preferably a phenoxycarbonyl group or a 4-methoxyphenoxycarbonyl group. The carbamoyl group is preferably an unsubstituted carbamoyl group, an N,N-dimethylcarbamoyl group, an N,N-diethylcarbamoyl group, an morpholinocarbamoyl group, an N,N-di-n-octylcarbamoyl group, or an Nn-octylcarbamoyl group. The sulfonyl group is preferably a methanesulfonyl group, an ethanesulfonyl group, an octanesulfonyl group, or a benzenesulfonyl group. The sulfinyl group is preferably a methanesulfinyl group, an ethanesulfinyl group, an octanesulfinyl group, or a benzenesulfinyl group. The sulfamoyl group is preferably an unsubstituted sulfamoyl group or an N,N-dimethylsulfamoyl group. The electron-withdrawing group is preferably a cyano group or a carbamoyl group, and more preferably a carbamoyl group.

[0050] In equation (1), Y 1 and Y 2 They may be bonded together to form a ring, and Y is used because it can further improve the light resistance of the resulting cured product. 1 and Y 2 Preferably, they are bonded together to form a ring.

[0051] In equation (2), Y 11 and Y 12They may be bonded together to form a ring, and Y is used because it can further improve the light resistance of the resulting cured product. 11 and Y 12 It is preferable that they are bonded together to form a ring. Also, Y 13 and Y 14 They may be bonded together to form a ring, and Y is used because it can further improve the light resistance of the resulting cured product. 13 and Y 14 Preferably, they are bonded together to form a ring.

[0052] Y 1 and Y 2 A ring formed by the bonding of Y 11 and Y 12 The ring formed by the bonding of, and Y 13 and Y 14 The ring formed by the bonding of these groups is preferably a 5-membered or 6-membered ring. Specifically, examples include a 5-pyrazolone ring, an isoxazolin-5-one ring, a pyrazolidine-3,5-dione ring, a barbiturate ring, a thiobarbiturate ring, a dihydropyridine-2,6-dione ring, etc., with the 5-pyrazolone ring, isoxazolin-5-one ring, pyrazolidine-3,5-dione ring and barbiturate ring being preferred, the pyrazolidine-3,5-dione ring and barbiturate ring being more preferred, and the pyrazolidine-3,5-dione ring being particularly preferred. The ring formed by the bonding of the above groups may further have substituents. Examples of substituents include the group described in substituent T below.

[0053] (substituent T) Examples of substituent T include the following groups. Halogen atoms (e.g., chlorine atoms, bromine atoms, iodine atoms); Alkyl groups [linear, branched, and cyclic alkyl groups. Specifically, linear or branched alkyl groups (preferably linear or branched alkyl groups having 1 to 30 carbon atoms, e.g., methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl groups (preferably cycloalkyl groups having 3 to 30 carbon atoms, e.g., cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group), bicycloalkyl groups (preferably bicycloalkyl groups having 5 to 30 carbon atoms, i.e., monovalent groups obtained by removing one hydrogen atom from bicycloalkanes having 5 to 30 carbon atoms, e.g., bicyclo[1,2,2]heptan-2-yl group, bicyclo[2,2,2]octane-3-yl group), and also include tricyclo structures with many cyclic structures. The alkyl groups in the substituents described below (for example, alkyl groups of alkylthio groups) also represent alkyl groups of this concept. Alkenyl groups [including linear, branched, and cyclic alkenyl groups. Specifically, linear or branched alkenyl groups (preferably linear or branched alkenyl groups having 2 to 30 carbon atoms, e.g., vinyl group, allyl group, prenyl group, geranyl group, oleyl group), cycloalkenyl groups (preferably cycloalkenyl groups having 3 to 30 carbon atoms, i.e., monovalent groups obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms, e.g., 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group), and bicycloalkenyl groups (preferably bicycloalkenyl groups having 5 to 30 carbon atoms, i.e., monovalent groups obtained by removing one hydrogen atom from a bicycloalkene having one double bond, e.g., bicyclo[2,2,1]hepto-2-en-1-yl group, bicyclo[2,2,2]octo-2-en-4-yl group).] Alkynyl group (preferably a linear or branched alkynyl group having 2 to 30 carbon atoms; for example, an ethynyl group or a propargyl group);

[0054] Aryl group (preferably an aryl group having 6 to 30 carbon atoms; for example, phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl group); Heterocyclic groups (preferably monovalent groups obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound, and more preferably 5- or 6-membered aromatic heterocyclic groups having 1 to 20 carbon atoms; for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group); Cyano group; Hydroxyl group; Nitro group; Carboxyl group; Alkoxy groups (preferably linear or branched alkoxy groups having 1 to 30 carbon atoms; for example, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group); Aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms; for example, phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group); Heterocyclic oxy groups (preferably heterocyclic oxy groups having 2 to 30 carbon atoms; for example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group); Acyloxy group (preferably formyloxy group, C2-C30 alkylcarbonyloxy group, C6-C30 arylcarbonyloxy group; for example, formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group);

[0055] Carbamoyloxy group (preferably a carbamoyloxy group having 1 to 30 carbon atoms; for example, N,N-dimethylcarbamoyloxy group, N,N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N,N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group); Alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 30 carbon atoms; for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, t-butoxycarbonyloxy group, n-octylcarbonyloxy group); Aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 30 carbon atoms; for example, phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group); Amino group (preferably an amino group, an alkylamino group having 1 to 30 carbon atoms, or an anilino group having 6 to 30 carbon atoms; for example, an amino group, a methylamino group, a dimethylamino group, anilino group, an N-methyl-anilinino group, or a diphenylamino group); Acylamino group (preferably formylamino group, C2-C30 alkylcarbonylamino group, C6-C30 arylcarbonylamino group; for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group);

[0056] Aminocarbonylamino group (preferably an aminocarbonylamino group having 1 to 30 carbon atoms; for example, carbamoylamino group, N,N-dimethylaminocarbonylamino group, N,N-diethylaminocarbonylamino group, morpholinocarbonylamino group); Alkoxycarbonylamino groups (preferably alkoxycarbonylamino groups having 2 to 30 carbon atoms; for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group); Aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms; for example, phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group); Sulfamoylamino group (preferably a sulfamoylamino group having 0 to 30 carbon atoms; for example, sulfamoylamino group, N,N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group); Alkyl or arylsulfonylamino groups (preferably alkylsulfonylamino groups having 1 to 30 carbon atoms, or arylsulfonylamino groups having 6 to 30 carbon atoms; for example, methylsulfonylamino groups, butylsulfonylamino groups, phenylsulfonylamino groups, 2,3,5-trichlorophenylsulfonylamino groups, p-methylphenylsulfonylamino groups); Mercapto group; Alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms; for example, methylthio group, ethylthio group, n-hexadecylthio group); Arylthio group (preferably an arylthio group having 6 to 30 carbon atoms; for example, phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group); Heterocyclic thio group (preferably a heterocyclic thio group having 2 to 30 carbon atoms; for example, 2-benzothiazolylthio group, 1-phenyltetrazole-5-ylthio group);

[0057] Sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms; for example, N-ethylsulfamoyl group, N-(3-dodecyloxypropyl)sulfamoyl group, N,N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N-(N'-phenylcarbamoyl)sulfamoyl group); sulfo group; Alkyl or arylsulfinyl groups (preferably alkylsulfinyl groups having 1 to 30 carbon atoms, or arylsulfinyl groups having 6 to 30 carbon atoms; for example, methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group); Alkyl or arylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms, or an arylsulfonyl group having 6 to 30 carbon atoms; for example, a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, or a p-methylphenylsulfonyl group);

[0058] Acyl group (preferably formyl group, C2-C30 alkylcarbonyl group, C7-C30 arylcarbonyl group, or C4-C30 heterocyclic carbonyl group bonded to a carbonyl group at a carbon atom. For example, acetyl group, pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, 2-pyridylcarbonyl group, 2-furylcarbonyl group); Aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms; for example, phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group); Alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 30 carbon atoms; for example, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group, n-butoxycarbonyl group, 2-ethylhexyloxycarbonyl group); Carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms; for example, carbamoyl group, N-methylcarbamoyl group, N,N-dimethylcarbamoyl group, N,N-di-n-octylcarbamoyl group, N-(methylsulfonyl)carbamoyl group); Aryl or heterocyclic azo group (preferably an arylazo group having 6 to 30 carbon atoms, or a heterocyclic azo group having 3 to 30 carbon atoms; for example, a phenylazo group, a p-chlorophenylazo group, or a 5-ethylthio-1,3,4-thiadiazole-2-ylazo group); Imide group (preferably N-succinimide group, N-phthalimide group); Phosphino group (preferably a phosphino group having 2 to 30 carbon atoms; for example, dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group) A phosphinyle group (preferably a phosphinyle group having 2 to 30 carbon atoms; for example, a phosphinyle group, a dioctyloxyphosphinyle group, or a diethoxyphosphinyle group); A phosphenyloxy group (preferably a phosphenyloxy group having 2 to 30 carbon atoms; for example, a diphenoxyphosphenyloxy group or a dioctyloxyphosphenyloxy group); A phosphenylamino group (preferably a phosphenylamino group having 2 to 30 carbon atoms; for example, a dimethoxyphosphenylamino group or a dimethylaminophosphenylamino group); Ethylene unsaturated bond-containing groups (e.g., vinyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamino group, and vinylphenyl group).

[0059] Of the groups listed above, those having hydrogen atoms may have one or more hydrogen atoms substituted with the substituent T mentioned above. Examples of such substituents include alkylcarbonylaminosulfonyl groups, arylcarbonylaminosulfonyl groups, alkylsulfonylaminocarbonyl groups, and arylsulfonylaminocarbonyl groups. Specific examples include methylsulfonylaminocarbonyl groups, p-methylphenylsulfonylaminocarbonyl groups, acetylaminosulfonyl groups, and benzoylaminosulfonyl groups.

[0060] The specific compound is preferably the compound represented by formula (1) because it has high solubility in solvents and readily forms a cured product with suppressed surface irregularities.

[0061] Furthermore, for the reason that it is easy to form a cured product with excellent light resistance, the compound represented by formula (1) above is preferably the compound represented by formula (3) below. Furthermore, for the reason that it is easy to form a cured product with excellent light resistance, the compound represented by formula (2) above is preferably the compound represented by formula (4) below. [ka] In equations (3) and (4), R 1 , R 2 , R 11 and R 12 Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an ethylenically unsaturated bond-containing group. R3 and R 4 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, or an ethylenically unsaturated bond-containing group. R 5 , R 6 , R 13 , R 14 , R 15 and R 16 Each of these independently represents a hydrogen atom or a substituent; R 1 and R 3 They may be joined together to form a ring; R 3 and R 4 They may be joined together to form a ring; R 2 and R 4 They may be joined together to form a ring; R 5 and R 6 They may be joined together to form a ring; R 13 and R 14 They may be joined together to form a ring; R 15 and R 16 They may be joined together to form a ring.

