Photopolymerizable composition, cured product, and optical member

Abstract

A photopolymerizable composition, a cured product and an optical member using the same, the photopolymerizable composition containing at least one compound selected from a compound represented by formula (1) and a compound represented by formula (2), a polymerizable compound and a photopolymerization initiator.

Description

Technical Field

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

[0002] The effects of light of various wavelengths directly incident on the human eye on the retina have garnered significant attention, particularly the potential for ultraviolet (UV) and blue light damage to the retina and the resulting eye diseases. When using display devices such as liquid crystal displays (LCDs), electroluminescent displays, smartphones, and tablets, users must look at the screen, which is illuminated by a light source. In recent years, the effects of UV radiation on the retina during prolonged use of display devices and small terminals have become a concern. Therefore, efforts are underway to incorporate UV-blocking filters into these devices to reduce the impact of UV radiation on the user's eyes. UV absorbers are used in these UV-blocking filters.

[0003] Furthermore, in recent years, there has been an increasing demand for ultraviolet cutoff filters that cut off ultraviolet light in the long wavelength region around 400nm.

[0004] Patent document 1 discloses an invention relating to a photopolymerizable composition containing: an ultraviolet absorber with a specific structure that selectively absorbs light with a wavelength around 400 nm; a polymerizable monomer; a photopolymerization initiator; and a solvent.

[0005] Previous technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2017-119700 Summary of the Invention

[0008] The technical problem to be solved by the invention

[0009] Ultraviolet (UV) absorbers sometimes experience a decrease in UV absorption performance over time due to light exposure. In particular, UV absorbers with their maximum absorption wavelength located on the longer wavelength side of the UV region tend to have poor photosensitivity and their UV absorption performance tends to decline easily over time. Therefore, in recent years, there has been a desire to further improve the photosensitivity of UV absorbers.

[0010] Furthermore, when a photopolymerizable composition contains an ultraviolet absorber, the light is absorbed by the absorber during curing by irradiating the composition with light. This makes it difficult to generate active species such as free radicals from the photopolymerization initiator that are generated by the light, resulting in insufficient curing degree of the cured product. Therefore, the cured product obtained by curing a photopolymerizable composition containing an ultraviolet absorber has insufficient solvent resistance.

[0011] Furthermore, when a photopolymerizable composition contains an ultraviolet absorber, the resulting cured product is prone to contain a large amount of decomposition products of the photopolymerization initiator or residues of unreacted photopolymerization initiators. Therefore, when the cured product is irradiated with light for a long time, the decomposition products of the photopolymerization initiator or residues of unreacted photopolymerization initiators in the cured product decompose over time and generate active species such as free radicals. Due to the attack of these active species, the ultraviolet absorber tends to have a tendency to decrease its ultraviolet absorption performance over time.

[0012] Therefore, the object of the present invention is to provide a photopolymerizable composition capable of forming a cured product with excellent lightfastness and solvent resistance. Furthermore, the object of the present invention is to provide a cured product and an optical component.

[0013] means for solving technical problems

[0014] The present invention provides the following.

[0015] <1> A photopolymerizable composition comprising:

[0016] At least one compound selected from the compounds represented by formula (1) and the compounds represented by formula (2);

[0017] Polymer compounds; and

[0018] Photopolymerization initiator,

[0019] [Chemical Formula 1]

[0020]

[0021] In equations (1) and (2), R 1 R 2 R 11 and R 12 Each of these groups independently represents a hydrogen atom, alkyl, aryl, acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, or a group containing an alkene unsaturated bond.

[0022] R 3 and R 4Each of these groups 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 aniline group, an acylamino group, an alkylsulfonamide group, an arylsulfonamide group, an alkylthio group, an arylthio group, or a group containing an alkene unsaturated bond.

[0023] Y 1 Y 2 Y 11 Y 12 Y 13 and Y 14 Each group can be represented independently as an electron-withdrawing group.

[0024] Y 1 and Y 2 They can bond together to form a ring.

[0025] Y 11 and Y 12 They can bond together to form a ring.

[0026] Y 13 and Y 14 They can bond together to form a ring.

[0027] R 1 and R 3 They can bond together to form a ring.

[0028] R 3 and R 4 They can bond together to form a ring.

[0029] R 2 and R 4 They can bond together to form a ring.

[0030] <2> according to <1> The photopolymerizable composition, wherein,

[0031] The compound represented by formula (1) is the compound represented by formula (3) below.

[0032] The compound represented by formula (2) above is the same as the compound represented by formula (4) below.

[0033] [Chemical Formula 2]

[0034]

[0035] In equations (3) and (4), R 1 R 2 R 11 and R 12 Each of these groups independently represents a hydrogen atom, alkyl, aryl, acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, or a group containing an alkene unsaturated bond.

[0036] R 3and R 4 Each of these groups 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 aniline group, an acylamino group, an alkylsulfonamide group, an arylsulfonamide group, an alkylthio group, an arylthio group, or a group containing an alkene unsaturated bond.

[0037] R 5 R 6 R 13 R 14 R 15 and R 16 Each can be used independently to represent a hydrogen atom or a substituent.

[0038] R 1 and R 3 They can bond together to form a ring.

[0039] R 3 and R 4 They can bond together to form a ring.

[0040] R 2 and R 4 They can bond together to form a ring.

[0041] R 5 and R 6 They can bond together to form a ring.

[0042] R 13 and R 14 They can bond together to form a ring.

[0043] R 15 and R 16 They can bond together to form a ring.

[0044] <3> according to <2> The photopolymerizable composition, wherein,

[0045] R in equation (3) 3 and R 4 One of them is a hydrogen atom, and the other is a halogen atom, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylamino, aniline, acylamino, alkylsulfonamide, arylsulfonamide, alkylthio, arylthio, or a group containing an alkene unsaturated bond.

[0046] <4> according to <1> to <3> The photopolymerizable composition described in any one of the following statements, wherein,

[0047] The aforementioned polymerizable compounds are compounds having two or more groups containing olefinic unsaturated bonds.

[0048] <5> according to <1> to <4> The photopolymerizable composition described in any one of the following statements, wherein,

[0049] The aforementioned photopolymerization initiator is at least one selected from acetophenone compounds, acylphosphine compounds, and benzophenone compounds.

[0050] <6> according to <1> to <5> The photopolymerizable composition described in any one of the following statements further comprises a resin.

[0051] <7> according to <6> The photopolymerizable composition wherein the resin contains an alkali-soluble resin.

[0052] <8> according to <6> or <7> Photopolymerizable composition, wherein,

[0053] The resin mentioned above is selected from at least one of (meth)acrylic resins, polystyrene resins, polyester resins, polyurethane resins, polysulfide urethane resins, polyimide resins, epoxy resins, polycarbonate resins, cyclic olefin resins, and acylated cellulose resins.

[0054] <9> according to <1> to <8> The photopolymerizable composition described in any one of the above statements is an adhesive or bonding agent.

[0055] <10> A solidified substance, which is obtained by... <1> to <9> The photopolymerizable composition described in any one of the above statements is obtained by curing.

[0056] <11> An optical component containing <10> The solidified product.

[0057] Invention Effects

[0058] According to the present invention, a photopolymerizable composition capable of forming a cured product with excellent lightfastness and solvent resistance can be provided. Furthermore, the present invention can provide a cured product and an optical component. Detailed Implementation

[0059] The present invention will now be described in detail.

[0060] In the designation of groups (atomic groups) in this specification, the designations without indicating whether they are substituted or unsubstituted include groups without substituents and groups with substituents. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0061] In this specification, the numerical range indicated by “~” refers to the range including the values ​​recorded before and after “~” as the lower and upper limits.

[0062] In this specification, total solids content refers to the total amount of components after removing the solvent from the total components of the composition.

[0063] In this specification, “(meth)acrylate” means either or both of acrylate and methacrylate, “(meth)acrylic acid” means either or both of acrylic acid and methacrylic acid, “(meth)allyl” means either or both of allyl and methallyl, and “(meth)acryloyl” means either or both of acryloyl and methacryloyl.

[0064] In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the expected function of the process can be achieved.

[0065] In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as the converted values ​​of polystyrene measured by gel permeation chromatography (GPC).

[0066] <Photopolymerizable Compositions>

[0067] The photopolymerizable composition of the present invention is characterized in that it contains

[0068] A photopolymerizable composition comprising:

[0069] At least one compound selected from the compounds represented by formula (1) and the compounds represented by formula (2);

[0070] Polymer compounds; and

[0071] Photopolymerization initiator,

[0072] Hereinafter, the compounds represented by formula (1) and the compounds represented by formula (2) will be referred to as specific compounds.

[0073] The photopolymerizable composition according to the present invention can form a cured product with excellent lightfastness and solvent resistance. The specific compound contained in the photopolymerizable composition of the present invention exhibits excellent lightfastness, making it difficult for the specific compound to decompose or be modified by light irradiation, thus enabling the formation of a cured product with excellent lightfastness. Furthermore, because this specific compound has relatively high transmittance to short-wave ultraviolet light (e.g., light with wavelengths below 350 nm), when the photopolymerizable composition is cured by irradiation, it is less likely to hinder the generation of active species such as free radicals from the photopolymerization initiator caused by the exposure light, allowing the photopolymerizable composition to be fully cured by light irradiation. Moreover, because the specific compound has excellent absorption properties for light around 400 nm, it is presumed to act as a sensitizer for the photopolymerization initiator and to further promote the generation of active species such as free radicals from the photopolymerization initiator caused by the exposure light. Therefore, the photopolymerizable composition according to the present invention can form a cured product with excellent solvent resistance. Furthermore, the specific compound exhibits excellent light absorption properties around a wavelength of 400 nm. By using the photopolymerizable composition of the present invention, a cured product with excellent light-shielding properties around a wavelength of 400 nm can be formed.

[0074] 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.

[0075] The following describes the components contained in the photopolymerizable composition.

[0076] Specific Compounds

[0077] The photopolymerizable composition of the present invention contains at least one compound (specific compound) selected from the compounds represented by formula (1) and the compounds represented by formula (2).

[0078] [Chemical Formula 3]

[0079]

[0080] In equations (1) and (2), R 1 R 2 R 11 and R 12 Each of these groups independently represents a hydrogen atom, alkyl, aryl, acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, or a group containing an alkene unsaturated bond.

[0081] R 3 and R 4Each of these groups 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 aniline group, an acylamino group, an alkylsulfonamide group, an arylsulfonamide group, an alkylthio group, an arylthio group, or a group containing an alkene unsaturated bond.

[0082] Y 1 Y 2 Y 11 Y 12 Y 13 and Y 14 Each group can be represented independently as an electron-withdrawing group.

[0083] Y 1 and Y 2 They can bond together to form a ring.

[0084] Y 11 and Y 12 They can bond together to form a ring.

[0085] Y 13 and Y 14 They can bond together to form a ring.

[0086] R 1 and R 3 They can bond together to form a ring.

[0087] R 3 and R 4 They can bond together to form a ring.

[0088] R 2 and R 4 They can bond together to form a ring.

[0089] R in equation (1) 1 and R 2 The alkyl group represented and R in formula (2) 11 and R 12The alkyl group represented 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 can be any of straight-chain, branched, or cyclic, and is preferably a straight-chain or branched alkyl group. The alkyl group may also have substituents. Examples of substituents listed in the substituent T section below include alkoxy, aryloxy, acyl, acyloxy, alkoxycarbonyl, and aryloxycarbonyl groups, with alkoxycarbonyl groups being more preferred. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, n-decyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, benzyl, 2-ethylbutyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, 2-hexyldecyl, 2-octyldecyl, 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctyl, isostearyl, isopalmityl, vinyl, allyl, isopreneyl, geranyl, oleyl, propargyl, cyclohexyl, cyclopentyl, ethoxycarbonylpropyl, ethoxycarbonylpentyl, butoxycarbonylpropyl, 2-ethylhexoxycarbonylpropyl, etc.

[0090] R in equation (1) 1 and R 2 The aryl group represented and R in formula (2) 11 and R 12 The aryl group represented is preferably an aryl group with 6 to 30 carbon atoms, more preferably an aryl group with 6 to 10 carbon atoms. The aryl group may also have substituents. Examples of substituents listed under substituent T below include phenyl, p-tolyl, naphthyl, m-chlorophenyl, and n-hexadecanoylaminophenyl. The aryl group is preferably phenyl.