[0062] R in equation (3) 1 and R 2 R in equation (1) 1 and R 2 It is synonymous with [the above].

[0063] R in equation (3) 3 and R 4 R in equation (1) 3 and R 4 This is synonymous with the same thing. From the perspective of extending the maximum absorption wavelength, R 3 and R 4Preferably, one of the atoms is a hydrogen atom, and the other is a halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, alkylamino group, anilino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, or an ethylenically unsaturated bond-containing group. 3 and R 4 It is more preferable that one of them is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an aryloxy group, R 3 and R 4 It is even more preferable that one of the atoms is a hydrogen atom and the other is an alkyl group.

[0064] R in equation (3) 1 and R 3 They may be bonded together to form a ring, R 3 and R 4 They may be bonded together to form a ring, R 2 and R 4 These groups may be bonded together to form a ring. The ring formed by the bonding of these groups is preferably a 5-membered or 6-membered ring. The formed ring may have substituents. Examples of substituents include the group described in substituent T below.

[0065] R in equation (4) 11 and R 12 R in equation (2) 11 and R 12 It is synonymous with [the above].

[0066] R in equation (3) 5 and R 6 , and also R in equation (4) 13 , R 14 , R 15 and R 16 Examples of substituents represented by include the groups described above for substituent T, and are preferably alkyl groups, aryl groups, or heterocyclic groups, more preferably alkyl groups or aryl groups, and even more preferably alkyl groups.

[0067] The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, and most preferably an alkyl group having 1 to 8 carbon atoms. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched. The alkyl group may have substituents. Examples of substituents include the group described above as substituent T.

[0068] The aryl group is preferably an aryl group having 6 to 40 carbon atoms, more preferably an aryl group having 6 to 30 carbon atoms, even more preferably an aryl group having 6 to 20 carbon atoms, particularly preferably an aryl group having 6 to 15 carbon atoms, and most preferably an aryl group having 6 to 12 carbon atoms. The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. The aryl group may have substituents. Examples of substituents include the group described above as substituent T.

[0069] The heterocyclic group preferably contains a 5-membered or 6-membered saturated or unsaturated heterocyclic ring. An aliphatic ring, aromatic ring, or other heterocyclic ring may be fused to the heterocyclic ring. Examples of heteroatoms constituting the ring of the heterocyclic ring include B, N, O, S, Se, and Te, with N, O, and S being preferred. The heterocyclic ring preferably has a free valence (monovalent) carbon atom (the heterocyclic group is bonded at the carbon atom). The preferred number of carbon atoms in the heterocyclic group is 1 to 40, more preferably 1 to 30, and even more preferably 1 to 20. Examples of saturated heterocyclic rings in the heterocyclic group include a pyrrolidine ring, a morpholine ring, a 2-bora-1,3-dioxolane ring, and a 1,3-thiazolidined ring. Examples of unsaturated heterocyclic groups include imidazole rings, thiazole rings, benzothiazole rings, benzoxazole rings, benzotriazole rings, benzoselenaazole rings, pyridine rings, pyrimidine rings, and quinoline rings. Heterocyclic groups may have substituents. Examples of substituents include those described above under substituent T.

[0070] R in equation (3) 5 and R 6 They may be bonded together to form a ring, and R in equation (4) 13 and R 14 They may be bonded together to form a ring, and R in equation (4) 15 and R 16 These groups may bond to form a ring. The ring formed by the bonding of these groups is preferably a 5-membered or 6-membered ring. Specific examples of the ring include a hexahydropyridazine ring, a tetrahydropyridazine ring, and a tetrahydrophthalazine ring. The formed ring may have substituents. Examples of substituents include the group described in substituent T below.

[0071] R in equation (3) 5 and R 6 , and also R in equation (4) 13 , R 14 , R 15 and R 16 Each of these is preferably independently a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group or an aryl group, and even more preferably an alkyl group.

[0072] The maximum absorption wavelength of a particular compound is preferably in the wavelength range of 360 to 430 nm, more preferably in the wavelength range of 370 to 420 nm, even more preferably in the wavelength range of 380 to 420 nm, and particularly preferably in the wavelength range of 380 to 405 nm.

[0073] The molar extinction coefficient at the maximum absorption wavelength of a particular compound is preferably 10,000 L / mol·cm or more, more preferably 20,000 L / mol·cm or more, and even more preferably 30,000 L / mol·cm or more. Furthermore, the molar extinction coefficient of the specific compound at a wavelength of 400 nm is preferably 1000 L / mol·cm or higher, more preferably 3000 L / mol·cm or higher, and even more preferably 5000 L / mol·cm or higher.

[0074] The maximum absorption wavelength and molar extinction coefficient of a specific compound can be determined by dissolving the specific compound in ethyl acetate and measuring the spectral spectrum of the solution using a 1 cm quartz cell at room temperature (25°C). Examples of measuring instruments include the UV-1800PC (manufactured by Shimadzu Corporation).

[0075] The specific compounds can be manufactured in accordance with the methods described in Japanese Patent Publication No. 2009-067984, Japanese Patent Publication No. 2009-263616, Japanese Patent Publication No. 2009-263617, and International Publication No. 2017 / 122503.

[0076] Specific examples of particular compounds include compounds with the following structure. In the structural formula shown below, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, and tBu is a tert-butyl group. n Bu is a n-butyl group, Bn is a benzyl group, and Ph is a phenyl group. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0077] The content of the specific compound in the total solids of the photopolymerizable composition is preferably 0.01 to 50% by mass. The lower limit is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. The photopolymerizable composition may contain only one specific compound or two or more specific compounds. If it contains two or more specific compounds, it is preferable that their total amount is within the above range.

[0078] <<Polymerizable compounds>> The photopolymerizable composition of the present invention contains a polymerizable compound. Any compound capable of polymerization and curing by energy application can be used as the polymerizable compound without limitation. The polymerizable compound may be a radical polymerizable compound or a cationic polymerizable compound. Examples of radical polymerizable compounds include compounds having an ethylenically unsaturated bond-containing group. The polymerizable compound is preferably a compound having an ethylenically unsaturated bond-containing group, and more preferably a compound having two or more ethylenically unsaturated bond-containing groups. The upper limit of the number of ethylenically unsaturated bond-containing groups in the polymerizable compound is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less. Examples of ethylenically unsaturated bond-containing groups in the polymerizable compound include vinyl groups, allyl groups, and (meth)acryloyl groups.

[0079] The polymerizable compound may be a monomer, a prepolymer (i.e., a dimer, trimer, or oligomer), a mixture thereof, or a (co)polymer of a compound selected from monomers and prepolymers, but a monomer is preferred.

[0080] The molecular weight of the polymerizable compound is preferably between 100 and 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.

[0081] (Radical polymerizable compounds) Examples of radical polymerizable compounds include compounds having ethylenically unsaturated bond-containing groups. Radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters of unsaturated carboxylic acids, amides of unsaturated carboxylic acids, and (co)polymers of unsaturated carboxylic acids or their esters or amides. Among these, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohols, amides of unsaturated carboxylic acids and aliphatic polyhydric amines, and homopolymers or copolymers thereof are preferred.

[0082] Furthermore, as radical polymerizable compounds, the following can also be used: addition reaction products of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent (e.g., hydroxyl group, amino group, mercapto group, etc.) with a monofunctional or polyfunctional isocyanate compound or epoxy compound; dehydration condensation reaction products of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent with a monofunctional or polyfunctional carboxylic acid; addition reaction products of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having an electrophilic substituent (e.g., isocyanate group, epoxy group, etc.) with a monofunctional or polyfunctional alcohol, amine, or thiol; substitution reaction products of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a leaving substituent (e.g., halogen group, tosyloxy group, etc.) with a monofunctional or polyfunctional alcohol, amine, or thiol; and so on. Moreover, compounds obtained by substituting the above unsaturated carboxylic acid with unsaturated phosphonic acid, styrene, or vinyl ether, etc., can also be used.

[0083] Furthermore, the radical polymerizable compound may be a combination of multiple compounds with different functional numbers or multiple compounds with different types of polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds, etc.).

[0084] The radical polymerizable compound is preferably a (meth)acrylate compound, more preferably a (meth)acrylate compound with two or more functions, even more preferably a (meth)acrylate compound with 2 to 15 functions, even more preferably a (meth)acrylate compound with 2 to 10 functions, and particularly preferably a (meth)acrylate compound with 2 to 6 functions. A monofunctional (meth)acrylate compound can also be used as the polymerizable compound. A monofunctional (meth)acrylate compound and a (meth)acrylate compound with two or more functions can also be used in combination.

[0085] Specific examples of radical polymerizable compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri((meth)acryloyloxyethyl) isocyanurate, pentaerythritol tetra(meth)acrylate ethylene oxide EO (ethylene oxide) modified, and dipentaerythritol hexa(meth)acrylate EO (ethylene oxide) Modified oxides, benzyl (meth)acrylate, 1,3-butylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, hexadiol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth) Acrylate, trimethylolpropane tri(meth)acrylate, tripropylene glycol tri(meth)acrylate, butyl(meth)acrylate, isobornyl(meth)acrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl(meth)acrylate, 4-tert-butylcyclohexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, isobutyl(meth) Examples include acrylate, t-butyl (meth)acrylate, isooctyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, etc.

[0086] Commercially available radical polymerizable compounds include the KAYARAD series from Nippon Kayaku Co., Ltd. (e.g., D-330, D-320, D-310, PET-30, TPA-330, DPHA, DPHA-40H, etc.), the NK ester series from Shin Nakamura Chemical Industry Co., Ltd. (e.g., A-DPH-12E, A-TMMT, A-TMM-3, etc.), the Light Acrylate series from Kyoeisha Chemical Co., Ltd. (e.g., DCP-A, etc.), and Toagosei Co., Ltd. Examples of polyfunctional (meth)acrylate compounds include the Aronics series from ) (e.g., M-305, M-306, M-309, M-450, M-402, TO-1382, etc.), the Viscoat series from Osaka Organic Chemical Industry Co., Ltd. (e.g., V#802, etc.), the Beamset series from Arakawa Chemical Industries, Ltd. (e.g., 504H, 550B, 575, 577, etc.), and the EBECRYL series from Daicel Corporation.

[0087] Radical polymerizable compounds can include (meth)acrylate compounds described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490, as well as compounds introduced as photocurable monomers and oligomers in the Journal of the Adhesion Society of Japan, Vol. 20, No. 7, pp. 300-308 (1984).

[0088] (Cationic polymerizable compounds) Examples of cationic polymerizable compounds include compounds having cationic polymerizable groups. Examples of cationic polymerizable groups include epoxy groups, cyclic ether groups such as oxetanyl groups, and vinyl ether groups, with cyclic ether groups being preferred. Furthermore, it is preferable that the cationic polymerizable compound is a polyfunctional cationic polymerizable compound having two or more cationic polymerizable groups.

[0089] Examples of cationic polymerizable compounds include polyfunctional alicyclic epoxy compounds, polyfunctional heterocyclic epoxy compounds, polyfunctional oxetane compounds, alkylene glycol diglycidyl ethers, and alkylene glycol monovinyl monoglycidyl ethers.

[0090] Specific examples of cationic polymerizable compounds include 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, xylylene bisoxetane, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, cyclohexanedimethanol divinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, 4-hydroxybutyl vinyl ether, and the compounds described in paragraphs 0029 to 0058 of Japanese Patent Application Publication No. 2012-046577.

[0091] Cationic polymerizable compounds can also be (meth)acrylate compounds having cationic polymerizable groups. Specific examples of (meth)acrylate compounds having cationic polymerizable groups include 3,4-epoxycyclohexylmethyl methacrylate. Commercially available examples include Cyclomer M100 manufactured by Daicel Corporation.

[0092] Cationic polymerizable compounds such as the Aronoxetane series (OXT-101, OXT-121, OXT-221, etc.) from Toagosei Co., Ltd., the Celoxide series (2021P) from Daicel Corporation, and alkyl divinyl ether CHDVE, alkyl monovinyl ether EHVE, hydroxyalkyl vinyl ether CHMVE, and hydroxyalkyl vinyl ether HBVE from Nippon Carbide Industries, Ltd. can also be used. Furthermore, the specific examples of epoxy resins described later can also be used.

[0093] The content of polymerizable compounds in the total solids of the photopolymerizable composition is preferably 0.1 to 90% by mass. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less. The photopolymerizable composition may contain only one polymerizable compound or two or more. If it contains two or more polymerizable compounds, it is preferable that their total amount is within the above range.

[0094] <<Photopolymerization initiator>> The photopolymerizable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is a compound that is photosensitive to exposure light and initiates or promotes the polymerization of a polymerizable compound. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. When a radical polymerizable compound is used as the polymerizable compound, the photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is preferably a compound that generates radicals in response to active light with a wavelength of 300 nm or more. When a cationic polymerizable compound is used as the polymerizable compound, the photopolymerization initiator is preferably a photocationic polymerization initiator.

[0095] (Photoradical polymerization initiator) Examples of photoradical polymerization initiators include oxime compounds, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organoboric acid compounds, disulfonic acid compounds, onium salt compounds, acetophenone compounds, acylphosphine compounds, and benzophenone compounds. For the reason that a cured product with superior light resistance and solvent resistance can be formed, acetophenone compounds, acylphosphine compounds, benzophenone compounds, or hexaarylbiimidazole compounds are preferred, acetophenone compounds, acylphosphine compounds, or benzophenone compounds are more preferred, and acetophenone compounds or acylphosphine compounds are even more preferred.

[0096] Examples of acetophenone compounds include aminoacetophenone compounds and hydroxyacetophenone compounds. Examples of acetophenone compounds include those described in Japanese Patent Publication No. 2009-191179 and Japanese Patent Publication No. 10-291969. Examples of commercially available aminoacetophenone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV). Examples of commercially available hydroxyacetophenone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV).

[0097] Examples of acylphosphine compounds include those described in Japanese Patent Publication No. 4225898. Examples of commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins BV).

[0098] Examples of benzophenone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dialkylamino)benzophenones (e.g., 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone), 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, etc., and 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of sensitivity and lightfastness of the resulting cured product.

[0099] Examples of oxime compounds include those described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, and Japanese Patent Publication No. 2016-006475, paragraphs 0073 to 0075. Among oxime compounds, oxime ester compounds are preferred. Examples of commercially available oxime compounds include Irgacure OXE01, Irgacure OXE02 (manufactured by BASF), and Irgacure OXE03 (manufactured by BASF).

[0100] Examples of halogenated hydrocarbon derivatives include Wakabayashi et al., "Bull Chem. Soc. Japan" 42, 2924 (1969), U.S. Patent No. 3905815, Japanese Patent Publication No. 46-004605, Japanese Unexamined Patent Publication No. 48-036281, Japanese Unexamined Patent Publication No. 55-032070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-058241, Japanese Unexamined Patent Publication No. 62-212401, Japanese Unexamined Patent Publication No. 63-070243, Japanese Unexamined Patent Publication No. 63-298339, and MPHutt, "Journal of Heterocyclic Examples of compounds include those described in "Chemistry" 1 (No. 3), (1970), and are preferably oxazole or triazine compounds substituted with a trihalomethyl group.

[0101] Examples of hexaarylbiimidazole compounds include those described in Japanese Patent Publication No. 06-029285, U.S. Patent No. 3,479185, U.S. Patent No. 4,311783, and U.S. Patent No. 4,622286. Specifically, these include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl))4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyphenyl)biimidazole. Examples include 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

[0102] (Photocationic polymerization initiator) The photocationic polymerization initiator is not particularly limited as long as it is a compound that generates a protic acid or Lewis acid upon light irradiation. The photoacid generator is preferably a compound that is sensitive to active light with a wavelength of 300 nm or more, more preferably 300 to 450 nm, and generates an acid. The photoacid generator is preferably a compound that generates an acid with a pKa of 4 or less upon light irradiation, more preferably a compound that generates an acid with a pKa of 3 or less, and even more preferably a compound that generates an acid with a pKa of 2 or less.

[0103] Examples of photocationic polymerization initiators include oximesulfonate compounds, triazine compounds, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, iminosulfonic acid ester compounds, carboxylic acid ester compounds, and sulfonimide compounds.

[0104] Specific examples of photocationic polymerization initiators include compounds described in paragraphs 0061 to 0108 of Japanese Patent Publication No. 2012-046577, paragraphs 0029 to 0030 of Japanese Patent Publication No. 2002-122994, compounds described in paragraphs 0037 to 0063 of Japanese Patent Publication No. 2002-122994, and oximesulfonate compounds described in paragraphs 0081 to 0108 of Japanese Patent Publication No. 2013-210616. A commercially available photocationic polymerization initiator is CPI-210S (manufactured by Sunapro Co., Ltd.).

[0105] The content of the photopolymerization initiator in the total solids of the photopolymerizable composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.3% by mass or more, and more preferably 0.4% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. The photopolymerizable composition may contain only one type of photopolymerization initiator, or it may contain two or more types. If it contains two or more types of photopolymerization initiators, it is preferable that their total amount is within the above range.

[0106] <<Resin>> The photopolymerizable composition of the present invention preferably contains a resin. The resin can be appropriately selected from resins that satisfy various physical properties such as transparency, refractive index, and processability, depending on the application or purpose of the photopolymerizable composition.

[0107] Examples of resins include (meth)acrylic resins, ene-thiol resins, polyester resins, polycarbonate resins, vinyl polymers [e.g., polydiene resins, polyalkene resins, polystyrene resins, polyvinyl ether resins, polyvinyl alcohol resins, polyvinyl ketone resins, polyfluorovinyl resins and polybrominated vinyl resins, etc.], polythioether resins, polyphenylene resins, polyurethane resins, polysulfonate resins, nitrosopolymer resins, polysiloxane resins, polysulfide resins, polythioester resins, polysulfone resins, polysulfonamide resins, polyamide resins, polyimine resins, polyurea resins, polyphosphazene resins, polysilane resins, polysilazane resins, polyfuran resins, polybenzoxazole resins, polyoxadiazole resins, polybenzothiadinophenothiazine resins, polybenzothiazole resins, polypyradinoquinoxaline resins, polyquinoxaline resins, polybenzimidazole resins, polyoxoisoindoline resins, polydioxoisoindoline resins, and polytriazine resins. Examples include polypyridazine resin, polypiperazine resin, polypyridine resin, polypiperidine resin, polytriazole resin, polypyrazole resin, polypyrrolidine resin, polycarborane resin, polyoxabicyclononane resin, polydibenzofuran resin, polyphthalide resin, polyacetal resin, polyimide resin, polyamideimide resin, olefin resin, cyclic olefin resin, epoxy resin, and cellulose acylate resin. It is preferable that the resin be at least one selected from (meth)acrylic resin, polystyrene resin, polyester resin, polyurethane resin, polythiourethane resin, polyimide resin, epoxy resin, polycarbonate resin, and cellulose acylate resin, and more preferably at least one selected from (meth)acrylic resin, polystyrene resin, polyester resin, polyurethane resin, polythiourethane resin, polycarbonate resin, and cellulose acylate resin, for the reasons that it has good compatibility with the specific compounds mentioned above and easily forms a cured product with suppressed surface unevenness.

[0108] Examples of (meth)acrylic resins include polymers containing constituent units derived from (meth)acrylic acid and / or its esters. Specifically, examples include polymers obtained by polymerizing at least one compound selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile.

[0109] Examples of polyester resins include polymers obtained by the reaction of polyols (e.g., ethylene glycol, propylene glycol, glycerin, and trimethylolpropane) with polybasic acids (e.g., aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, etc., and dicarboxylic acids in which the hydrogen atoms of these aromatic rings are substituted with methyl groups, ethyl groups, or phenyl groups, etc.), aliphatic dicarboxylic acids having 2 to 20 carbon atoms (e.g., adipic acid, sebatic acid, and dodecanedicarboxylic acid), or alicyclic dicarboxylic acids (e.g., cyclohexanedicarboxylic acid, etc.)), as well as polymers obtained by ring-opening polymerization of cyclic ester compounds such as caprolactone monomers (e.g., polycaprolactone).

[0110] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and aliphatic epoxy resin. Commercially available epoxy resins may also be used; examples of such commercial products are listed below.

[0111] Examples of commercially available bisphenol A type epoxy resins include jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, and jER1010 (all manufactured by Mitsubishi Chemical Corporation), as well as EPICLON860, EPICLON1050, EPICLON1051, and EPICLON1055 (all manufactured by DIC Corporation). Examples of commercially available bisphenol F type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, and jER4010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON830 and EPICLON835 (both manufactured by DIC Corporation), and LCE-21 and RE-602S (both manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available phenol novolac type epoxy resins include jER152, jER154, jER157S70, and jER157S65 (all manufactured by Mitsubishi Chemical Corporation), and EPICLON N-740, EPICLON N-770, and EPICLON N-775 (both manufactured by DIC Corporation). Examples of commercially available cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, and EPICLON N-695 (all manufactured by DIC Corporation), as well as EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).Examples of commercially available aliphatic epoxy resins include ADEKA RESIN EP series (e.g., EP-4080S, EP-4085S, and EP-4088S; manufactured by ADEKA Corporation), EHPE3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (all manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by Nagase ChemteX Corporation), and ADEKA RESIN. Examples of commercially available epoxy resins include the EP series (e.g., EP-4000S, EP-4003S, EP-4010S, and EP-4011S, etc.; manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, and EPPN-502 (all manufactured by ADEKA Corporation), and jER1031S (manufactured by Mitsubishi Chemical Corporation). Other examples of commercially available epoxy resins include Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).