[0091] R in equation (1) 1 and R 2 The acyl group represented and R in formula (2) 11 and R 12 The acyl group represented is preferably an acyl group with 2 to 30 carbon atoms. The acyl group may have substituents. Examples of substituents can be the groups listed in Substituent T below. Specific examples of acyl groups include acetyl, trimethylacetyl, 2-ethylhexanoyl, stearyl, benzoyl, and p-methoxyphenylcarbonyl.

[0092] R in equation (1) 1 and R 2 The carbamoyl group represented and R in formula (2) 11 and R 12The carbamoyl group represented is preferably a carbamoyl group with 1 to 30 carbon atoms. The carbamoyl group may have substituents. Examples of substituents include those listed under substituent T below. Specific examples of carbamoyl groups include N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, morpholinylcarbonyl, N,N-di-n-octylaminocarbonyl, and N-n-octylcarbamoyl.

[0093] R in equation (1) 1 and R 2 The alkoxy carbonyl group represented and R in formula (2) 11 and R 12 Examples of alkoxycarbonyl groups represented include those with 2 to 30 carbon atoms. Alkoxycarbonyl groups may have substituents. Examples of substituents listed under substituent T below are examples of substituents.

[0094] R in equation (1) 1 and R 2 The aryloxycarbonyl group represented and R in formula (2) 11 and R 12 The aryloxycarbonyl group represented can be aryloxycarbonyl groups with 7 to 30 carbon atoms. The aryloxycarbonyl group may have substituents. Substituents can be groups listed in the substituent T section below.

[0095] R as in equation (1) 1 and R 2 The groups represented by the olefinic unsaturated bonds and R in formula (2) 11 and R 12 Examples of groups containing olefinic unsaturated bonds include vinyl, (meth)allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acryloylamino, vinylphenyl, and groups represented by formula (R100).

[0096] *-X R1 -Y R1 -Z R1 ...(R100)

[0097] In formula (R100), Y R1 Indicates a single bond, -C (=O)- ＊1 -C(=O)O- ＊1 or -C(=O)NRx 1 - ＊1 Rx 1 Indicates hydrogen atom, alkyl or aryl, ＊1 Indicates Y R1 The bond,

[0098] Y R1 Indicates a linker base that is either a single bond or divalent.

[0099] Z R1 It represents vinyl, (meth)allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acryloylamino, or vinylphenyl.

[0100] Rx 1 The alkyl group represented is preferably an alkyl group having 1 to 30 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, and n-butyl. As Rx 1 The aryl group represented is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Specific examples include phenyl, p-tolyl, and naphthyl. Rx 1 Hydrogen atoms are preferred.

[0101] X R1 Preferably -C(=O)NH- ＊1 .

[0102] As Y R1 Examples of divalent linking groups include hydrocarbon groups, -NH-, -S(=O)2-, -O-, -C(=O)-, -OC(=O)-, -C(=O)O-, -NHC(=O)-, -C(=O)NH-, and groups 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 aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group can be straight-chain, branched, or cyclic. Furthermore, cyclic aliphatic hydrocarbon groups can be monocyclic or fused-ring. Furthermore, cyclic aliphatic hydrocarbon groups can have a cross-linked structure. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group can have substituents. Examples of substituents include the substituent T described later. For example, hydroxyl groups can be used as substituents.

[0103] Y R1 The divalent linker is preferably a hydrocarbon group or a group consisting of a single bond or a divalent linker connecting two or more hydrocarbon groups. Examples of linkers connecting two or more hydrocarbon groups include -NH-, -S(=O)2-, -O-, -C(=O)-, -OC(=O)-, -C(=O)O-, -NHC(=O)-, and -C(=O)NH-, with -O-, -C(=O)-, -OC(=O)-, -C(=O)O-, -NHC(=O)-, or -C(=O)NH- being more preferred.

[0104] Z R1 Preferably, it is (meth)acryloyloxy or vinylphenyl, more preferably (meth)acryloyloxy.

[0105] R in equation (1) 1 and R 2 and R in equation (2) 11 and R 12 Each group is preferably an alkyl group, an acyl group, an carbamoyl group, or a group containing an olefinic unsaturated bond.

[0106] R as in equation (1) 3 and R 4 The halogen atoms represented can be fluorine, chlorine, and bromine atoms.

[0107] R in equation (1) 3 and R 4 The alkyl group represented 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 straight-chain or branched alkyl group, more preferably a straight-chain alkyl group. The alkyl group may also have substituents. As substituents, groups listed in Substituent T below can be cited. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-cyanoethyl, benzyl, 2-ethylhexyl, vinyl, allyl, isoprenyl, geranyl, oleyl, propargyl, cyclohexyl, cyclopentyl, 2-hydroxyethyl, 2-hydroxypropyl, preferably methyl or tert-butyl, and more preferably methyl from the viewpoint of ease of synthesis.

[0108] R in equation (1) 3 and R 4 The aryl group represented is preferably an aryl group with 6 to 30 carbon atoms, and more preferably an aryl group with 6 to 10 carbon atoms. The aryl group may also have substituents. As substituents, groups listed in Substituent T below can be cited. Specific examples of aryl groups include phenyl, p-tolyl, and naphthyl.

[0109] R in equation (1) 3 and R 4 The alkoxy group represented is preferably an alkoxy group having 1 to 30 carbon atoms. Alkoxy groups may also have substituents. Examples of substituents include those listed under substituent T below. Specific examples of alkoxy groups include methoxy and ethoxy.

[0110] 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 also have substituents. Examples of substituents include those listed under substituent T below. Specific examples of aryloxy groups include phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, and 2-tetradecanoylaminophenoxy.

[0111] R in equation (1) 3 and R 4 The acyloxy group represented is preferably an acyloxy group having 2 to 30 carbon atoms. The acyloxy group may have substituents. Examples of substituents listed in Substituent T below can be cited as substituents.

[0112] R in equation (1) 3 and R 4 The alkylamino group represented is preferably an alkylamino group having 1 to 30 carbon atoms. The alkylamino group may have substituents. Examples of substituents listed under substituent T below can be cited as substituents.

[0113] R in equation (1) 3 and R 4 The aniline group represented is preferably an aniline group with 6 to 40 carbon atoms, more preferably an aniline group with 6 to 30 carbon atoms, even more preferably an aniline group with 6 to 20 carbon atoms, particularly preferably an aniline group with 6 to 15 carbon atoms, and most preferably an aniline group with 6 to 12 carbon atoms. The aniline group may have substituents. Examples of substituents can be found in the substituent T section described below.

[0114] R in equation (1) 3 and R 4 The amide group represented is preferably an amide group with 2 to 30 carbon atoms, more preferably an amide group with 2 to 20 carbon atoms, even more preferably an amide group with 2 to 15 carbon atoms, and particularly preferably an amide group with 2 to 10 carbon atoms. The amide group may have substituents. Examples of substituents can be found in the substituent T section described below.

[0115] R in equation (1) 3 and R 4 The alkylsulfonamide represented is preferably an alkylsulfonamide with 2 to 30 carbon atoms, more preferably an alkylsulfonamide with 2 to 20 carbon atoms, even more preferably an alkylsulfonamide with 2 to 15 carbon atoms, and particularly preferably an alkylsulfonamide with 2 to 10 carbon atoms. The alkylsulfonamide may have substituents. Examples of substituents can be found in the substituent T section described below.

[0116] R in equation (1) 3 and R 4 The arylsulfonamide represented is preferably an arylsulfonamide with 6 to 40 carbon atoms, more preferably an arylsulfonamide with 6 to 30 carbon atoms, even more preferably an arylsulfonamide with 6 to 20 carbon atoms, particularly preferably an arylsulfonamide with 6 to 15 carbon atoms, and most preferably an arylsulfonamide with 6 to 12 carbon atoms. The arylsulfonamide may have substituents. Examples of substituents can be found in the substituent T section described below.

[0117] R in equation (1) 3 and R 4 The alkylthio group represented is preferably an alkylthio group with 1 to 30 carbon atoms, more preferably an alkylthio group with 1 to 20 carbon atoms, even more preferably an alkylthio group with 1 to 15 carbon atoms, particularly preferably an alkylthio group with 1 to 10 carbon atoms, and most preferably an alkylthio group with 1 to 8 carbon atoms. The alkylthio group can be either straight-chain or branched. The alkylthio group can have substituents. Examples of substituents are those described in Substituent T below.

[0118] R in equation (1) 3 and R 4 The arylthio group represented is preferably an arylthio group with 6 to 40 carbon atoms, more preferably an arylthio group with 6 to 30 carbon atoms, even more preferably an arylthio group with 6 to 20 carbon atoms, particularly preferably an arylthio group with 6 to 15 carbon atoms, and most preferably an arylthio group with 6 to 12 carbon atoms. The arylthio group may have substituents. Examples of substituents can be found in the substituent T section described later.

[0119] R as in equation (1) 3 and R 4 The group containing an olefinic unsaturated bond represented can be exemplified by R in formula (1). 1 and R 2 The groups represented by the olefinic unsaturated bonds and R in formula (2) 11 and R 12 The groups represented are those containing olefinic unsaturated bonds.

[0120] R in equation (1) 3 and R 4 Preferably, each is independently a hydrogen atom, alkyl group, alkoxy group, or aryloxy group.

[0121] Furthermore, from the viewpoint of increasing the wavelength of maximum absorption, R is preferred in (1). 3 and R 4 One of the atoms is a hydrogen atom, and the other is an aryl, alkoxy, aryloxy, acyloxy, alkylamino, aniline, acylamino, alkylsulfonamide, arylsulfonamide, alkylthio, arylthio, or a group containing an alkene unsaturated bond, more preferably R. 3 and R 4 One of them is a hydrogen atom, and the other is an alkyl, alkoxy, or aryloxy group, with R being more preferred. 3 and R 4 One is a hydrogen atom, and the other is a tetraalkyl group.

[0122] R in equation (1) 1 and R 3 They can bond together to form a ring, R 3 and R4 They can bond together to form a ring, R 2 and R 4 These groups can be bonded 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 can be found in the substituent T section described later.

[0123] Y in equation (1) 1 and Y 2 and Y in equation (2) 11 Y 12 Y 13 and Y 14 Each group represents an electron-withdrawing group independently. These electron-withdrawing groups are preferably substituents with a positive Hammett substituent constant σp. Examples of electron-withdrawing groups include cyano, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfonyl, thionyl, and aminosulfonyl. Acyl groups are preferably acetyl, propionyl, neopentyl, benzoyl, and 4-methoxybenzoyl. Alkoxycarbonyl groups are preferably methoxycarbonyl, ethoxycarbonyl, 2-hydroxyethoxycarbonyl, 2-(3-trimethoxysilylpropylaminocarbonyloxy)ethoxycarbonyl, 2-(3-triethoxysilylpropylaminocarbonyloxy)ethoxycarbonyl, and 2-ethylhexylcarbonyloxy. Aryloxycarbonyl groups are preferably phenoxycarbonyl and 4-methoxyphenoxycarbonyl. The carbamoyl group is preferably unsubstituted carbamoyl, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, morpholinocarbamoyl, N,N-di-n-octylcarbamoyl, or N-n-octylcarbamoyl. The sulfonyl group is preferably methanesulfonyl, ethanesulfonyl, octylsulfonyl, or benzenesulfonyl. The thionyl group is preferably methanethionyl, ethanethionyl, octanethionyl, or benzenethionyl. The aminosulfonyl group is preferably unsubstituted aminosulfonyl or N,N-dimethylaminosulfonyl. The electron-withdrawing group is preferably cyano or carbamoyl, more preferably carbamoyl.

[0124] In equation (1), Y 1 With Y 2 Y can bond to form a ring, and considering that it can further improve the lightfastness of the obtained cured product, Y is preferred. 1 With Y 2 They can bond together to form a ring.

[0125] In equation (2), Y 11 With Y 12 Y can bond to form a ring, and considering that it can further improve the lightfastness of the obtained cured product, Y is preferred. 11 With Y 12 They can bond together to form a ring. Furthermore, Y 13 With Y 14Y can bond to form a ring, and considering that it can further improve the lightfastness of the obtained cured product, Y is preferred. 13 With Y 14 They can bond together to form a ring.

[0126] Y 1 With Y 2 The rings and Y formed by bonding 11 With Y 12 The rings formed by bonding, and Y 13 With Y 14 The ring formed by bonding is preferably a 5-membered or 6-membered ring. Specifically, examples include 5-pyrazolinone rings, isoxazoline-5-one rings, pyrazolidine-3,5-dione rings, barbiturate rings, thiobarbiturate rings, and dihydropyridine-2,6-dione rings, with 5-pyrazolinone rings, isoxazoline-5-one rings, pyrazolidine-3,5-dione rings, and barbiturate rings being more preferred, and pyrazolidine-3,5-dione rings and barbiturate rings being even more preferred, and pyrazolidine-3,5-dione rings being particularly preferred. The ring formed by bonding the above groups together may further have substituents. Examples of substituents are those described in Substituent T below.

[0127] (Substituent T)

[0128] The following groups can be cited as substituents T.

[0129] Halogen atoms (e.g., chlorine, bromine, iodine);

[0130] Alkyl [straight-chain, branched, cyclic alkyl groups. Specifically, straight-chain or branched alkyl groups (preferably straight-chain or branched alkyl groups with 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl groups (preferably cycloalkyl groups with 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), bicycloalkyl groups (preferably bicycloalkyl groups with 5 to 30 carbon atoms, i.e., a monovalent group formed by removing one hydrogen atom from a bicycloalkanes with 5 to 30 carbon atoms. For example, bicyclo[1,2,2]heptane-2-yl, bicyclo[2,2,2]octane-3-yl), and further including tricyclic structures with multiple ring structures. The alkyl groups (e.g., alkylthioyl groups) in the following description of substituents also refer to alkyl groups of this concept.]

[0131] Alkenyl [straight-chain, branched, cyclic alkenyl groups. Specifically, straight-chain or branched alkenyl groups (preferably straight-chain or branched alkenyl groups with 2 to 30 carbon atoms, such as vinyl, allyl, isoprene, gerany, oleyl), cycloalkenyl groups (preferably cycloalkenyl groups with 3 to 30 carbon atoms, i.e., cycloalkenyl groups with one monovalent group removed from a hydrogen atom of a cycloalkenyl group with 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl groups (preferably bicycloalkenyl groups with 5 to 30 carbon atoms, i.e., bicycloalkenyl groups with one monovalent group removed from a hydrogen atom of a bicycloalkenyl group having one double bond, such as bicyclo[2,2,1]hept-2-en-1-yl, bicyclo[2,2,2]oct-2-en-4-yl).];

[0132] Alkynyl (preferably a straight-chain or branched alkynyl group with 2 to 30 carbon atoms. For example, ethynyl or propynyl);

[0133] Aryl (preferably aryl with 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecylaminophenyl);

[0134] Heterocyclic groups (preferably monovalent groups formed by removing one hydrogen atom from 5- or 6-membered aromatic or non-aromatic heterocyclic compounds, more preferably 5- or 6-membered aromatic heterocyclic groups having 1 to 20 carbon atoms. Examples include 2-furanyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl);

[0135] Cyano;

[0136] hydroxyl group;

[0137] Nitro;

[0138] carboxyl;

[0139] Alkoxy groups (preferably straight-chain or branched alkoxy groups with 1 to 30 carbon atoms. For example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octoxy, 2-methoxyethoxy);

[0140] Aryloxy group (preferably an aryloxy group with 6 to 30 carbon atoms. For example, phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy);

[0141] Heterocyclic oxides (preferably heterocyclic oxides with 2 to 30 carbon atoms. For example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranoxy);

[0142] Acyloxy group (preferably formyloxy, alkyl carbonyloxy with 2 to 30 carbon atoms, or aryl carbonyloxy with 6 to 30 carbon atoms. For example, formyloxy, acetoxy, trimethylacetoxy, stearyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy);

[0143] Carbamoyloxy (preferably carbamoyloxy with 1 to 30 carbon atoms. For example, N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinylcarbonyloxy, N,N-di-n-octylaminocarbonyloxy, N-n-octylcarbamoyloxy);

[0144] Alkoxycarbonyloxy group (preferably alkoxycarbonyloxy group with 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy);

[0145] Aryloxycarbonyloxy (preferably aryloxycarbonyloxy with 7 to 30 carbon atoms. For example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, p-hexadecyloxyphenoxycarbonyloxy);

[0146] Amino groups (preferably amino groups, alkylamino groups with 1 to 30 carbon atoms, or phenylamino groups with 6 to 30 carbon atoms. For example, amino, methylamino, dimethylamino, phenylamino, N-methyl-phenylamino, diphenylamino);

[0147] Acylamino group (preferably formamide, alkyl carbonylamino group with 2 to 30 carbon atoms, or aryl carbonylamino group with 6 to 30 carbon atoms. For example, formamide, acetamido, trimethylacetamido, lauroylamino, benzoylamino, 3,4,5-tris-n-octyloxyphenyl carbonylamino);

[0148] Aminocarbonylamino (preferably an aminocarbonylamino with 1 to 30 carbon atoms. For example, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino);

[0149] Alkoxycarbonylamino (preferably alkoxycarbonylamino with 2 to 30 carbon atoms. For example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino);

[0150] Aryloxycarbonylamino (preferably aryloxycarbonylamino with 7 to 30 carbon atoms. For example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxycarbonylamino);

[0151] Aminosulfonylamino (preferably an aminosulfonylamino with 0 to 30 carbon atoms. For example, aminosulfonylamino, N,N-dimethylaminosulfonylamino, N-n-octylaminosulfonylamino);

[0152] Alkyl or aryl sulfonamides (preferably alkyl sulfonamides with 1 to 30 carbon atoms or aryl sulfonamides with 6 to 30 carbon atoms. For example, methyl sulfonamides, butyl sulfonamides, phenyl sulfonamides, 2,3,5-trichlorophenyl sulfonamides, and p-methylphenyl sulfonamides);

[0153] thiol;

[0154] Alkylthio group (preferably an alkylthio group with 1 to 30 carbon atoms, such as methylthio, ethylthio, and n-hexadecylthio);

[0155] Arylthio (preferably arylthio with 6 to 30 carbon atoms. For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio);

[0156] Heterocyclic thio groups (preferably heterocyclic thio groups with 2 to 30 carbon atoms. For example, 2-benzothiazolyl thio group, 1-phenyltetrazole-5-ylthio group);

[0157] Aminosulfonyl group (preferably an aminosulfonyl group with 0 to 30 carbon atoms. For example, N-ethylaminosulfonyl, N-(3-dodecyloxypropyl)aminosulfonyl, N,N-dimethylaminosulfonyl, N-acetamidesulfonyl, N-benzamidesulfonyl, N-(N'-phenylcarbamoyl)aminosulfonyl);

[0158] sulfonyl;

[0159] Alkyl sulfinyl or aryl sulfinyl (preferably alkyl sulfinyl with 1 to 30 carbon atoms or aryl sulfinyl with 6 to 30 carbon atoms. For example, methyl sulfinyl, ethyl sulfinyl, phenyl sulfinyl, p-methylphenyl sulfinyl);

[0160] Alkyl or aryl sulfonyl groups (preferably alkyl sulfonyl groups with 1 to 30 carbon atoms or aryl sulfonyl groups with 6 to 30 carbon atoms. For example, methyl sulfonyl, ethyl sulfonyl, phenyl sulfonyl, p-methylphenyl sulfonyl);

[0161] Acyl group (preferably formyl group, alkyl carbonyl group with 2 to 30 carbon atoms, aryl carbonyl group with 7 to 30 carbon atoms, or heterocyclic carbonyl group bonded to a carbonyl group through a carbon atom with 4 to 30 carbon atoms. For example, acetyl group, trimethylacetyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, p-octyloxyphenyl carbonyl group, 2-pyridyl carbonyl group, 2-furanyl carbonyl group);

[0162] Aryloxycarbonyl (preferably an aryloxycarbonyl group with 7 to 30 carbon atoms. For example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl);

[0163] Alkoxycarbonyl (preferably an alkoxycarbonyl group with 2 to 30 carbon atoms. For example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, n-butoxycarbonyl, 2-ethylhexyloxycarbonyl);

[0164] Carbamoyl group (preferably carbamoyl group with 1 to 30 carbon atoms. For example, carbamoyl group, N-methylcarbamoyl group, N,N-dimethylcarbamoyl group, N,N-di-n-octylcarbamoyl group, N-(methanesulfonyl)carbamoyl group);

[0165] Aryl or heterocyclic azo group (preferably aryl azo group with 6 to 30 carbon atoms, or heterocyclic azo group with 3 to 30 carbon atoms. For example, phenyl azo group, p-chlorophenyl azo group, 5-ethylthio-1,3,4-thiadiazol-2-yl azo group);

[0166] Imide (preferably N-succinimide or N-phthalimide);

[0167] Phosphin group (preferably a phosphin group with 2 to 30 carbon atoms. For example, dimethylphosphin, diphenylphosphin, methylphenoxyphosphin).

[0168] Phosphonoyl group (preferably a phosphonoyl group with 2 to 30 carbon atoms. For example, phosphonoyl, dioctyloxyphosphonoyl, diethoxyphosphonoyl);

[0169] Phosphonoyloxy group (preferably a phosphonoyloxy group with 2 to 30 carbon atoms. For example, diphenoxyphosphonoyloxy group, dioctyloxyphosphonoyloxy group);

[0170] Phosphonoamino (preferably phosphonoamino with 2 to 30 carbon atoms. For example, dimethoxyphosphonoamino, dimethylaminophosphonoamino);

[0171] Groups containing olefinic unsaturated bonds (e.g., vinyl, (meth)allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acryloylamino, and vinylphenyl).

[0172] Among the groups listed above, for groups having hydrogen atoms, one or more hydrogen atoms can be replaced by the substituent T described above. Examples of such substituents include alkylcarbonylaminosulfonyl, arylcarbonylaminosulfonyl, alkylsulfonylaminocarbonyl, and arylsulfonylaminocarbonyl. Specific examples include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl.

[0173] Regarding a specific compound, considering its high solubility in solvents and its ease of forming a cured product that suppresses planar inhomogeneity, the compound represented by formula (1) is preferred.

[0174] Furthermore, considering that it is easy to form a cured product with excellent lightfastness, the compound represented by formula (1) above is preferably the compound represented by formula (3) below. Furthermore, considering that it is easy to form a cured product with excellent lightfastness, the compound represented by formula (2) above is preferably the compound represented by formula (4) below.

[0175] [Chemical Formula 4]

[0176]

[0177] In equations (3) and (4), R 1 R 2 R 11 and R 12 Each of these groups independently represents a hydrogen atom, alkyl, aryl, acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, or a group containing an alkene unsaturated bond.

[0178] R 3 and R 4 Each of these groups 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 aniline group, an acylamino group, an alkylsulfonamide group, an arylsulfonamide group, an alkylthio group, an arylthio group, or a group containing an alkene unsaturated bond.

[0179] R 5 R 6 R 13 R 14 R 15 and R 16 Each can be used independently to represent a hydrogen atom or a substituent.

[0180] R 1 and R 3 They can bond together to form a ring.

[0181] R 3 and R 4 They can bond together to form a ring.

[0182] R 2 and R 4 They can bond together to form a ring.

[0183] R 5 and R 6 They can bond together to form a ring.

[0184] R 13 and R 14 They can bond together to form a ring.

[0185] R 15 and R 16 They can bond together to form a ring.

[0186] R in equation (3) 1 and R 2 The meaning of R in equation (1) 1 and R 2 same.

[0187] R in equation (3)3 and R 4 The meaning of R in equation (1) 3 and R 4 The same. From the viewpoint of extending the wavelength of maximum absorption, R is preferred. 3 and R 4 One of them is a hydrogen atom, and the other is an aryl, alkoxy, aryloxy, acyloxy, alkylamino, aniline, acylamino, alkylsulfonamide, arylsulfonamide, alkylthio, arylthio, or a group containing an alkene unsaturated bond.