[0112] As the cellulose acylate resin, the cellulose acylate described in paragraphs 0016 to 0021 of Japanese Patent Publication No. 2012-215689 is preferably used. As the polyester resin, commercially available products such as the Byron series (e.g., Byron 500) manufactured by Toyobo Co., Ltd. can also be used. As the (meth)acrylic resin, the SK Dyne series (e.g., SK Dyne-SF2147) manufactured by Soken Chemical Co., Ltd. can also be used.

[0113] The polystyrene resin is preferably a resin containing 50% by mass or more of repeating units derived from styrene monomers, more preferably a resin containing 70% by mass or more of repeating units derived from styrene monomers, and even more preferably a resin containing 85% by mass or more of repeating units derived from styrene monomers.

[0114] Specific examples of styrene monomers include styrene and its derivatives. Here, styrene derivatives are compounds in which other groups are bonded to styrene, such as alkylstyrenes like o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, and p-ethylstyrene, and substituted styrenes such as hydroxystyrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, and p-chlorostyrene, in which a hydroxyl group, alkoxy group, carboxyl group, halogen, etc., is introduced to the benzene ring of styrene.

[0115] Furthermore, polystyrene resins may contain repeating units derived from monomers other than styrene monomers. Examples of other monomers include alkyl(meth)acrylates such as methyl(meth)acrylate, cyclohexyl(meth)acrylate, methylphenyl(meth)acrylate, and isopropyl(meth)acrylate; unsaturated carboxylic acid monomers such as methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, and cinnamic acid; unsaturated dicarboxylic acid anhydride monomers, which are anhydrides such as maleic anhydride, itaconic acid, ethyl maleic acid, methylitaconic acid, and chloromaleic acid; unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile; and conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene.

[0116] Commercially available polystyrene resins include AS-70 (acrylonitrile-styrene copolymer resin, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) and SMA2000P (styrene-maleic acid copolymer, manufactured by Kawahara Oil & Chemical Co., Ltd.).

[0117] Examples of cyclic olefin resins include (1) polymers containing structural units derived from norbornene compounds, (2) polymers containing structural units derived from monocyclic cyclic olefin compounds other than norbornene compounds, (3) polymers containing structural units derived from cyclic conjugated diene compounds, (4) polymers containing structural units derived from vinyl alicyclic hydrocarbon compounds, and hydrides of polymers containing structural units derived from each of the compounds in (1) to (4). In this specification, polymers containing structural units derived from norbornene compounds and polymers containing structural units derived from monocyclic cyclic olefin compounds include ring-opened polymers of each compound.

[0118] Addition (co)polymers of norbornene compounds are described in Japanese Patent Publication No. 10-007732, Japanese Patent Publication No. 2002-504184, U.S. Patent Publication No. 2004 / 229157, or International Publication No. 2004 / 070463, etc. Polymers of norbornene compounds are obtained by addition polymerization of norbornene compounds (e.g., polycyclic unsaturated compounds of norbornene).

[0119] Hydrogenated polymers of norbornene compounds can be synthesized by addition polymerization or metathesis ring-opening polymerization of norbornene compounds, etc., followed by hydrogenation. Synthesis methods are described, for example, in Japanese Patent Publication Nos. 01-240517, 07-196736, 60-026024, 62-019801, 2003-159767, and 2004-309979.

[0120] Commercially available cyclic olefin resins include the Arton series from JSR Corporation (e.g., Arton G, Arton F, Arton RX4500, etc.) and Zeon Corporation's Zeonor ZF14, ZF16, Zeonex 250, and Zeonex 280.

[0121] The weight-average molecular weight of the resin is preferably 3,000 to 2,000,000. The lower limit of the weight-average molecular weight of the resin is preferably 5,000 or more. The upper limit of the weight-average molecular weight of the resin is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less. Furthermore, when epoxy resin is used, the weight-average molecular weight of the epoxy resin is preferably 100 or more, more preferably 200 to 2,000,000. The upper limit of the weight-average molecular weight of the epoxy resin is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit of the weight-average molecular weight of the epoxy resin is preferably 2,000 or more.

[0122] The weight-average molecular weight of the resin is measured by gel permeation chromatography (GPC). For GPC measurement, an HLC(registered trademark)-8020GPC (manufactured by Tosoh Corporation) is used as the measuring instrument, three TSKgel(registered trademark) Super Multipore HZ-H columns (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation) are used as the columns, and THF (tetrahydrofuran) is used as the eluent. The measurement conditions are a sample concentration of 0.45 mass%, a flow rate of 0.35 ml / min, a sample injection volume of 10 μl, and a measurement temperature of 40°C, and the measurement is performed using an RI detector. A calibration curve is prepared from eight samples of Tosoh Corporation's "Standard Samples TSK standard, polystyrene": "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000", and "n-propylbenzene".

[0123] The resin may be an alkali-soluble resin. Examples of alkali-soluble resins include resins having acidic groups. Examples of acidic groups include carboxyl groups, phosphate groups, sulfonic acid groups, and phenolic hydroxyl groups. There may be only one type of acidic group or two or more types.

[0124] Preferably, the alkali-soluble resin is a linear organic polymer that is soluble in organic solvents and can be developed in a weakly alkaline aqueous solution. Examples of such linear organic polymers include polymers having carboxyl groups in their side chains, such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having carboxyl groups in their side chains, as described in Japanese Patent Publication No. 59-044615, Japanese Patent Publication No. 54-034327, Japanese Patent Publication No. 58-012577, Japanese Patent Publication No. 54-025957, Japanese Patent Publication No. 59-053836, and Japanese Patent Publication No. 59-071048.

[0125] Furthermore, as alkali-soluble resins, resins obtained by adding acid anhydrides to polymers having hydroxyl groups are also useful.

[0126] Alkali-soluble resins may also be resins copolymerized with hydrophilic monomers. Examples of hydrophilic monomers include alkoxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, glycerol (meth)acrylates, (meth)acrylamides, N-methylolacrylamides, secondary or tertiary alkylacrylamides, dialkylaminoalkyl (meth)acrylates, morpholine (meth)acrylates, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazoles, vinyltriazoles, methyl (meth)acrylates, ethyl (meth)acrylates, branched or linear propyl (meth)acrylates, branched or linear butyl (meth)acrylates, or phenoxyhydroxypropyl (meth)acrylates. Other useful hydrophilic monomers include monomers containing tetrahydrofurfuryl groups, phosphate groups, phosphate ester groups, quaternary ammonium bases, ethylene oxy chains, propylene oxy chains, sulfonic acid groups and groups derived from their salts, morpholinoethyl groups, etc.

[0127] Alkali-soluble resins may have ethylenically unsaturated bond-containing groups such as vinyl groups, styrene groups, allyl groups, methallyl groups, and (meth)acryloyl groups in order to improve crosslinking efficiency. Commercially available alkali-soluble resins containing ethylenically unsaturated bond groups include the Dianaal BR series (polymethyl methacrylate (PMMA), e.g., Dianaal BR-80, BR-83, and BR-87; manufactured by Mitsubishi Chemical Corporation), Photomer 6173 (carboxyl group-containing polyurethane acrylic oligomer; manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, and KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (e.g., ACA230AA), Praxel CF200 series (all manufactured by Daicel Corporation), and Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), as well as Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

[0128] Among these various alkali-soluble resins, polyhydroxystyrene resins, (meth)acrylic resins, polystyrene resins, and polysiloxane resins are preferred from the viewpoint of heat resistance, and (meth)acrylic resins are more preferred from the viewpoint of developingability control.

[0129] The weight-average molecular weight of the alkali-soluble resin is preferably 3,000 to 200,000, and more preferably 5,000 to 50,000.

[0130] The acid value of alkali-soluble resins is preferably 30 to 200 mg KOH / g. The lower limit of the acid value is preferably 50 mg KOH / g or higher, and more preferably 70 mg KOH / g or higher. The upper limit of the acid value is preferably 150 mg KOH / g or lower, and more preferably 120 mg KOH / g or lower. The acid value of the resin is measured in accordance with JIS K0070 (1992) and calculated by converting using the formula 1 mmol / g = 56.1 mg KOH / g.

[0131] With regard to alkali-soluble resins, reference can be made to paragraphs 0558 to 0571 of Japanese Patent Application Publication No. 2012-208494 (paragraphs 0685 to 0700 of the corresponding U.S. Patent Application Publication No. 2012 / 0235099) and paragraphs 0076 to 0099 of Japanese Patent Application Publication No. 2012-198408, the contents of which are incorporated herein by reference.

[0132] When the photopolymerizable composition of the present invention is used for lens applications (e.g., eyeglass lenses), the resin is preferably a thermoplastic resin such as a carbonate resin or (meth)acrylic resin (e.g., polymethyl methacrylate (PMMA)), or a thermosetting resin such as a urethane resin. Examples of commercially available carbonate resins include polycarbonate resin composition (trade name: Caliber 200-13, manufactured by Sumitomo Dow Ltd.) and diethylene glycol bisallyl carbonate resin (trade name: CR-39, manufactured by PPG Industries). As for urethane resins, thiourethane resin is preferred. Examples of commercially available thiourethane resins include thiourethane resin monomers (trade names: MR-7, MR-8, MR-10, and MR-174; all are trade names; manufactured by Mitsui Chemicals, Inc.).

[0133] Furthermore, adhesives can be used with the resin. Examples of adhesives include acrylic adhesives, rubber adhesives, and silicone adhesives. Acrylic adhesives are adhesives containing polymers of (meth)acrylic monomers ((meth)acrylic polymers). Examples of adhesives include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, and silicone adhesives. Among these, urethane resin adhesives or silicone adhesives are preferred as adhesives due to their high adhesive strength. Commercially available adhesives may be used, and examples of commercially available products include Toyo Ink Co., Ltd.'s urethane resin adhesive (LIS-073-50U: product name) and Soken Chemical Co., Ltd.'s acrylic adhesive (SK Dyne-SF2147: product name).