[0188] More preferably R 3 and R 4 One of them is a hydrogen atom, and the other is an alkyl, alkoxy, or aryloxy group, with R being more preferred. 3 and R 4 One is a hydrogen atom, and the other is a tetraalkyl group.

[0189] R in equation (3) 1 and R 3 They can bond together to form a ring, R 3 and R 4 They can bond together to form a ring, R 2 and R 4 These groups can be bonded to form rings. The rings formed by the bonding of these groups are preferably 5-membered or 6-membered rings. The formed rings may have substituents. Examples of substituents can be found in the substituent T section described later.

[0190] R in equation (4) 11 and R 12 The meaning of R in equation (2) 11 and R 12 same.

[0191] R as in equation (3) 5 and R 6 and R in equation (4) 13 R 14 R 15 and R 16 The substituents referred to can be the groups described by the substituent T above, preferably alkyl, aryl or heterocyclic, more preferably alkyl or aryl, and even more preferably alkyl.

[0192] 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 can be straight-chain, branched, or cyclic, preferably straight-chain or branched. The alkyl group may have substituents. Examples of substituents described in Substituent T above are examples of substituents.

[0193] The aryl group is preferably an aryl group with 6 to 40 carbon atoms, more preferably an aryl group with 6 to 30 carbon atoms, even more preferably an aryl group with 6 to 20 carbon atoms, particularly preferably an aryl group with 6 to 15 carbon atoms, and most preferably an aryl group with 6 to 12 carbon atoms. The aryl group is preferably phenyl or naphthyl, more preferably phenyl. The aryl group may have substituents. Examples of substituents described in substituent T above are possible substituents.

[0194] The heterocycle in the heterocyclic group preferably includes a 5- or 6-membered saturated or unsaturated heterocycle. Aliphatic rings, aromatic rings, or other heterocycles may be condensed within the heterocycle. Examples of heteroatoms constituting the heterocycle include B, N, O, S, Se, and Te, with N, O, and S being preferred. The carbon atoms of the heterocycle preferably have a free valence (monovalent) (the heterocyclic group is bonded to a 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 heterocycles in the heterocyclic group include pyrrolidine rings, morpholine rings, 2-boron-1,3-dioxolane rings, and 1,3-tetrahydrothiazole rings. Examples of unsaturated heterocycles in the heterocyclic group include imidazole rings, thiazole rings, benzothiazole rings, benzoxazole rings, benzotriazole rings, benzoselenazole rings, pyridine rings, pyrimidine rings, and quinoline rings. The heterocyclic group may have substituents. Examples of substituents include the groups described in substituent T above.

[0195] R in equation (3) 5 With R 6 They can bond to form a ring, R in equation (4) 13 With R 14 They can bond to form a ring, R in equation (4) 15 With R 16 They can also be bonded to form rings. The rings formed by the bonding of these groups are preferably 5-membered or 6-membered rings. Specific examples of rings include hexahydropyridazine rings, tetrahydropyridazine rings, and tetrahydrophthalazine rings. The formed rings may have substituents. Examples of substituents are those described in Substituent T below.

[0196] R in equation (3) 5 and R 6 and R in equation (4) 13 R 14 R 15 and R 16 Each of the following is preferably a hydrogen atom, alkyl, aryl or heterocyclic group, more preferably alkyl or aryl, and even more preferably alkyl.

[0197] The maximum absorption wavelength of a particular compound is preferably in the wavelength range of 360–430 nm, more preferably in the wavelength range of 370–420 nm, even more preferably in the wavelength range of 380–420 nm, and especially preferably in the wavelength range of 380–405 nm.

[0198] The molar absorptivity of the specific compound at the maximum absorption wavelength is preferably 10,000 L / mol·cm or higher, more preferably 20,000 L / mol·cm or higher, and even more preferably 30,000 L / mol·cm or higher.

[0199] Furthermore, the molar absorptivity of the specific compound at a wavelength of 400 nm is preferably 1000 L / mol·cm or more, more preferably 3000 L / mol·cm or more, and even more preferably 5000 L / mol·cm or more.

[0200] The maximum absorption wavelength and molar absorptivity of a specific compound can be determined by measuring the spectrum of a solution prepared by dissolving the specific compound in ethyl acetate at room temperature (25°C) using a 1 cm quartz cell. Examples of suitable measuring devices include the UV-1800PC (manufactured by SHIMADZU CORPORATION).

[0201] The specific compound can be manufactured according to the methods described in Japanese Patent Application Publication No. 2009-067984, Japanese Patent Application Publication No. 2009-263616, Japanese Patent Application Publication No. 2009-263617, and International Publication No. 2017 / 122503.

[0202] As specific examples of particular compounds, compounds with the following structures can be cited. In the structural formulas shown below, Me is methyl, Et is ethyl, Pr is propyl, and tBu is tert-butyl. n Bu is n-butyl, Bn is benzyl, and Ph is phenyl.

[0203] [Chemical Formula 5]

[0204]

[0205] [Chemical Formula 6]

[0206]

[0207] [Chemical Formula 7]

[0208]

[0209] [Chemical Formula 8]

[0210]

[0211] [Chemical Formula 9]

[0212]

[0213] [Chemical Formula 10]

[0214]

[0215] [Chemical Formula 11]

[0216]

[0217] [Chemical Formula 12]

[0218]

[0219] [Chemical Formula 13]

[0220]

[0221] [Chemical Formula 14]

[0222]

[0223] [Chemical Formula 15]

[0224]

[0225] [Chemical Formula 16]

[0226]

[0227] [Chemical Formula 17]

[0228]

[0229] [Chemical Formula 18]

[0230]

[0231] [Chemical Formula 19]

[0232]

[0233] [Chemical Formula 20]

[0234]

[0235] [Chemical Formula 21]

[0236]

[0237] The content of the specific compound in the total solids component of the photopolymerizable composition is preferably 0.01 to 50% by mass. The lower limit is preferably 0.05% by mass or more, 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. When it contains two or more specific compounds, their total amount is preferably within the above-mentioned range.

[0238] Polymer Compounds

[0239] The photopolymerizable composition of the present invention contains a polymerizable compound. As the polymerizable compound, compounds that can be polymerized and cured by imparting energy can be used without limitation. The polymerizable compound can be a free radical polymerizable compound or a cationic polymerizable compound. Examples of free radical polymerizable compounds include compounds having groups containing olefinic unsaturated bonds.

[0240] The polymerizable compound is preferably a compound having a group containing an olefinic unsaturated bond, more preferably a compound having two or more groups containing an olefinic unsaturated bond. The maximum number of groups containing an olefinic unsaturated bond in the polymerizable compound is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less. Examples of groups containing an olefinic unsaturated bond in the polymerizable compound include vinyl, allyl, and (meth)acryloyl groups.

[0241] The polymerizable compound can be any of monomers, prepolymers (i.e., dimers, trimers or oligomers) and mixtures thereof, as well as (co)polymers of compounds selected from monomers and prepolymers, preferably monomers.

[0242] The molecular weight of the polymerizable compound is preferably between 100 and 3000. More preferably, it is below 2000, and even more preferably below 1500. More preferably, it is above 150, and even more preferably above 250.

[0243] (Free radical polymeric compounds)

[0244] Examples of free radical polymerizable compounds include compounds with groups containing olefinic unsaturated bonds.

[0245] Examples of free 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. Preferably, these are esters of unsaturated carboxylic acids and aliphatic polyols, amides of unsaturated carboxylic acids and aliphatic polyamines, and homopolymers or copolymers thereof.

[0246] Furthermore, as free radical polymerizable compounds, the following can also be used: addition reactions of unsaturated carboxylic acid esters or unsaturated carboxylic acid amides with nucleophilic substituents (e.g., hydroxyl, amino, mercapto groups, etc.) with monofunctional or polyfunctional isocyanate compounds or epoxy compounds; dehydration condensation reactions of unsaturated carboxylic acid esters or unsaturated carboxylic acid amides with nucleophilic substituents with monofunctional or polyfunctional carboxylic acids; addition reactions of unsaturated carboxylic acid esters or unsaturated carboxylic acid amides with electrophilic substituents (e.g., isocyanate groups, epoxy groups, etc.) with monofunctional or polyfunctional alcohols, amines, or thiols; substitution reactions of unsaturated carboxylic acid esters or unsaturated carboxylic acid amides with leaving substituents (e.g., halogroups, toluenesulfonyloxy groups, etc.) with monofunctional or polyfunctional alcohols, amines, or thiols; etc. Furthermore, compounds obtained by replacing the aforementioned unsaturated carboxylic acids with unsaturated phosphonic acids, styrene, or vinyl ethers can also be used.

[0247] Furthermore, free radical polymerizable compounds can also be made from multiple compounds with different functional numbers or multiple compounds with different types of polymerizable groups (e.g., acrylates, methacrylates, styrene compounds, vinyl ether compounds, etc.).

[0248] Furthermore, the free radical polymerizable compound is preferably a (meth)acrylate compound, more preferably a (meth)acrylate compound with two or more functional groups, even more preferably a (meth)acrylate compound with two to 15 functional groups, even more preferably a (meth)acrylate compound with two to 10 functional groups, and particularly preferably a (meth)acrylate compound with two to six functional groups. Monofunctional (meth)acrylate compounds can also be used as the polymerizable compound. Monofunctional (meth)acrylate compounds and (meth)acrylate compounds with two or more functional groups can also be used in combination.

[0249] Specific examples of free radical polymerizable compounds include pentaerythritol triester (meth)acrylate, pentaerythritol tetraester (meth)acrylate, dipentaerythritol pentaester (meth)acrylate, dipentaerythritol hexaester (meth)acrylate, tris((meth)acryloyloxyhexyl)isocyanurate, ethylene oxide EO (ethylene oxide) modified pentaerythritol tetraester (meth)acrylate, EO (ethylene oxide) modified dipentaerythritol hexaester (meth)acrylate, benzyl methacrylate, 1,3-butanediol diester (meth)acrylate, diethylene glycol diester (meth)acrylate, neopentyl glycol diester (meth)acrylate, triethylene glycol diester (meth)acrylate, bisphenol A (meth)acrylate polyethoxylate, hexanediol diester (meth)acrylate, polyethylene glycol diester (meth)acrylate, polypropylene glycol diester (meth)acrylate, and 1,4-meth)acrylate. Butylene glycol diester, trimethylolpropane triester (meth)acrylate, tripropylene glycol triester (meth)acrylate, butyl triester (meth)acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, dicyclopentyl acrylate, dicyclopentenyloxyethyl methacrylate, 4-tert-butylcyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 3-methoxybutyl methacrylate, cyclohexyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, etc.

[0250] Commercially available free radical polymerizable compounds include Nippon Kayaku Co., Ltd.'s KAYARAD series (e.g., D-330, D-320, D-310, PET-30, TPA-330, DPHA, DPHA-40H, etc.), Shin-Nakamura Chemical Co., Ltd.'s NK Ester series (e.g., A-DPH-12E, A-TMMT, A-TMM-3, etc.), KYOEISHA CHEMICAL CO.,LTD.'s LIGHT ACRYLATE series (e.g., DCP-A, etc.), TOAGOSEICO.,LTD.'s ARONIX series (e.g., M-305, M-306, M-309, M-450, M-402, TO-1382, etc.), and OsakaOrganic Chemical Industry. Multifunctional (meth)acrylate compounds manufactured by Co., Ltd., including the Biscoat series (e.g., V#802, etc.), the Beamset series (e.g., 504H, 550B, 575, 577, etc.) manufactured by ARAKAWACHEMICAL INDUSTRIES, LTD., and the EBECRYL series manufactured by Daicel Corporation.

[0251] Free radical polymerizable compounds may include (meth)acrylate compounds described in Japanese Patent Application Publication No. 48-064183, Japanese Patent Application Publication No. 49-043191, and Japanese Patent Application 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).

[0252] (Catonic polymeric compounds)

[0253] Examples of cationic polymerizable compounds include compounds having cationic polymerizable groups. Examples of cationic polymerizable groups include cyclic ether groups such as epoxy groups and oxetyl groups, and vinyl ether groups, with cyclic ether groups being preferred. Furthermore, the cationic polymerizable compound is preferably a multifunctional cationic polymerizable compound having two or more cationic polymerizable groups.

[0254] Examples of cationic polymerizable compounds include polyfunctional alicyclic epoxy compounds, polyfunctional heterocyclic epoxy compounds, polyfunctional oxoheterocyclic butane compounds, alkylene glycol diglycidyl ethers, and alkylene glycol monovinyl monoglycidyl ethers.

[0255] Specific examples of cationic polymerizable compounds include 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, xylene dioxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, cyclohexanediethanol diethylene ether, 2-ethylhexylethylene ether, cyclohexanediethanol monoethylene ether, 4-hydroxybutylethylene ether, and compounds described in paragraphs 0029 to 0058 of Japanese Patent Application Publication No. 2012-046577.

[0256] Cationic polymerizable compounds can also be (meth)acrylate compounds having cationic polymerizable groups. Specific examples of (meth)acrylate compounds having cationic polymerizable groups include methyl 3,4-epoxycyclohexyl methacrylate. Commercially available examples include, for instance, CYCLOMER M100 manufactured by Daicel Corporation.

[0257] Cationic polymerizable compounds can also be the ARON OXETANE series (OXT-101, OXT-121, OXT-221, etc.) manufactured by TOAGOSEI CO., LTD., the CELLOXIDE series (2021P) manufactured by Daicel Corporation, and alkyl divinyl ethers CHDVE, alkyl monovinyl ethers EHVE, hydroxyalkyl vinyl ethers CHMVE, hydroxyalkyl vinyl ethers HBVE, etc. manufactured by Nippon Carbide Industries Co., Inc. Furthermore, substances specifically exemplified as epoxy resins described later can also be used.

[0258] The content of the polymerizable compound in the total solids component of the photopolymerizable composition is preferably 0.1% to 90% by mass. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less. The photopolymerizable resin composition may contain only one polymerizable compound or two or more polymerizable compounds. When it contains two or more polymerizable compounds, their total amount is preferably within the above-mentioned range.

[0259] Photopolymerization Initiators

[0260] The photopolymerizable composition of the present invention contains a photopolymerization initiator. A photopolymerization initiator is a compound that, upon exposure to light, initiates or promotes the polymerization of a polymerizable compound. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. When a radical polymerization compound is used as the polymerizable compound, a photoradical polymerization initiator is preferred. A photoradical polymerization initiator is preferably a compound that generates free radicals upon sensing photochemical rays with a wavelength of 300 nm or higher. When a cationic polymerization compound is used as the polymerizable compound, a photocationic polymerization initiator is preferred.

[0261] (Photoradical polymerization initiator)

[0262] Examples of photoradical polymerization initiators include oxime compounds, halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), oxadiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azido compounds, metallocene compounds, hexaarylbisimidazole compounds, organoboronic acid compounds, disulfonic acid compounds, onium salt compounds, acetophenone compounds, acylphosphine compounds, and benzophenone compounds. Considering the ability to form cured products with superior light resistance and solvent resistance, acetophenone compounds, acylphosphine compounds, benzophenone compounds, or hexaarylbisimidazole compounds are preferred, more preferably acetophenone compounds, acylphosphine compounds, or benzophenone compounds, and even more preferably acetophenone compounds or acylphosphine compounds.

[0263] Examples of acetophenone compounds include aminoacetophenone compounds and hydroxyacetophenone compounds. Examples of acetophenone compounds include those described in Japanese Patent Application Publication Nos. 2009-191179 and 2009-291969. Commercially available aminoacetophenone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV). Commercially available hydroxyacetophenone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV).

[0264] Examples of acylphosphine compounds include those described in Japanese Patent No. 4225898. Commercially available examples of acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins B.V.).

[0265] 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, and 4,4'-bis(dialkylamino)benzophenones (e.g., 4,4'-bis(dimethylamino)benzophenone, 4, 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., are preferred from the viewpoint of sensitivity and the lightfastness of the obtained cured product.

[0266] Examples of oxime compounds include those described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, and compounds described in paragraphs 0073 to 0075 of Japanese Patent Application Publication No. 2016-006475. Among oxime compounds, oxime ester compounds are preferred. Commercially available oxime compounds include Irgacure OXE01, Irgacure OXE02 (manufactured by BASF), and Irgacure OXE03 (manufactured by BASF).

[0267] Examples of halogenated hydrocarbon derivatives include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Patent No. 3905815, Japanese Patent Publication No. 46-004605, Japanese Patent Application Publication No. 48-036281, Japanese Patent Application Publication No. 55-032070, Japanese Patent Application Publication No. 60-239736, Japanese Patent Application Publication No. 61-169835, Japanese Patent Application Publication No. 61-169837, Japanese Patent Application Publication No. 62-058241, Japanese Patent Application Publication No. 62-212401, Japanese Patent Application Publication No. 63-070243, Japanese Patent Application Publication No. 63-298339, and MP Hutt's “Journal of Heterocyclic The compounds described in Chemistry 1 (No. 3), (1970), etc., are preferably oxazole compounds or triazine compounds substituted with trihalomethyl groups.

[0268] Examples of hexaaryl diimidazole compounds include those described in Japanese Patent Publication No. 06-029285, US Patent No. 3,479,185, US Patent No. 4,311,783, and US Patent No. 4,622,286. Specifically, examples include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyphenyl)biimidazole, 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, etc.

[0269] (Photocationic polymerization initiator)

[0270] As a photocationic polymerization initiator, there is no particular limitation as long as the compound generates a protic acid or Lewis acid upon receiving light irradiation. The photoacid-generating agent is preferably a compound that generates an acid in response to photochemical rays with a wavelength of 300 nm or higher, more preferably 300–450 nm. The photoacid-generating agent is preferably a compound that generates an acid with a pKa of 4 or lower upon light irradiation, more preferably a compound that generates an acid with a pKa of 3 or lower, and even more preferably a compound that generates an acid with a pKa of 2 or lower.

[0271] Examples of photocationic polymerization initiators include oxime sulfonates, triazine compounds, sulfonium salts, iodine salts, quaternary ammonium salts, diazomethane compounds, sulfonates, iminosulfonates, carboxylic acid esters, and sulfonylimides.

[0272] Specific examples of photocationic polymerization initiators include compounds described in paragraphs 0061 to 0108 of Japanese Patent Application Publication No. 2012-046577, paragraphs 0029 to 0030 of Japanese Patent Application Publication No. 2002-122994, paragraphs 0037 to 0063 of Japanese Patent Application Publication No. 2002-122994, and oxime sulfonate compounds described in paragraphs 0081 to 0108 of Japanese Patent Application Publication No. 2013-210616. Commercially available photocationic polymerization initiators include CPI-210S (manufactured by San-Apro Ltd.).

[0273] The content of the photopolymerization initiator in the total solids component of the photopolymerizable composition is preferably 0.1% to 30% by mass. The lower limit is preferably 0.3% by mass or more, more preferably 0.4% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. The photopolymerizable composition may contain only one photopolymerization initiator or may contain two or more photopolymerization initiators. When containing two or more photopolymerization initiators, their total amount is preferably within the above-mentioned range.

[0274] Resin

[0275] 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.

[0276] Examples of resins include (meth)acrylic resins, olefin-thiol resins, polyester resins, polycarbonate resins, vinyl polymers [e.g., polydiene resins, polyolefin resins, polystyrene resins, polyvinyl ether resins, polyvinyl alcohol resins, polyvinyl ketone resins, polyvinyl fluoride resins, and polybrominated vinyl resins, etc.], polysulfide resins, polystyrene resins, polysulfonate resins, polynitrosopolymer resins, polysiloxane resins, polysulfide resins, polysulfide ester resins, polysulfone resins, polysulfonamide resins, polyamide resins, polyimide resins, polyurea resins, polyphosphonadenene resins, polysilane resins, polysilazane resins, polyfuran resins, polybenzoxazole resins, polyoxadiazole resins, polybenzothiazide-phenothiazine resins, polybenzothiazide resins, polypyrazine-quinoxaline resins, polyquinoxaline resins, polybenzimidazole resins, polyoxyisoindoline resins, polydioxoisoindoline resins, polytriazine resins, and polypyridazine resins. The resins include piperazine resins, polypyridine resins, polypiperidine resins, polytriazole resins, polypyrazole resins, polypyrrolidone resins, polycarboborane resins, polyoxabicyclononane resins, polydibenzofuran resins, polyphthalol resins, polyacetal resins, polyimide resins, polyamide-imide resins, olefin resins, cyclic olefin resins, epoxy resins, and acylated cellulose resins. The preferred curing method is selected from at least one of (meth)acrylic resins, polystyrene resins, polyester resins, polyurethane resins, polysulfurethane resins, polyimide resins, epoxy resins, polycarbonate resins, and acylated cellulose resins, considering the ease of forming a curing physiology that exhibits good compatibility with the aforementioned specific compounds and suppresses planar inhomogeneity. More preferably, the resins are selected from at least one of (meth)acrylic resins, polystyrene resins, polyester resins, polyurethane resins, polysulfurethane resins, polycarbonate resins, and acylated cellulose resins.

[0277] As a (meth)acrylic resin, examples include polymers containing structural 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)acrylates, (meth)acrylamide, and (meth)acrylonitrile.

[0278] Examples of polyester resins include polymers obtained by reacting polyols (e.g., ethylene glycol, propylene glycol, glycerol, and trimethylolpropane) with polyacids (e.g., aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, as well as dicarboxylic acids in which the hydrogen atoms of these aromatic rings are replaced by methyl, ethyl, or phenyl, etc.), aliphatic dicarboxylic acids with 2 to 20 carbon atoms (e.g., adipic acid, sebacic acid, and dodecanedicarboxylic acid) or alicyclic dicarboxylic acids (e.g., cyclohexanedicarboxylic acid, etc.)), and polymers obtained by ring-opening polymerization of cyclic ester compounds such as caprolactone monomers (e.g., polycaprolactone).

[0279] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, and aliphatic epoxy resin. Commercially available epoxy resins can be used; examples of commercially available products include the following resins.

[0280] Examples of commercially available bisphenol A epoxy resins include jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009 and jER1010 (all manufactured by Mitsubishi Chemical Corporation), and 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 (manufactured by Mitsubishi Chemical Corporation), EPICLON830 and EPICLON835 (manufactured by DIC Corporation), and LCE-21 and RE-602S (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available phenolic varnish type epoxy resins include jER152, jER154, jER157S70, and jER157S65 (manufactured by Mitsubishi Chemical Corporation), and EPICLON N-740, EPICLON N-770, and EPICLON N-775 (manufactured by DIC Corporation). Examples of commercially available cresol varnish-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 the ADEKARESIN EP series (e.g., EP-4080S, EP-4085S, and EP-4088S; manufactured by ADEKA CORPORATION), EHPE3150, EPOLEAD PB 3600, and EPOLEAD PPB 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. EP series (e.g., EP-4000S, EP-4003S, EP-4010S, and EP-4011S; 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 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 (manufactured by NOFCORPORATION, epoxy-containing polymers), etc.

[0281] As a cellulose acylated resin, the cellulose acylated resins described in paragraphs 0016 to 0021 of Japanese Patent Application Publication No. 2012-215689 may be used appropriately. As a polyester resin, commercially available products such as the Byron series manufactured by TOYOBO CO., LTD. (e.g., Byron 500) may also be used. As a commercially available (meth)acrylic resin, the SK Dyne series manufactured by Soken Chemical & Engineering Co., LTD. (e.g., SK Dyne-SF2147) may also be used.

[0282] As a polystyrene resin, a resin containing 50% by mass or more of repeating units derived from styrene monomers is preferred, a resin containing 70% by mass or more of repeating units derived from styrene monomers is more preferred, and a resin containing 85% by mass or more of repeating units derived from styrene monomers is even more preferred.

[0283] Specific examples of styrene monomers include styrene and its derivatives. Styrene derivatives are compounds to which other groups are bonded, such as alkylstyrene like o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, and p-ethylstyrene, as well as substituted styrene such as hydroxyl styrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, and p-chlorostyrene, which have hydroxyl, alkoxy, carboxyl, or halogen groups introduced onto the benzene ring of styrene.