[0134] The total light transmittance of the resin is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. In this specification, the total light transmittance of the resin is a value measured based on the content described on pages 225 to 232 of "Experimental Chemistry Course 29 Polymer Materials Medium, 4th Edition" edited by the Chemical Society of Japan (Maruzen, 1992).

[0135] When the photopolymerizable composition contains a resin, the content of the resin in the total solid content of the photopolymerizable composition is preferably 1 to 99% by mass. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less. The photopolymerizable composition may contain only one kind of resin or two or more kinds of resins. When two or more kinds of resins are contained, the total amount thereof is preferably within the above range.

[0136] <<Solvent>> The photopolymerizable composition of the present invention preferably contains a solvent. The solvent can be basically used without particular limitation as long as it can satisfy the solubility of each coexisting component and the coating property when the photopolymerizable composition is formed. The solvent is preferably an organic solvent.

[0137] Examples of the organic solvent include alcohol solvents, ester solvents, ether solvents, ketone solvents, amide solvents, hydrocarbon solvents, halogen solvents, and the like. Specific examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol, propylene glycol, glycerin, and the like. Specific examples of ester solvents include methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionates, and alkyl 2-oxypropionates. Examples include methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethylene carbonate. Specific examples of ether-based solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polyethylene glycol, polypropylene glycol, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, and dioxane. Specific examples of amide solvents include N-methylpyrrolidone, dimethylformamide, and dimethylacetamide. Specific examples of the ketone solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like. Specific examples of the hydrocarbon solvents include toluene, xylene and the like. Specific examples of the halogen solvents include chloroform, methylene chloride and the like. These organic solvents may be used in combination of two or more.

[0138] The organic solvent preferably contains at least one selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

[0139] The content of the solvent in the photopolymerizable composition is preferably 10 to 90% by mass, more preferably 30 to 90% by mass, and still more preferably 50 to 90% by mass. The photopolymerizable composition may contain only one kind of solvent or two or more kinds of solvents. When the photopolymerizable composition contains two or more kinds of solvents, the total amount thereof is preferably within the above range.

[0140] <<Sensitizer>> The photopolymerizable composition of the present invention may contain a sensitizer. Typical sensitizers include compounds described in Crivello [JV Crivello, Adv. in Polymer Sci, 62,1 (1984)]. Specific examples of sensitizers include pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphaquinone, and phenothiazine derivatives. When a sensitizer is included, the sensitizer content is preferably 50 to 200 parts by mass per 100 parts by mass of the photopolymerization initiator.

[0141] <<Other UV absorbers>> The photopolymerizable composition of the present invention may contain ultraviolet absorbers other than the specified compounds described above (hereinafter also referred to as other ultraviolet absorbers).

[0142] The maximum absorption wavelength of other ultraviolet absorbers is preferably in the range of 300 to 380 nm, more preferably in the range of 300 to 370 nm, even more preferably in the range of 310 to 360 nm, and particularly preferably in the range of 310 to 350 nm.

[0143] Other UV absorbers include aminobutadiene-based UV absorbers, dibenzoylmethane-based UV absorbers, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylic acid-based UV absorbers, acrylate-based UV absorbers, and triazine-based UV absorbers, with benzotriazole-based UV absorbers, benzophenone-based UV absorbers, and triazine-based UV absorbers being preferred, and benzotriazole-based UV absorbers and triazine-based UV absorbers being more preferred. Specific examples of other UV absorbers include compounds described in paragraphs 0065 to 0070 of Japanese Patent Publication No. 2009-263616 and compounds described in paragraph 0065 of International Publication No. 2017 / 122503, the contents of which are incorporated herein by reference. Other preferred UV absorbers include 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(4-butoxy-2-hydroxyphenyl)-4,6-di(4-butoxyphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0144] If the photopolymerizable composition contains other ultraviolet absorbers, the content of the other ultraviolet absorbers in the total solids of the photopolymerizable composition is preferably 0.01 to 50% by mass. The lower limit is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less. Furthermore, the total content of the above-mentioned specific compound and other ultraviolet absorbers in the total solid content of the photopolymerizable composition is preferably 0.01 to 50% by mass. The lower limit is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less. The photopolymerizable composition may contain only one other UV absorber, or it may contain two or more other UV absorbers. If it contains two or more other UV absorbers, it is preferable that their total amount is within the above range.

[0145] <<Compounds containing epoxy groups>> The photopolymerizable composition of the present invention may contain a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of epoxy compounds include monofunctional or polyfunctional glycidyl ether compounds and polyfunctional aliphatic glycidyl ether compounds. In addition, compounds having alicyclic epoxy groups may be used as epoxy compounds. Examples of epoxy compounds include compounds having one or more epoxy groups per molecule. Preferably, the epoxy compound has 1 to 100 epoxy groups per molecule. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. The lower limit of epoxy groups is preferably 2 or more. Specific examples of monofunctional epoxy compounds include 2-ethylhexylglycidyl ether. Specific examples of polyfunctional epoxy compounds include 1,4-cyclohexanedimethanol diglycidyl ether and 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

[0146] The epoxy compound may be a low molecular weight compound (e.g., molecular weight less than 1000) or a high molecular weight compound (macromolecule) (e.g., molecular weight of 1000 or more; in the case of a polymer, weight-average molecular weight of 1000 or more). The weight-average molecular weight of the epoxy compound is preferably between 2000 and 100000. The upper limit of the weight-average molecular weight is preferably 10000 or less, more preferably 5000 or less, and even more preferably 3000 or less. Examples of commercially available epoxy compounds include polyfunctional epoxy compounds such as Celoxide 2021P (trade name, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) from Daicel Corporation and Rikaresin DME-100 (trade name, mainly containing 1,4-cyclohexanedimethanol diglycidyl ether) from Shin Nippon Rika Co., Ltd.

[0147] When a photopolymerizable composition contains a compound having an epoxy group, the content of the compound having an epoxy group in the total solid content of the photopolymerizable composition is preferably 0.1 to 50% by mass. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The photopolymerizable composition may contain only one compound having an epoxy group, or it may contain two or more. When it contains two or more compounds having epoxy groups, it is preferable that their total amount is within the above range.

[0148] <<Acid Generator>> The photopolymerizable composition of the present invention may contain an acid generator. The acid generator may be a photoacid generator or a thermal acid generator. In this specification, an acid generator means a compound that generates acid when energy such as heat or light is applied. A thermal acid generator means a compound that generates acid by thermal decomposition. A photoacid generator means a compound that generates acid by light irradiation. Examples of types of acid generators, specific compounds, and preferred examples include compounds described in paragraphs 0066 to 0122 of Japanese Patent Application Publication No. 2008-013646, and these can also be applied to the present invention.

[0149] The thermal acid generator is preferably a compound having a thermal decomposition temperature in the range of 130°C to 250°C, more preferably in the range of 150°C to 220°C. Examples of thermal acid generators include compounds that generate low nucleophilic acids such as sulfonic acids, carboxylic acids, and disulfonylimides upon heating. The acid generated from the thermal acid generator is preferably an acid with a pKa of 4 or less, more preferably an acid with a pKa of 3 or less, and even more preferably an acid with a pKa of 2 or less. For example, sulfonic acids, alkylcarboxylic acids, arylcarboxylic acids, and disulfonylimides substituted with electron-withdrawing groups are preferred. Examples of electron-withdrawing groups include halogen atoms such as fluorine atoms, haloalkyl groups such as trifluoromethyl groups, nitro groups, and cyano groups.

[0150] Examples of photoacid generators include onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, and sulfonate compounds such as imidosulfonates, oximesulfonates, diazodisulfones, disulfones, and ortho-nitrobenzylsulfonates, which decompose upon light irradiation to generate acid. Commercially available photoacid generators include WPAG-469 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), CPI-100P (manufactured by Sunapro Co., Ltd.), and Irgacure290 (BASF Japan Ltd.). In addition, 2-isopropylthioxanthone can also be used as a photoacid generator.

[0151] When the photopolymerizable composition contains an acid generator, the amount of the acid generator is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymerizable compound. The photopolymerizable composition may contain only one type of acid generator or two or more types. When two or more types of acid generators are included, it is preferable that their total amount falls within the above range.

[0152] <<Catalyst>> The photopolymerizable composition of the present invention may contain a catalyst. Examples of catalysts include acid catalysts such as hydrochloric acid, sulfuric acid, acetic acid, and propionic acid, and base catalysts such as sodium hydroxide, potassium hydroxide, and triethylamine. When the photopolymerizable composition contains a catalyst, the catalyst content is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymerizable compound. The photopolymerizable composition may contain only one type of catalyst or two or more types. When two or more types of catalysts are included, it is preferable that their total amount is within the above range.

[0153] <<Silane coupling agent>> The photopolymerizable composition of the present invention can contain a silane coupling agent. According to this aspect, the adhesion of the resulting cured product to the support can be further improved. In the present specification, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, etc., and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Further, examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, a phenyl group, etc., and an amino group, a (meth)acryloyl group and an epoxy group are preferred. Specific examples of the silane coupling agent include the compounds described in paragraph numbers 0018 to 0036 of JP-A No. 2009-288703 and the compounds described in paragraph numbers 0056 to 0066 of JP-A No. 2009-242604, and the contents thereof are incorporated herein. Commercially available products of the silane coupling agent include A-50 (organosilane) of Soken Chemical & Engineering Co., Ltd. The content of the silane coupling agent in the total solid content of the photopolymerizable composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The silane coupling agent may be only one kind or two or more kinds. In the case of two or more kinds, the total amount is preferably within the above range.

[0154] <<Surfactant>> The photopolymerizable composition of the present invention can contain a surfactant. Examples of the surfactant include the surfactants described in paragraph number 0017 of Japanese Patent No. 4502784 and paragraph numbers 0060 to 0071 of JP-A No. 2009-237362.

[0155] As the surfactant, nonionic surfactants, fluorinated surfactants, or silicone surfactants are preferred.

[0156] Commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-5 60, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futegent Examples include 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, and 681 (all manufactured by NEOS Corporation).

[0157] Acrylic compounds that have a molecular structure containing a functional group with a fluorine atom, and in which the fluorine atom-containing functional group is cleaved and the fluorine atom volatilizes when heated, can also be suitably used as fluorine-based surfactants. Examples of such fluorine-based surfactants include the MegaFac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as MegaFac DS-21.

[0158] It is also preferable to use a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorine-based surfactant.

[0159] Block polymers can also be used as fluorinated surfactants.

[0160] Fluorine-based surfactants can also be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom, and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups).

[0161] Fluorine-based surfactants can also be made from fluorine-containing polymers that have ethylenically unsaturated bond-containing groups in their side chains. Examples of commercially available products include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0162] Furthermore, since compounds having linear perfluoroalkyl groups with 7 or more carbon atoms raise concerns regarding their environmental suitability, it is preferable to use fluorine-based surfactants that utilize alternative materials such as perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS).