[0284] Furthermore, polystyrene resins may also contain repeating units derived from monomers other than styrene-based monomers. Examples of such monomers include alkyl methacrylates such as methyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, and isopropyl methacrylate; unsaturated carboxylic acid monomers such as methacrylic acid, acrylic acid, itconic acid, maleic acid, fumaric acid, and cinnamic acid; anhydrides, i.e., unsaturated dicarboxylic acid anhydrides, such as maleic anhydride, itconic acid, ethyl maleic acid, methyl itconic 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.

[0285] Commercially available polystyrene resins include AS-70 (acrylonitrile / styrene copolymer resin, manufactured by NIPPONSTEEL Chemical & Material Co., Ltd.) and SMA2000P (styrene / maleic acid copolymer, manufactured by KAWAHARAPETROCHEMICAL CO., LTD.).

[0286] 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 (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-opening polymers containing each compound.

[0287] Addition (co)polymers of norbornene compounds are described in Japanese Patent Application Publication No. 10-007732, Japanese Patent Publication No. 2002-504184, U.S. Patent Publication No. 2004 / 229157A, or International Patent Publication No. 2004 / 070463, etc. Polymers of norbornene compounds are obtained by adding norbornene compounds (e.g., polycyclic unsaturated compounds of norbornene) to each other.

[0288] Hydrogenates of polymers of norbornene compounds can be synthesized by hydrogenation following addition polymerization or translocation ring-opening polymerization of norbornene compounds. Synthetic methods are described, for example, in Japanese Patent Application Publication Nos. 01-240517, 07-196736, 60-026024, 62-019801, 2003-159767, and 2004-309979.

[0289] Commercially available cyclic olefin resins include the ARTON series (e.g., ARTON G, ARTON F, ARTON RX4500, etc.) manufactured by JSR Corporation, and ZEONOR (Zeonor) ZF14, ZF16, ZEONEX (Zeonex) 250, ZEONEX 280, etc. manufactured by Zeon Corporation.

[0290] 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 using epoxy resin, the weight-average molecular weight (Mw) 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.

[0291] The weight-average molecular weight of the resin was measured by gel permeation chromatography (GPC). For the GPC-based measurements, an HLC-8020GPC (manufactured by Tosoh Corporation) was used as the measuring apparatus, three TSKgel Super Multipore HZ-H columns (4.6mm ID × 15cm, manufactured by Tosoh Corporation) were used as the column, and THF (tetrahydrofuran) was used as the eluent. The measurement conditions were set as follows: sample concentration 0.45% by mass, flow rate 0.35 ml / min, sample injection volume 10 μl, and measurement temperature 40°C, using an RI detector. Calibration curves were constructed using eight samples from 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".

[0292] The resin can be an alkali-soluble resin. Examples of alkali-soluble resins include those containing acid groups. Examples of acid radicals include carboxyl groups, phosphate groups, sulfonate groups, and phenolic hydroxyl groups. There can be only one type of acid radical, or there can be two or more.

[0293] The alkali-soluble resin is a linear organic polymer, preferably a resin that is soluble in organic solvents and can be developed by 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 anhydride copolymers, etc., as described in Japanese Patent Application Publication Nos. 59-044615, 54-034327, 58-012577, 54-025957, 59-053836, and 59-071048, as well as acidic cellulose derivatives having carboxyl groups in their side chains.

[0294] Furthermore, as an alkali-soluble resin, resins obtained by adding anhydrides to polymers containing hydroxyl groups can also be used.

[0295] Alkali-soluble resins can be resins copolymerized from hydrophilic monomers. Examples of hydrophilic monomers include alkoxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, glyceryl (meth)acrylates, methacrylamide, N-hydroxymethylacrylamide, secondary or tert-alkylacrylamide, dialkylaminoalkyl (meth)acrylates, morpholine (meth)acrylates, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear (meth)acrylate, branched or linear (meth)acrylate, butyl (meth)acrylate, or phenoxyhydroxypropyl (meth)acrylate. Other hydrophilic monomers may include those containing tetrahydrofurfuryl, phosphate, phosphate ester, quaternary ammonium salt, ethylene oxy chain, propylene oxy chain, sulfonic acid group and groups derived from their salts, morpholinoethyl, etc.

[0296] To improve crosslinking efficiency, alkali-soluble resins can have groups containing olefinic unsaturated bonds, such as vinyl, styrene, allyl, methallyl, and (meth)acryloyl groups. Commercially available alkali-soluble resins containing olefinically unsaturated groups include: the Dianal BR series (polymethyl methacrylate (PMMA), such as Dianal BR-80, BR-83 and BR-87; manufactured by Mitsubishi Chemical Corporation); Photomer 6173 (carboxyl-containing polyurethane acrylic oligomer; Diamond Shamrock Co., Ltd.); Viscoat R-264 and KS Resist 106 (both manufactured by OSAKAORGANIC CHEMICAL INDUSTRY LTD); the CYCLOMER P series (e.g. ACA230AA), the PLACACCEL CF200 series (both 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.), etc.

[0297] Among these various alkali-soluble resins, from the viewpoint of heat resistance, polyhydroxystyrene resins, (meth)acrylic resins, polystyrene resins and polysiloxane resins are preferred, and from the viewpoint of controlling developability, (meth)acrylic resins are more preferred.

[0298] The weight-average molecular weight of the alkali-soluble resin is preferably 3,000 to 200,000, more preferably 5,000 to 50,000.

[0299] The acid value of the alkali-soluble resin is preferably 30 to 200 mg KOH / g. As the lower limit of the acid value, it is preferably 50 mg KOH / g or more, more preferably 70 mg KOH / g or more. Furthermore, as the upper limit of the acid value, it is preferably 150 mg KOH / g or less, more preferably 120 mg KOH / g or less. The acid value of the resin is measured according to JIS K0070 (1992) and calculated to be 1 mmol / g = 56.1 mg KOH / g.

[0300] Regarding alkali-soluble resins, reference can be made to the descriptions in Japanese Patent Application Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to paragraphs 0685 to 0700 of U.S. Patent Application Publication No. 2012 / 0235099), and paragraphs 0076 to 0099 of Japanese Patent Application Publication No. 2012-198408, and these contents are incorporated herein by reference.

[0301] When using the photopolymerizable composition of the present invention for lenses (e.g., spectacle lenses), the resin is preferably a thermoplastic resin such as a carbonate resin, a (meth)acrylic resin (e.g., polymethyl methacrylate (PMMA)), or a thermosetting resin such as a polyurethane resin. Examples of commercially available carbonate resins include polycarbonate resin compositions (trade name: Calibur 200-13, manufactured by Sumitomo Dow Limited) and diethylene glycol dielyl carbonate resin (trade name: CR-39, manufactured by PPG Industries). As for the polyurethane resin, a 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; manufactured by Mitsui Chemicals, Inc.).

[0302] Furthermore, the resin can also be used with adhesives and bonding agents. Examples of adhesives include acrylic adhesives, rubber adhesives, and silicone adhesives. Acrylic adhesives refer to adhesives containing polymers ((meth)acrylic acid polymers) containing (meth)acrylic acid monomers. Examples of bonding agents include polyurethane resin adhesives, polyester adhesives, acrylic resin adhesives, vinyl ethylene acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, and silicone adhesives. Among these, considering high adhesive strength, polyurethane resin adhesives or silicone adhesives are preferred. Commercially available adhesives can be used; examples of commercially available adhesives include TOYO INK CO., LTD.'s polyurethane resin adhesive (LIS-073-50U: trade name) and Soken Chemical & Engineering Co., Ltd.'s acrylic adhesive (SK Dyne-SF2147: trade name).

[0303] The total light transmittance of the resin is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. Furthermore, in this specification, the total light transmittance of the resin is a value measured according to the content described on pages 225-232 of "Experimental Chemistry Lecture 29: Polymer Materials and Media" (Maruzen, 1992), edited by the Chemical Society of Japan.

[0304] When the photopolymerizable composition contains a resin, the resin content in the total solids component 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 one resin or two or more resins. When it contains two or more resins, their total amount is preferably within the above-mentioned range.

[0305] Solvent

[0306] The photopolymerizable composition of the present invention preferably contains a solvent. The solvent can be used without particular limitation, as long as it satisfies the solubility of the coexisting components or the coatability as a photopolymerizable composition. Organic solvents are preferred.

[0307] Examples of organic solvents include alcohol solvents, ester solvents, ether solvents, ketone solvents, amide solvents, hydrocarbon solvents, and halogen solvents.

[0308] Specific examples of alcohol-based solvents 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, glycerol, etc.

[0309] Specific examples of ester-based 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, and alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate). More specifically, examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate. (etc.), alkyl 3-oxypropionic acid esters, alkyl 2-oxypropionic acid esters, methyl 2-oxy-2-methylpropionic acid, ethyl 2-oxy-2-methylpropionic acid, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, methyl cellosol acetate, ethyl cellosol acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl 3-ethoxypropionic acid, ethyl 3-ethoxypropionic acid, ethylene carbonate, etc.

[0310] 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, dioxane, etc.

[0311] Specific examples of amide solvents include N-methylpyrrolidone, dimethylformamide, and dimethylacetamide.

[0312] Specific examples of ketone solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

[0313] Specific examples of hydrocarbon solvents include toluene and xylene.

[0314] Specific examples of halogen-based solvents include chloroform and dichloromethane.

[0315] Two or more of these organic solvents can be used simultaneously.

[0316] The organic solvent is preferably a solvent containing 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, cyclopentanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

[0317] The solvent content in the photopolymerizable composition is preferably 10-90% by mass, more preferably 30-90% by mass, and even more preferably 50-90% by mass. The photopolymerizable composition may contain one solvent or two or more solvents. When it contains two or more solvents, their total amount is preferably within the above range.

[0318] Senses enhancers

[0319] The photopolymerizable composition of the present invention can contain a sensitizer. Typical sensitizers include compounds described in Krivello [JVCrivello, Adv. in Polymer Sci., 62, 1 (1984)]. Specific examples of sensitizers include pyrene, dinaphthalene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocumarin, phenothiazine, camphorquinone, and phenothiazine derivatives. When containing a sensitizer, the content of the sensitizer is preferably 50 to 200 parts by weight relative to 100 parts by weight of the photopolymerization initiator.

[0320] Other UV absorbers

[0321] The photopolymerizable compositions of the present invention can contain ultraviolet absorbers (hereinafter also referred to as other ultraviolet absorbers) other than the specific compounds described above.

[0322] The maximum absorption wavelength of other ultraviolet absorbers is preferably in the wavelength range of 300 to 380 nm, more preferably in the wavelength range of 300 to 370 nm, even more preferably in the wavelength range of 310 to 360 nm, and particularly preferably in the wavelength range of 310 to 350 nm.

[0323] Other ultraviolet absorbers include aminobutadiene-based ultraviolet absorbers, benzoylmethane-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, acrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers, with benzotriazole-based, benzophenone-based, and triazine-based ultraviolet absorbers being more preferred. Specific examples of other ultraviolet absorbers include compounds described in paragraphs 0065 to 0070 of Japanese Patent Application Publication No. 2009-263616 and compounds described in paragraph 0065 of International Patent Publication No. 2017 / 122503, the contents of which are incorporated herein by reference. Other preferred ultraviolet absorbers include 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(4-butoxy-2-hydroxyphenyl)-4,6-bis(4-butoxyphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butoxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0324] When the photopolymerizable composition contains other ultraviolet absorbers, the content of other ultraviolet absorbers in the total solids component of the photopolymerizable composition is preferably 0.01 to 50% by mass. The lower limit is preferably 0.05% by mass or more, 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.

[0325] Furthermore, the total content of the aforementioned specific compounds and other ultraviolet absorbers in the total solids component of the photopolymerizable composition is preferably 0.01 to 50% by mass. The lower limit is preferably 0.05% by mass or more, 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.

[0326] The photopolymerizable composition may contain only one other ultraviolet absorber or two or more. When it contains two or more other ultraviolet absorbers, their total amount is preferably within the range described above.