[0163] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into the side chains or terminals. Commercially available silicone-based surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, and KF-94. Examples include 5. KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (all manufactured by BIC Chemie), etc.

[0164] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Examples of commercially available nonionic surfactants include Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), Solspers 20000 (all manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (all manufactured by Nisshin Chemical Industry Co., Ltd.).

[0165] The surfactant content in the total solids of the photopolymerizable composition is preferably 0.01 to 3.0% by mass, more preferably 0.05 to 1.0% by mass, and even more preferably 0.10 to 0.80% by mass. The surfactant may be one type or two or more types. If two or more types are used, it is preferable that the total amount falls within the above range.

[0166] <<Other additives>> The photopolymerizable composition of the present invention may optionally contain any additives such as antioxidants, light stabilizers, processing stabilizers, anti-aging agents, compatibilizers, and polymerization inhibitors. By appropriately including these components, the various properties of the resulting cured product can be appropriately adjusted.

[0167] <Method for preparing a photopolymerizable composition> The method for preparing the photopolymerizable composition of the present invention is not particularly limited, but for example, it can be prepared by mixing a compound represented by formula (1) or (2), a polymerizable compound, a photopolymerization initiator, and optionally the above-mentioned components.

[0168] When preparing a photopolymerizable composition, each component may be blended together at once, or each component may be dissolved or dispersed in a solvent and then blended sequentially. Furthermore, there are no particular restrictions on the order of addition or working conditions during blending. For example, the photopolymerizable composition may be prepared by simultaneously dissolving or dispersing all components in a solvent, or, if necessary, each component may be prepared as two or more solutions or dispersions and mixed at the time of use (coating) to prepare the photopolymerizable composition.

[0169] When preparing a photopolymerizable composition, it is preferable to mix the components and then filter them using a filter in order to remove foreign matter and reduce defects. Any filter that has been conventionally used for filtration purposes can be used without any particular limitations. For example, filters made of materials such as fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight polyolefin resins) can be used. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0170] The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 2.5 μm, and even more preferably 0.01 to 2.0 μm. If the filter pore size is within the above range, fine foreign matter can be removed more reliably. The nominal value of the filter pore size can be referred to from the filter manufacturer. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), and KITZ Microfilter Corporation can be used.

[0171] Furthermore, it is also preferable to use fibrous filter media as a filter. Examples of fibrous filter media include polypropylene fiber, nylon fiber, and glass fiber. Commercially available products include the SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) from Rokitechno Co., Ltd.

[0172] When using filters, different filters (for example, a first filter and a second filter) may be combined. In this case, filtration may be performed only once or two or more times with each filter. Furthermore, filters with different pore sizes within the range described above may be combined.

[0173] <<Application>> The photopolymerizable composition of the present invention can also be suitably used in applications that may be exposed to sunlight or light including ultraviolet rays. Specific examples include coating materials or films for window glass in residences, facilities, and transportation equipment; interior and exterior materials and paints for residences, facilities, and transportation equipment; components for ultraviolet light sources such as fluorescent lamps and mercury lamps; components for solar cells, precision machinery, electronic and electrical equipment, and display devices; containers or packaging materials for food, chemicals, and pharmaceuticals; agricultural and industrial sheets; textile products and fibers for clothing such as sportswear, stockings, and hats; lenses or coating materials for plastic lenses, contact lenses, eyeglasses, and artificial eyes; optical products such as optical filters, prisms, mirrors, and photographic materials; stationery such as tapes and inks; and signboards, indicators, and their surface coating materials. For further details, please refer to paragraphs 0158 to 0218 of Japanese Patent Application Publication No. 2009-263617, the contents of which are incorporated herein by reference.

[0174] The photopolymerizable composition of the present invention can be preferably used in optical components and the like. For example, it can be preferably used as a photopolymerizable composition for ultraviolet cut filters, lenses, or protective materials. The form of the protective material is not particularly limited, but examples include coating films, films, and sheets. Furthermore, the photopolymerizable composition of the present invention can also be used as an adhesive or bonding agent.

[0175] The photopolymerizable composition of the present invention can also be used in various components of display devices. For example, in the case of liquid crystal display devices, it can be used in various components constituting the liquid crystal display device, such as anti-reflective films, polarizing plate protective films, optical films, phase difference films, adhesives, and tacks. In the case of organic electroluminescent display devices, it can be used in various components constituting the organic electroluminescent display device, such as optical films, polarizing plate protective films in circular polarizers, phase difference films such as quarter-wave plates, adhesives, or tacks.

[0176] <Cured products and their applications> The cured product of the present invention is obtained by curing the photopolymerizable composition of the present invention described above.

[0177] The cured product of the present invention may also be obtained as a molded article formed by molding a photopolymerizable composition into a desired shape. The shape of the molded article can be appropriately selected depending on the application and purpose. Examples include coating film, film, sheet, plate, lens, tubular, and fibrous forms.

[0178] The cured product of the present invention is preferably used as an optical component. Examples of optical components include ultraviolet cut filters, lenses, and protective materials. It can also be used as a polarizing plate.

[0179] Ultraviolet-cutting filters can be used in items such as optical filters, display devices, solar cells, and window glass. While not particularly limited to specific types of display devices, examples include liquid crystal displays and organic electroluminescent displays.

[0180] When the cured product of the present invention is used in a lens, the cured product itself may be formed into a lens shape and used. Alternatively, the cured product of the present invention may be used as a coating film on the lens surface or as an intermediate layer (adhesive layer) in a bonded lens. Examples of bonded lenses include those described in paragraphs 0094 to 0102 of International Publication No. 2019 / 131572, the contents of which are incorporated herein by reference.

[0181] The types of protective materials are not particularly limited, but include protective materials for display devices, protective materials for solar cells, protective materials for window glass, and organic electroluminescent display devices. The shape of the protective material is not particularly limited, but includes coating films, films, and sheets.

[0182] <Optical components> The optical component of the present invention includes the cured product of the present invention described above. The cured product of the present invention may also be obtained as a molded product obtained by molding the photopolymerizable composition of the present invention described above into a desired shape. The shape of the molded product can be appropriately selected depending on the application and purpose. Examples include coating film, film, sheet, plate, lens, tubular, and fibrous shapes.

[0183] The optical component of the present invention may be a component obtained by bonding a polarizing plate and a polarizing plate protective film using the photopolymerizable composition of the present invention.

[0184] Examples of optical components include UV-cut filters, lenses, and protective materials.

[0185] Ultraviolet-cutting filters can be used in items such as optical filters, display devices, solar cells, and window glass. While not particularly limited to specific types of display devices, examples include liquid crystal displays and organic electroluminescent displays.

[0186] Examples of lenses include those formed by shaping the cured product of the present invention into a lens form, and those in which a coating film on the lens surface or an intermediate layer (adhesive layer or bonding layer) of a bonded lens is formed using the photopolymerizable composition of the present invention.

[0187] The types of protective materials are not particularly limited, but include protective materials for display devices, protective materials for solar cells, and protective materials for window glass. The shape of the protective material is not particularly limited, but includes coating films, films, and sheets.

[0188] Another form of optical component is a resin film. Examples of resins used in the photopolymerizable composition for forming the resin film include the resins mentioned above, with (meth)acrylic resins, polyester fibers, cyclic olefin resins, and cellulose acylate resins being preferred, and cellulose acylate resins being more preferred. The photopolymerizable composition containing the cellulose acylate resin may include additives described in paragraphs 0022 to 0067 of Japanese Patent Application Publication No. 2012-215689. Examples of such additives include sugar esters. By adding sugar ester compounds to the photopolymerizable composition containing the cellulose acylate resin, it is possible to reduce overall haze and internal haze without impairing the expression of optical properties, even when heat treatment is not performed before the stretching process. Furthermore, a resin film (cellulose acylate film) using a photopolymerizable composition containing the cellulose acylate resin can be manufactured by the method described in paragraphs 0068 to 0096 of Japanese Patent Application Publication No. 2012-215689. Furthermore, the resin film may have a hard coat layer, as described in paragraphs 0097 to 0113 of Japanese Patent Publication No. 2012-215689, further laminated on it.

[0189] Another form of optical component is an optical component having a laminate of a support and a resin layer.

[0190] The thickness of the resin layer in the above laminate is preferably 1 μm to 2500 μm, and more preferably 10 μm to 500 μm.

[0191] The support material in the above laminate is preferably a material that is transparent to the extent that it does not impair the optical performance. Transparency of the support means that it is optically transparent, and specifically refers to a total light transmittance of 85% or more. The total light transmittance of the support is preferably 90% or more, and more preferably 95% or more.

[0192] A suitable support is a resin film. Examples of resins that make up the resin film include ester resins (e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexanedimethylene terephthalate (PCT), etc.), olefin resins (e.g., polypropylene (PP), polyethylene (PE), etc.), polyvinyl chloride (PVA), and tricellulose acetate (TAC). Among these, PET is preferred in terms of versatility.

[0193] The thickness of the support can be appropriately selected depending on the application or purpose. Generally, a thickness of 5 μm to 2500 μm is preferred, and 20 μm to 500 μm is more preferred.

[0194] Furthermore, the above-mentioned support can also be a peelable support. Such laminates are preferably used in polarizing plates and the like. Here, a peelable support is a support that can be peeled off from the ultraviolet shielding material. The stress when peeling the support from the ultraviolet shielding material is preferably 0.05 N / 25 mm or more and 2.00 N / 25 mm or less, more preferably 0.08 N / 25 mm or more and 0.50 N / 25 mm or less, and even more preferably 0.11 N / 25 mm or more and 0.20 N / 25 mm or less. The stress when peeling the support from the UV shielding material was evaluated by first fixing the surface of a laminate cut to a width of 25 mm and a length of 80 mm to a glass substrate via an acrylic adhesive sheet, and then using a tensile testing machine (RTF-1210 manufactured by A&D Co., Ltd.), gripping one end in the longitudinal direction of the test piece (one side of the 25 mm width), and performing a 90° peel test (in accordance with Japanese Industrial Standard (JIS) K 6854-1:1999 "Adhesives - Test methods for peel strength - Part 1: 90-degree peel") in an atmosphere of 23°C and 60% relative humidity with a crosshead speed (gripping movement speed) of 200 mm / min.

[0195] As a releaseable support, one containing polyethylene terephthalate (PET) as the main component (the component with the highest mass content among the components constituting the support) is preferred. From the viewpoint of mechanical strength, the weight-average molecular weight of PET is preferably 20,000 or more, more preferably 30,000 or more, and even more preferably 40,000 or more. The weight-average molecular weight of PET can be determined by dissolving the support in hexafluoroisopropanol (HFIP) and using the GPC method described above. The thickness of the support is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 0.1 to 75 μm, even more preferably 0.1 to 55 μm, and particularly preferably 0.1 to 10 μm. Furthermore, the support may be subjected to known surface treatments such as corona treatment, glow discharge treatment, or undercoating.

[0196] Another form of the optical component is a laminate having a hard coat layer, a transparent support, and an adhesive or bonding layer laminated in that order. Such a laminate is preferably used as an ultraviolet cut filter or a protective material (protective film, protective sheet). In this form of optical component, it is sufficient if any of the support, hard coat layer, or adhesive or bonding layer contains the cured product of the present invention described above.

[0197] As a hard coat layer, for example, Japanese Patent Publication No. 2013-045045, Japanese Patent Publication No. 2013-043352, Japanese Patent Publication No. 2012-232459, Japanese Patent Publication No. 2012-128157, Japanese Patent Publication No. 2011-131409, Japanese Patent Publication No. 2011-131404, Japanese Patent Publication No. 2011-126162, Japanese Patent Publication No. 2011-075705, Japanese Patent Publication No. 2009-286981, Japanese Patent Publication No. 2009-263567, Japanese Patent Publication No. 2009 The hard coat layers described in Japanese Patent Publication No. 075248, Japanese Patent Publication No. 2007-164206, Japanese Patent Publication No. 2006-096811, Japanese Patent Publication No. 2004-075970, Japanese Patent Publication No. 2002-156505, Japanese Patent Publication No. 2001-272503, International Publication No. 2012 / 018087, International Publication No. 2012 / 098967, International Publication No. 2012 / 086659, and International Publication No. 2011 / 105594 can be applied. The thickness of the hard coat layer is preferably 5 μm to 100 μm in terms of further improving scratch resistance.

[0198] The optical member in this form has an adhesive layer or bonding layer on the side of the support substrate opposite to the side having the hard coat layer. The type of adhesive or bonding agent used for the adhesive layer or bonding layer is not particularly limited, and known adhesives or bonding agents can be used. It is also preferable to use an adhesive or bonding agent that contains the acrylic resin described in paragraphs 0056 to 0076 of Japanese Patent Application Publication No. 2017-142412 and the crosslinking agent described in paragraphs 0077 to 0082 of Japanese Patent Application Publication No. 2017-142412. Furthermore, the adhesive or bonding agent may also contain an adhesion improver (silane compound) described in paragraphs 0088 to 0097 of Japanese Patent Application Publication No. 2017-142412 and an additive described in paragraph 0098 of Japanese Patent Application Publication No. 2017-142412. The adhesive layer or bonding layer can be formed by the method described in paragraphs 0099 to 0100 of Japanese Patent Publication No. 2017-142412. The thickness of the adhesive layer or bonding layer is preferably 5 μm to 100 μm in terms of achieving both adhesive strength and handling properties.

[0199] The optical component of the present invention can be preferably used as a component of a display such as a liquid crystal display (LCD) or an organic electroluminescent display (OLED).

[0200] Examples of liquid crystal display devices include those containing the cured product of the present invention in components such as anti-reflective films, polarizing plate protective films, optical films, phase difference films, adhesives, and bonding agents. The optical component of the present invention may be positioned on either the viewer side (front side) or the backlight side relative to the liquid crystal cell, and it may also be positioned on either the side farther from the liquid crystal cell (outer side) or the side closer to the liquid crystal cell (inner side) relative to the polarizer.

[0201] Examples of organic electroluminescent display devices include those containing the cured product of the present invention in components such as optical films, polarizing plate protective films in circular polarizers, phase difference films such as quarter-wave plates, adhesives, and tacks. By including the cured product of the present invention in the above configuration, degradation of the organic electroluminescent display device due to ambient light can be suppressed. [Examples]

[0202] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the structural formulas shown below, Me is a methyl group, Et is an ethyl group, Bu is a butyl group, tBu is a tert-butyl group, Pr is a propyl group, Ph is a phenyl group, and Ac is an acetyl group.

[0203] <Example of synthesis> (Synthesis Example 1) (Synthesis of Compound (1)-52) Intermediate 1-1 was synthesized according to the following scheme. In the scheme below, the synthesis from p-tholquinone to intermediate 1-1 was carried out by referring to the method described in paragraph 0176 of Japanese Patent Application Publication No. 2016-081035, using p-tholquinone instead of 2-tert-butyl-1,4-benzoquinone. [ka]

[0204] Next, intermediates 1-3 were synthesized according to the following synthesis scheme. 90 g of intermediate 1-1, 73.7 g of intermediate 1-2, and 300 ml of N-methylpyrrolidone were added and mixed, then stirred at 60°C for 1 hour. After cooling to room temperature, 2700 ml of water was added and stirred for 30 minutes. After filtering off the precipitated solid, 300 ml of acetonitrile was added and the mixture was heated under a nitrogen atmosphere under reflux for 1 hour. After cooling to room temperature, the mixture was stirred at room temperature for 1 hour, the solid was filtered off, and washed with 150 ml of acetonitrile to obtain 106 g of intermediate 1-3 (yield 85%). [ka]

[0205] Under a nitrogen atmosphere, 4.0 g of intermediate 1-3, 2.55 g of triethylamine, and 40 ml of N,N-dimethylacetamide were added to a flask and mixed, then stirred for 10 minutes under ice cooling. 3.82 g of 2-ethylhexanoyl chloride was added to the mixture in the flask, and the mixture was stirred at room temperature for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, and then 20 ml of water was added and the mixture was stirred for 30 minutes. After filtering off the precipitated solid, 50 ml of methanol was added, and the mixture was heated under a nitrogen atmosphere for 1 hour under reflux. After cooling to room temperature, the mixture was stirred at room temperature for 1 hour, and then the solid was filtered off and washed with 25 ml of methanol to obtain 5.2 g of compound (1)-52 (yield 85%). 1H-NMR(CDCl3):δ 7.26(m, 6H), 7.18(s, 1H), 7.10(m, 4H), 4.75(2, 4H), 2.62(m, 2H), 2.27(s, 3H), 1.8~1.6(m, 8H), 1.5~1.3(m, 8H), 1.10(m, 6H), 0.94(m, 6H) [ka]

[0206] (Synthesis Example 2) (Synthesis of Compound (1)-64) Intermediate 2 was synthesized using the same method as in Synthesis Example 1, according to the following scheme. [ka] Under a nitrogen atmosphere, 3.0 g of intermediate 2, 1.97 g of triethylamine, and 30 ml of N,N-dimethylacetamide were added to a flask and mixed, then stirred for 10 minutes under ice cooling. 2.95 g of 2-ethylhexanoyl chloride was added to the mixture in the flask, and the mixture was stirred at room temperature for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, and then 15 ml of water was added and the mixture was stirred for 30 minutes. After filtering off the precipitated solid, 40 ml of methanol was added, and the mixture was heated under a nitrogen atmosphere for 1 hour under reflux. After cooling to room temperature, the mixture was stirred at room temperature for 1 hour, and then the solid was filtered off and washed with 20 ml of methanol to obtain 4.1 g of compound (1)-64 (yield 88%). 1 H-NMR (CDCl3): δ 7.30(s, 2H) 7.26(m, 6H), 7.10(m, 4H), 4.76(2, 4H), 2.62(m, 2H), 1.9~1.6(m, 8H), 1.5~1.3(m, 8H), 1.07(t, 6H), 0.94(t, 6H) [ka]

[0207] (Synthesis Example 3) (Synthesis of Compound (1)-46) Compound (1)-46 was synthesized in the same manner as in Synthesis Example 1, except that 2-ethylhexyl bromide was used instead of 2-ethylhexanoyl chloride. 1 H-NMR(CDCl3):δ 7.26(m, 6H)7.11(m, 4H), 6.70(s, 1H), 4.77(s, 2H), 4.75(s, 2H), 3.97(dd, 2H), 3.83(d, 2H), 2.37(s, 3H), 1.8~1.6(m, 18H), 1.0~0.9(m, 12H) [ka]

[0208] <Measurement of maximum absorption wavelength (λmax)> Two mg of each compound listed in the table below was dissolved in 100 mL of ethyl acetate, and then diluted with ethyl acetate to prepare a sample solution with an absorbance in the range of 0.6 to 1.2. The absorbance of each sample solution was measured using a UV-1800PC spectrophotometer (Shimadzu Corporation) in a 1 cm quartz cell. The maximum absorption wavelength (λmax) was measured from the absorption spectrum of each sample solution.

[0209] [Table 1]

[0210] (1)-5, (1)-8, (1)-11, (1)-46, (1)-49, (1)-52, (1)-53, (1)-60, (1)-64, (1)-65, (1)-69, A-1, A-35, A-71, (2)-1, (2)-6, (2)-8, (2)-9, (2)-11, (2)-12: Compounds with the structure shown in the specific examples of the above-mentioned compounds. C-1, C-3: Compounds with the following structures (comparative compounds) [ka]

[0211] <Preparation of photopolymerizable compositions> (Examples 1-50, Comparative Examples 1 and 2) The photopolymerizable compositions of Examples 1-50 and Comparative Examples 1 and 2 were prepared by mixing the following components. UV absorber ···2.0 parts by mass Polymerizable compound...2.6 parts by mass Resin...12.9 parts by mass Photopolymerization initiator ···2.5 parts by mass Solvent (propylene glycol monomethyl ether acetate) ···40.0 parts by mass Solvent (cyclopentanone) ···40.0 parts by mass Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with carbinols at both ends, hydroxyl value 62 mg KOH / g) ... 0.02 parts by mass

[0212] [Table 2] [Table 3]

[0213] (Example 51) The photopolymerizable composition of Example 51 was prepared by mixing the following components. UV absorber (1)-46 ···2.0 parts by mass Polymerizable compound T-2...0.5 part by mass Polymerizable compound T-4...1.5 parts by mass Resin U-3...13.5 parts by mass Photopolymerization initiator V-8 ···2.5 parts by mass Solvent (toluene) ···80.0 parts by mass Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with carbinols at both ends, hydroxyl value 62 mg KOH / g) ... 0.02 parts by mass

[0214] (Example 52) The photopolymerizable composition of Example 52 was prepared by mixing the following components. UV absorber (1)-46 ···2.0 parts by mass Polymerizable compound T-6...10.5 parts by mass Polymerizable compound T-1...5.0 parts by mass Photopolymerization initiator V-1 ···2.2 parts by mass Photopolymerization initiator V-5 ···0.3 parts by mass Solvent (ethyl acetate) ···40.0 parts by mass Solvent (cyclopentanone) ···40.0 parts by mass Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with carbinols at both ends, hydroxyl value 62 mg KOH / g) ... 0.02 parts by mass

[0215] (Example 53) The photopolymerizable composition of Example 53 was prepared by mixing the following components. UV absorber (1)-46 ···2.0 parts by mass Polymerizable compound T-5...5.0 parts by mass Polymerizable compound T-4...4.0 parts by mass Resin U-1...6.5 parts by mass Photopolymerization initiator V-1 ···2.0 parts by mass Photopolymerization initiator V-6 ···0.5 parts by mass Solvent (ethyl acetate) ···40.0 parts by mass Solvent (cyclopentanone) ···40.0 parts by mass Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with carbinols at both ends, hydroxyl value 62 mg KOH / g) ... 0.02 parts by mass

[0216] (Example 54) The photopolymerizable composition of Example 54 was prepared by mixing the following components. UV absorber (1)-46 ···2.0 parts by mass Polymerizable compound T-7...60 parts by mass Polymerizable compound T-8...25 parts by mass Polymerizable compound T-9...15 parts by mass Photopolymerization initiator V-9 ···8.0 parts by mass

[0217] (Examples 55-59) The photopolymerizable compositions of Examples 55 to 59 were prepared in the same manner as in Example 54, except that UV absorber (1)-46 was replaced with the same amount of UV absorber (1)-5, UV absorber (1)-52, UV absorber (1)-64, UV absorber A-71, or UV absorber (2)-8.