[0327] Compounds containing epoxy groups

[0328] The photopolymerizable composition of the present invention can 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 or polyfunctional aliphatic glycidyl ether compounds. Furthermore, compounds having alicyclic epoxy groups can also be used as epoxy compounds. Examples of epoxy compounds include compounds having one epoxy group per molecule. Epoxy compounds are preferably compounds having 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 the number of epoxy groups is preferably 2 or more. Specific examples of monofunctional epoxy compounds include 2-ethylhexyl epoxypropyl ether. Specific examples of polyfunctional epoxy compounds include 1,4-cyclohexanediethanol diepoxypropyl ether, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, etc.

[0329] Epoxy compounds can be low molecular weight compounds (e.g., molecular weight less than 1000) or high molecular weight compounds (macromolecules) (e.g., molecular weight of 1000 or more; when a polymer, the weight-average molecular weight is 1000 or more). The weight-average molecular weight of the epoxy compound is preferably 2000 to 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 CELLO XIDE 2021P (trade name, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate) manufactured by Daicel Corporation and RIKARESIN DME-100 (trade name, containing 1,4-cyclohexanediethanol diepoxypropyl ether as the main component) manufactured by New Japan Chemical Co., Ltd., and other multifunctional epoxy compounds.

[0330] When the photopolymerizable composition contains a compound with an epoxy group, the content of the compound with an epoxy group in the total solids component of the photopolymerizable composition is preferably 0.1% to 50% by mass. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The photopolymerizable resin composition may contain only one type of compound with an epoxy group, or it may contain two or more types. When it contains two or more types of compounds with epoxy groups, it is preferable that the total amount of these compounds is within the above range.

[0331] Acid-producing agents

[0332] The photopolymerizable composition of the present invention can contain an acid-generating agent. The acid-generating agent can be a photoacid-generating agent or a thermal acid-generating agent. Furthermore, in this specification, an acid-generating agent refers to a compound that generates acid by applying energy such as heat or light. A thermal acid-generating agent refers to a compound that generates acid through thermal decomposition. A photoacid-generating agent refers to a compound that generates acid through light irradiation. Examples of acid-generating agents, specific compounds, and preferred examples include compounds described in paragraphs 0066 to 0122 of Japanese Patent Application Publication No. 2008-013646, and these can be applied to the present invention.

[0333] Regarding thermally generated acid agents, compounds with a thermal decomposition temperature preferably in the range of 130°C to 250°C, more preferably in the range of 150°C to 220°C, can be cited as examples. Examples of thermally generated acid agents include compounds that produce low nucleophilic acids such as sulfonic acids, carboxylic acids, and disulfonyl imides upon heating. As for the acid produced from the thermally generated acid agent, acids with a pKa of 4 or less are preferred, more preferably acids with a pKa of 3 or less, and even more preferably acids with a pKa of 2 or less. Examples include sulfonic acids, alkyl carboxylic acids substituted with electron-withdrawing groups, aryl carboxylic acids, and disulfonyl imides. Examples of electron-withdrawing groups include halogen atoms such as fluorine atoms, halogenated alkyl groups such as trifluoromethyl groups, nitro groups, and cyano groups.

[0334] Examples of photoacid-generating agents include onium salts such as diazonium salts, phosphonium salts, sulfonium salts, and monazine salts, as well as sulfonate compounds such as imide sulfonates, oxime sulfonates, diazonium disulfones, disulfones, and o-nitrobenzyl sulfonates, which decompose to produce acids upon light irradiation. Commercially available photoacid-generating agents include WPAG-469 (manufactured by FUJIFILM Wako Pure Chemical Corporation), CPI-100P (manufactured by San-Apro Ltd.), and Irgacure290 (BASF Japan Ltd.). Furthermore, 2-isopropylthioxanthrone can also be used as a photoacid-generating agent.

[0335] When the photopolymerizable composition contains an acid-generating agent, the content of the acid-generating agent relative to 100 parts by weight of the polymerizable compound is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, and even more preferably 0.1 to 20 parts by weight. The photopolymerizable composition may contain only one acid-generating agent or may contain two or more acid-generating agents. When it contains two or more acid-generating agents, the total amount of these is preferably within the above-mentioned range.

[0336] "catalyst"

[0337] The photopolymerizable composition of the present invention can 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 content of the catalyst relative to 100 parts by mass of the polymerizable compound 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. The photopolymerizable composition may contain only one catalyst or may contain two or more catalysts. When two or more catalysts are contained, their total amount is preferably within the above-mentioned range.

[0338] Silane coupling agents

[0339] The photopolymerizable composition of the present invention can contain a silane coupling agent. According to this method, the adhesion between the obtained cured product and the support can be further improved. In this specification, a silane coupling agent refers to a silane compound having a hydrolyzable group and other functional groups. Furthermore, a hydrolyzable group refers to a substituent that directly bonds to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Furthermore, examples of functional groups other than the hydrolyzable group include vinyl, (meth)allyl, (meth)acryloyl, mercapto, epoxy, oxetyl, amino, urea, thioether, isocyanate, and phenyl groups, with amino, (meth)acryloyl, and epoxy groups being preferred. Specific examples of silane coupling agents include compounds described in paragraphs 0018 to 0036 of Japanese Patent Application Publication No. 2009-288703 and compounds described in paragraphs 0056 to 0066 of Japanese Patent Application Publication No. 2009-242604, the contents of which are incorporated herein by reference. Commercially available silane coupling agents include A-50 (organosilane) from Soken Chemical & Engineering Co., Ltd. The content of the silane coupling agent in the total solids composition 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. There may be only one type of silane coupling agent, or there may be two or more types. When there are two or more types, the total amount is preferably within the above-mentioned range.

[0340] Surfactants

[0341] The photopolymerizable composition of the present invention can contain a surfactant. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Application Publication No. 2009-237362.

[0342] The preferred surfactants are nonionic surfactants, fluorinated surfactants, or silicone surfactants.

[0343] Commercially available fluorinated 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, and F-5 59, F-560, 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 (the above are DIC) FLUORAD FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), Footgent 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 (all manufactured by NEOS COMPANY LIMITED), etc.

[0344] Fluorinated surfactants can also preferably use acrylic compounds that have a molecular structure with a fluorine-containing functional group, and whose fluorine-containing functional group is cleaved upon heating, causing the fluorine atom to volatilize. Examples of such fluorinated surfactants include the MEGAFAC DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), NIKKEI BUSINESSDAILY (February 23, 2016)), such as MEGAFAC DS-21.

[0345] Fluorinated surfactants are also preferably polymers of fluorinated vinyl ether compounds having fluorinated alkyl or fluorinated alkylene ether groups and hydrophilic vinyl ether compounds.

[0346] Fluorinated surfactants can also be used with block polymers.

[0347] Fluorinated surfactants can also use fluorinated polymers containing repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxide or propoxide).

[0348] Fluorinated surfactants can also be used on fluoropolymers with olefinically unsaturated groups in their side chains. Commercially available examples include MEGAFAC RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0349] Furthermore, due to concerns about the environmental suitability of compounds with straight-chain perfluoroalkyl groups having 7 or more carbon atoms, perfluorooctanoic acid (PFOA) or perfluorooctane sulfonic acid (PFOS) are preferred as fluorinated surfactants.

[0350] Examples of silicone surfactants include linear polymers formed by siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends. Commercially available silicone 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, and Toray Silicone SH8400 (all of which are Dow Corning Toray). (Manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (manufactured by BYKChemie), etc.

[0351] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. Commercially available nonionic surfactants include: PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), SOLSPERSE 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako PureChemical Corporation), PIONIND-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL&FAT CO., LTD), OLFINE1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry). Co., Ltd. (manufacturing), etc.

[0352] The surfactant content in the total solids component 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. There may be only one surfactant or two or more surfactants. When there are two or more surfactants, the total amount is preferably within the above range.

[0353] Other Additives

[0354] The photopolymerizable composition of the present invention may contain, as needed, any additives such as antioxidants, light stabilizers, processing stabilizers, anti-aging agents, compatibilizers, and polymerization inhibitors. By appropriately including these components, various properties of the obtained cured product can be appropriately adjusted.

[0355] <Preparation Method of Photopolymerizable Composition>

[0356] There are no particular limitations on the preparation method of the photopolymerizable composition of the present invention. For example, it can be prepared by mixing the compound represented by formula (1) or (2), the polymerizable compound, and the photopolymerization initiator, and further mixing the above-mentioned components as needed.

[0357] When preparing a photopolymerizable composition, all components can be combined together, or they can be dissolved or dispersed in a solvent and then combined sequentially. Furthermore, the order of addition or operating conditions during preparation are not particularly limited. For example, all components can be dissolved or dispersed in a solvent simultaneously to prepare the photopolymerizable composition, or the components can be appropriately formulated into two or more solutions or dispersions as needed, and then mixed together before use (during coating) to prepare the photopolymerizable composition.

[0358] When preparing a photopolymerizable composition, it is preferable to mix the components and then filter them through a filter with the aim of removing foreign matter and reducing defects. As for the filter, any filter that has been used for filtration purposes can be used without particular limitation. Examples include filters using materials such as fluoropolymers like polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins like nylon (e.g., nylon-6, nylon-6, 6), and polyolefin resins (containing high-density, ultra-high molecular weight polyolefin resins) such as polyethylene and polypropylene (PP). Among these raw materials, polypropylene (containing high-density polypropylene) and nylon are preferred.

[0359] The pore size of the filter is preferably 0.01–7.0 μm, more preferably 0.01–2.5 μm, and even more preferably 0.01–2.0 μm. As long as the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. The pore size value of the filter can be referenced from the filter manufacturer's specifications. Various filters supplied by NIHON PALL Corporation (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (Formerly Nippon on Mykrolis Corporation), and KITZ MICROFILTERC Corporation can be used.

[0360] Furthermore, fibrous filter media are preferred as filters. Examples of fibrous filter media include polypropylene fiber, nylon fiber, and glass fiber. Commercially available products include the SBP series (SBP008, etc.), TPR series (TPR002, TPR005, etc.), and SHPX series (SHPX003, etc.) manufactured by ROKI TECHNO CO., LTD.

[0361] When using filters, different filters can be combined (e.g., filter 1 and filter 2, etc.). Filtration can then be performed once or more using each filter. Furthermore, filters with different pore sizes within the aforementioned range can be combined.

[0362] "use"

[0363] The photopolymerizable compositions of the present invention can be suitably used for applications where exposure to light, including sunlight or ultraviolet light, is possible. Specific examples include coating materials or films for window glass in houses, facilities, and transport machinery; interior and exterior decorative materials and coatings for houses, facilities, and transport machinery; components for light sources emitting ultraviolet light, 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 their coating materials, such as plastic lenses, contact lenses, eyeglasses, and prosthetic eyes; optical products such as filters, prisms, mirrors, and photographic materials; stationery such as tape and ink; signs, markers, and their surface coating materials. For detailed information on these, please refer to paragraphs 0158 to 0218 of Japanese Patent Application Publication No. 2009-263617, which is incorporated herein by reference.

[0364] The photopolymerizable composition of the present invention can be suitably used in optical components, etc. For example, it can be suitably used as a photopolymerizable composition for ultraviolet cut-off filters, lenses, or protective materials. The form of the protective material is not particularly limited, and examples include coatings, films, sheets, etc. Furthermore, the photopolymerizable composition of the present invention can also be used as an adhesive, bonding agent, etc.

[0365] The photopolymerizable composition of the present invention can also be used in various components of display devices. For example, in a liquid crystal display device, it can be used in antireflective films, polarizer protective films, optical films, retardation films, adhesives, and bonding agents that constitute various components of the liquid crystal display device. Furthermore, in an organic electroluminescent display device, it can be used in optical films, polarizer protective films in circular polarizers, retardation films such as quarter-wave plates, adhesives, and bonding agents that constitute various components of the organic electroluminescent display device.

[0366] <Solidified Materials and Their Applications>

[0367] The cured product of the present invention is obtained by curing the above-described photopolymerizable composition of the present invention.

[0368] The cured product of the present invention can be a molded article obtained by shaping a photopolymerizable composition into a desired shape. The shape of the molded article can be appropriately selected according to its application and purpose. Examples include coatings, films, sheets, plates, lenses, tubes, and fibers.