[0218] The details of the ingredients listed using the abbreviations above are as follows:

[0219] (UV absorber) (1)-5, (1)-8, (1)-11, (1)-46, (1)-49, (1)-52, (1)-53, (1)-60, (1)-64, (1)-65, (1)-69, A-1, A-35, A-71, (2)-1, (2)-6, (2)-8, (2)-9, (2)-11, (2)-12: Compounds with the structure shown in the specific examples of the above-mentioned compounds. C-1, C-3: Compounds with the structures described above (comparative compounds) UV-1: Tinuvin 326 (manufactured by BASF)

[0220] (polymerizable compound) T-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a compound having two or more ethylenically unsaturated bond-containing groups) T-2:NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a compound having two or more ethylenically unsaturated bond-containing groups) T-3: Light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd., a compound having two or more ethylenically unsaturated bond-containing groups) T-4: Benzyl methacrylate T-5: Beamset 577 (3-6 functional urethane acrylate, manufactured by Arakawa Chemical Industries, Ltd.) T-6: FA-512M (Dicyclopentenyloxyethyl methacrylate, manufactured by Showa Denko Materials Co., Ltd.) T-7: Cyclomer M100 (3,4-Epoxycyclohexylmethyl methacrylate, manufactured by Daicel Corporation) T-8:OXT-221:3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, a bifunctional oxetane, manufactured by Toagosei Co., Ltd.) T-9: Celoxide 2021P (3',4'-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate, bifunctional epoxy, manufactured by Daicel Corporation)

[0221] (resin) U-1: 40% by mass propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid (75 / 25 [mass ratio]) copolymer (weight-average molecular weight 12000) U-2: Dianaal BR-80 (manufactured by Mitsubishi Chemical Corporation) U-3: Arton RX4500 (manufactured by JSR Corporation, Tg 140℃, cyclic polyolefin resin)

[0222] (Photopolymerization initiator) V-1: Omnirad TPO (manufactured by IGM Resins BV, a photoradical polymerization initiator, an acylphosphine compound) V-2: Omnirad 2959 (manufactured by IGM Resins BV, photoradical polymerization initiator, hydroxyacetophenone compound) V-3: 4,4'-Bis(diethylamino)benzophenone (photoradical polymerization initiator, benzophenone compound) V-4: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole(o-Cl-HABI) (photoradical polymerization initiator, hexaarylbiimidazole compound) V-5: IRGACURE-OXE01 (BASF Corporation, photoradical polymerization initiator, oxime compound) V-6 Omnirad 907 (manufactured by IGM Resins BV, photoradical polymerization initiator, aminoacetophenone compound) V-7 Omnirad 369 (manufactured by IGM Resins BV, photoradical polymerization initiator, aminoacetophenone compound) V-8 Omnirad 819 (manufactured by IGM Resins BV, photoradical polymerization initiator, acylphosphine compound) V-9: CPI-210S (manufactured by Sunapro Co., Ltd., photocationic polymerization initiator, sulfonium salt)

[0223] <Manufacturing of UV-cut filters> (Manufacturing Example 1) The photopolymerizable compositions from Examples 1 to 59 were spin-coated onto a 50 mm x 50 mm glass substrate (1737, Corning) to a film thickness of 1.5 μm after deposition, and dried at 100°C for 2 minutes to form a photopolymerizable composition layer. Subsequently, the photopolymerizable composition layer was exposed to 1000 mJ / cm² using an i-line stepper exposure system (UX-1000SM-EH04, Ushio Inc.). 2 The entire surface was exposed to the specified exposure level. Next, a UV-cut filter (cured product) was manufactured by heating it at 200°C for 8 minutes using a hot plate (post-bake). For the photopolymerizable compositions of Examples 1 to 59, the degree of change in transmittance at the maximum absorption wavelength (λmax) of the photopolymerizable composition layer before and after exposure (degree of change in transmittance 1) and the degree of change in transmittance at the maximum absorption wavelength (λmax) of the photopolymerizable composition layer before and after post-baking (degree of change in transmittance 2) were both 1% or less. Change in transmittance 1 = |Transmittance at λmax of the photopolymerizable composition layer before exposure - Transmittance at λmax of the photopolymerizable composition layer after exposure| Change in transmittance 2 = |Transmittance at λmax of the photopolymerizable composition layer before post-baking - Transmittance at λmax of the photopolymerizable composition layer after post-baking|

[0224] (Manufacturing example 2) A UV-cut filter (cured product) was manufactured in the same manner as in Manufacturing Example 1, except that the photopolymerizable compositions of Comparative Examples 1 and 2 were used as the photopolymerizable compositions, and the film thickness of the photopolymerizable composition layer was adjusted so that the transmittance of the photopolymerizable composition layer at the maximum absorption wavelength (λmax) before exposure was 5-20%.

[0225] <Rating> [Evaluation of lightfastness] The UV-cut filters obtained above were subjected to a lightfastness test under the following condition 1, and the degree of decrease in transmittance at the maximum absorption wavelength (λmax) was calculated. Specifically, after measuring the transmittance of the UV-cut filter at the maximum absorption wavelength (λmax), the UV-cut filter was subjected to a lightfastness test under condition 1. The transmittance of the UV-cut filter at the maximum absorption wavelength (λmax) after the lightfastness test was measured, and the degree of decrease in transmittance was calculated using the following formula. Degree of decrease in transmittance (%) = (Transmittance at λmax of the UV-cut filter after lightfastness test) - (Transmittance at λmax of the UV-cut filter before lightfastness test)

[0226] (Condition 1) Equipment: Xenon weather meter (manufactured by Suga Test Instruments Co., Ltd., XL75) Illuminance: 90klx Exam duration: 50 hours Environment: 23℃, relative humidity 50%

[0227] Furthermore, the degree of discoloration of the UV-cut filters after the lightfastness test was visually inspected, and the presence or absence of discoloration was evaluated according to the following criteria. A: No coloring B: There is a slight discoloration, but it is at a usable level.

[0228] [Evaluation of solvent resistance] The UV-cut filters obtained above were immersed in propylene glycol monomethyl ether acetate (PGMEA) for 10 minutes, and the retention rate of absorbance was calculated. Solvent resistance was then evaluated according to the following criteria. Absorbance retention rate (%) = (Absorbance at λmax of UV-cut filter after immersion in PGMEA / Absorbance at λmax of UV-cut filter before immersion in PGMEA) × 100 A: Absorbance retention rate of 85% or higher B: Absorbance retention rate is 70% or more but less than 85% C: Absorbance retention rate is less than 70%

[0229] [Table 4] [Table 5]

[0230] As shown in the table above, Examples 1 to 59 were able to achieve a high level of both light resistance and solvent resistance.

[0231] The photopolymerizable compositions of the examples can be suitably used in various components constituting liquid crystal display devices and organic electroluminescent display devices.

Claims

1. At least one compound selected from the compounds represented by formula (3) and the compounds represented by formula (4), Polymerizable compounds and Photopolymerization initiator, It contains resin, The polymerizable compound is at least one selected from radical polymerizable compounds and cationic polymerizable compounds. The aforementioned radical polymerizable compound is a compound having two or more ethylenically unsaturated bond-containing groups, The aforementioned cationic polymerizable compound is a compound having two or more cyclic ether groups, The photopolymerization initiator is at least one selected from photoradical polymerization initiators and photocationic polymerization initiators. If the polymerizable compound is a radical polymerizable compound, the photopolymerization initiator is a photoradical polymerization initiator; if the polymerizable compound is a cationic polymerizable compound, the photopolymerization initiator is a photocationic polymerization initiator. The photoradical polymerization initiator is at least one selected from acylphosphine compounds, hydroxyacetophenone compounds, benzophenone compounds, hexaarylbiimidazole compounds, oxime compounds, and aminoacetophenone compounds. The photocationic polymerization initiator is a sulfonium salt, The aforementioned resin includes an alkali-soluble resin. Photopolymerizable composition; 【Chemistry 1】 In equations (3) and (4), R １ , R ２ , R １１ and R １２ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an ethylenically unsaturated bond-containing group. R ３ and R ４ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylamino group, anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, or an ethylenically unsaturated bond-containing group. R ５ 、 R ６ 、 R １３ 、 R １４ 、 R １５ and R １６ each independently represents a hydrogen atom or a substituent; R １ and R ３ They may be joined together to form a ring; R ３ and R ４ They may be joined together to form a ring; R ２ and R ４ They may be joined together to form a ring; R ５ and R ６ They may be joined together to form a ring; R １３ and R １４ They may be joined together to form a ring; R １５ and R １６ They may be joined together to form a ring.

2. R in equation (3) ３ and R ４ The photopolymerizable composition according to claim 1, wherein one of the atoms is a hydrogen atom and the other is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino group, anilino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, or an ethylenically unsaturated bond-containing group.

3. The photopolymerizable composition according to claim 1 or 2, wherein the resin is at least one selected from (meth)acrylic resin, polystyrene resin, polyester resin, polyurethane resin, polythiourethane resin, polyimide resin, epoxy resin, polycarbonate resin, cyclic olefin resin, and cellulose acylate resin.

4. A photopolymerizable composition according to claim 1 or 2, which is an adhesive or bonding agent.

5. A cured product obtained by curing the photopolymerizable composition according to claim 1 or 2.

6. An optical component comprising the cured product described in claim 5.

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