[0369] The cured product of this invention can be suitably used as an optical component. Examples of optical components include ultraviolet cut-off filters, lenses, and protective materials. It can also be used for polarizers, etc.

[0370] Regarding ultraviolet cutoff filters, they can be used in items such as light filters, display devices, solar cells, and window glass. As for the types of display devices, there are no particular limitations; examples include liquid crystal displays and organic light-emitting diode (OLED) displays.

[0371] When the cured product of the present invention is used in a lens, the cured product itself can be formed into a lens shape for use. Furthermore, the cured product of the present invention can be used as a coating on the lens surface, an intermediate layer (adhesive layer) for bonding lenses, etc. Regarding bonding lenses, examples include those described in paragraphs 0094 to 0102 of International Publication No. 2019 / 131572, the contents of which are incorporated herein by reference.

[0372] There are no particular limitations on the types of protective materials used; examples include protective materials for display devices, protective materials for solar cells, protective materials for window glass, and organic electroluminescent display devices. There are also no particular limitations on the shape of the protective material; examples include coatings, films, and sheets.

[0373] <Optical Components>

[0374] The optical component of the present invention contains the cured product of the present invention described above. The cured product of the present invention can be a molded article obtained by molding the photopolymerizable composition of the present invention into a desired shape. The shape of the molded article can be appropriately selected according to the application and purpose. For example, coating-like, film-like, sheet-like, plate-like, lens-like, tubular, fibrous, etc., can be included.

[0375] The optical components of the present invention can also be components made by attaching polarizers and polarizer protective films using the photopolymerizable composition of the present invention.

[0376] Examples of optical components include ultraviolet cut-off filters, lenses, and protective materials.

[0377] Regarding ultraviolet cutoff filters, they can be used in items such as light filters, display devices, solar cells, and window glass. As for the types of display devices, there are no particular limitations; examples include liquid crystal displays and organic light-emitting diode (OLED) displays.

[0378] Examples of lenses include lenses in which the cured product of the present invention is itself formed into a lens shape; lenses in which a coating film on the lens surface is formed from the photopolymerizable composition of the present invention, and intermediate layers (adhesive layers, bonding layers) for bonding lenses are formed.

[0379] There are no particular limitations on the types of protective materials used; examples include protective materials for display devices, solar cells, and window glass. There are also no particular limitations on the shape of the protective material; examples include coatings, films, and sheets.

[0380] Furthermore, resin films can be cited as an example of optical components. The resins used in the photopolymerizable composition for forming the resin film can include the aforementioned resins, preferably (meth)acrylic resins, polyester fibers, cyclic olefin resins, and cellulose acylate resins, more preferably cellulose acylate resins. The photopolymerizable composition containing cellulose acylate resin can contain additives described in paragraphs 0022 to 0067 of Japanese Patent Application Publication No. 2012-215689. Examples of such additives include, for instance, sugar esters. By adding sugar ester compounds to the photopolymerizable composition containing cellulose acylate resin, the total haze and internal haze can be reduced without impairing the visibility of optical properties and without heat treatment before the stretching process. Furthermore, the resin film (cellulose acylate film) using the photopolymerizable composition containing 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 be further laminated with the hard coating described in paragraphs 0097 to 0113 of Japanese Patent Application Publication No. 2012-215689.

[0381] Furthermore, as another form of optical component, an optical component having a laminate of a support and a resin layer can be cited.

[0382] The thickness of the resin layer in the above-mentioned laminate is preferably 1 μm to 2500 μm, more preferably 10 μm to 500 μm.

[0383] The support material in the aforementioned laminate is preferably a transparent material that does not impair optical performance. Transparency of the support material refers to optical transparency; specifically, it means that the total light transmittance of the support material is 85% or more. The total light transmittance of the support material is preferably 90% or more, more preferably 95% or more.

[0384] Resin films are preferred examples of the support structure. Examples of resins constituting the resin film include ester resins (e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexanedimethyl terephthalate (PCT), etc.), olefin resins (e.g., polypropylene (PP), polyethylene (PE), etc.), polyvinyl chloride (PVA), cellulose triacetate (TAC), etc. Among these, PET is preferred from a versatility perspective.

[0385] The thickness of the support can be appropriately selected according to its application or purpose. Generally, the thickness is preferably 5 μm to 2500 μm, and more preferably 20 μm to 500 μm.

[0386] Furthermore, the aforementioned support can also be a peelable support. Such a laminate is suitable for use with polarizers, etc. Here, a peelable support refers to a support that can be peeled off from the UV-shielding material. The stress when peeling the support off the UV-shielding material is preferably 0.05 N / 25 mm or more and 2.0 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. After bonding and fixing a laminate cut to a width of 25 mm and a length of 80 mm onto a glass substrate using an acrylic adhesive sheet, a tensile testing machine (A&D Company, Limited RTF-1210) was used to clamp one end (25 mm wide side) of the test piece along its length. A 90° peel test was performed at a crosshead speed of 200 mm / min (clamping speed) in an atmosphere of 23°C and 60% relative humidity, in accordance with Japanese Industrial Standard (JIS) K 6854-1:1999 "Adhesives - Test Method for Peel Bond Strength - Part 1: 90° Peel"), thereby evaluating the stress when the support is peeled from the UV-shielding material.

[0387] As a peelable support, a support containing polyethylene terephthalate (PET) as the main component (the component with the highest content by weight 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. 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 can be subjected to known surface treatments such as corona treatment, glow discharge treatment, and primer coating.

[0388] Furthermore, as another form of optical component, a laminate consisting of a hard coating layer, a transparent support, and an adhesive layer or bonding layer stacked sequentially can be cited. Such a laminate can be appropriately used as an ultraviolet cut-off filter or a protective material (protective film, protective sheet). In this type of optical component, it is sufficient that any one of the support, hard coating, and adhesive layer or bonding layer contains the cured product of the present invention described above.

[0389] As a hard coating, for example, it is applicable to Japanese Patent Application Publication Nos. 2013-045045, 2013-043352, 2012-232459, 2012-128157, 2011-131409, 2011-131404, 2011-126162, 2011-075705, 2009-286981, and 2009-26356. The hard coatings described in Japanese Patent Application Publication No. 7, Japanese Patent Application Publication No. 2009-075248, Japanese Patent Application Publication No. 2007-164206, Japanese Patent Application Publication No. 2006-096811, Japanese Patent Application Publication No. 2004-075970, Japanese Patent Application Publication No. 2002-156505, Japanese Patent Application 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. From the viewpoint of further improving scratch resistance, the thickness of the hard coating is preferably 5 μm to 100 μm.

[0390] The optical component of this type has an adhesive layer or bonding layer on the side of the supporting substrate opposite to the side with the hard coating. There are no particular limitations on the type of adhesive or bonding agent used for the adhesive layer or bonding layer; known adhesives or bonding agents can be used. Furthermore, it is preferable to use an adhesive or bonding agent containing 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. Additionally, the adhesive or bonding agent may also contain the adhesion improver (silane compound) described in paragraphs 0088 to 0097 of Japanese Patent Application Publication No. 2017-142412 and the 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 Application Publication No. 2017-142412. From the viewpoint of balancing adhesion and workability, the thickness of the adhesive layer or bonding layer is preferably 5 μm to 100 μm.

[0391] The optical components of the present invention can be appropriately used as components of displays such as liquid crystal display devices (LCDs) and organic light-emitting diode (OLEDs).

[0392] Examples of liquid crystal display devices include those incorporating the cured material of the present invention in components such as antireflective films, polarizing protective films, optical films, retardation films, adhesives, and bonding agents. The optical components incorporating the present invention can be disposed in the liquid crystal cell on either the observer side (front side) or the backlight side, and in the polarizer, they can be disposed on either the side furthest from the liquid crystal cell (outer side) or the side closest to the liquid crystal cell (inner side).

[0393] Examples of organic electroluminescent display devices include those incorporating the cured material of the present invention in components such as optical films, polarizer protective films in circular polarizers, phase retardation films in quarter-wave plates, adhesives, and binders. By incorporating the cured material of the present invention into the above structures, degradation of the organic electroluminescent display device due to external light can be suppressed.

[0394] Example

[0395] The present invention will be further described in detail below with examples. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the 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 methyl, Et is ethyl, Bu is butyl, tBu is tert-butyl, Pr is propyl, Ph is phenyl, and Ac is acetyl.

[0396] <Synthesis example>

[0397] (Synthetic Example 1)(Synthesis of Compound (1)-52)

[0398] Intermediate 1-1 was synthesized according to the following scheme. In the following scheme, the method described in paragraph 0176 of Japanese Patent Application Publication No. 2016-081035 was used to synthesize intermediate 1-1 from methyl-p-benzoquinone instead of 2-tert-butyl-1,4-benzoquinone.

[0399] [Chemical Formula 22]

[0400]

[0401] Next, intermediates 1-3 were synthesized according to the following synthetic protocol. 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 the mixture was stirred for 30 minutes. The precipitated solid was filtered off, and 300 ml of acetonitrile was added. The mixture was then heated and refluxed under a nitrogen atmosphere for 1 hour. After cooling to room temperature, the mixture was stirred at room temperature for 1 hour, and the solid was filtered off and washed with 150 ml of acetonitrile, thus yielding 106 g of intermediate 1-3 (yield 85%).

[0402] [Chemical Formula 23]

[0403]

[0404] 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. The mixture was then stirred for 10 minutes under ice-cold conditions. 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, 20 ml of water was added, and the mixture was stirred for 30 minutes. The precipitated solid was filtered off, and 50 ml of methanol was added. The mixture was then heated and refluxed under a nitrogen atmosphere for 1 hour. After cooling to room temperature, the mixture was stirred at room temperature for 1 hour, and the solid was filtered off and washed with 25 ml of methanol, thus yielding 5.2 g of compound (1)-52 (85% yield).

[0405] 1 H-NMR (CDCl3): δ7.26 (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)

[0406] [Chemical Formula 24]

[0407]

[0408] (Synthetic Example 2)(Synthesis of Compound (1)-64)

[0409] Intermediate 2 was synthesized according to the same method as in Synthesis Example 1, following the same scheme.

[0410] [Chemical Formula 25]

[0411]

[0412] 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. The mixture was then stirred for 10 minutes under ice-cold conditions. 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, 15 ml of water was added, and the mixture was stirred for 30 minutes. The precipitated solid was filtered off, and 40 ml of methanol was added. The mixture was then heated and refluxed under a nitrogen atmosphere for 1 hour. After cooling to room temperature, the mixture was stirred at room temperature for 1 hour, and the solid was filtered off and washed with 20 ml of methanol to obtain 4.1 g of compound (1)-64 (88% yield).

[0413] 1 H-NMR (CDCl3): δ7.30 (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)

[0414] [Chemical Formula 26]

[0415]

[0416] (Synthetic Example 3)(Synthesis of Compound (1)-46)

[0417] In Synthesis Example 1, 2-ethylhexyl bromide was used instead of 2-ethylhexanoyl chloride. Otherwise, compound (1)-46 was synthesized by the same method as in Synthesis Example 1.

[0418] 1 H-NMR (CDCl3): δ7.26 (m, 6H), 7.11 (m, 4H), 6.70 (s, 1H), 4.77 (s, 2H), 4.75 (s, 2 H), 3.97(dd, 2H), 3.83(d, 2H), 2.37(s, 3H), 1.8~1.6(m, 18H), 1.0~0.9(m, 12H)

[0419] [Chemical Formula 27]

[0420]

[0421] Measurement of maximum absorption wavelength (λmax)

[0422] Two mg of each of the compounds listed in the table below were dissolved in 100 mL of ethyl acetate, and then diluted with ethyl acetate until the absorbance of the solution was in the range of 0.6–1.2 to prepare a sample solution. The absorbance of each sample solution was measured using a UV-1800PC spectrophotometer (manufactured by SHIMADZU CORPORATION) through a 1 cm quartz cuvette. The maximum absorption wavelength (λmax) was measured from the absorption spectrum of each sample solution.

[0423] [Table 1]

[0424] (1)-5 383 (1)-8 383 (1)-11 383 (1)-46 387 (1)-49 387 (1)-52 380 (1)-53 382 (1)-60 375 (1)-64 376 (1)-65 378 (1)-69 383 A-1 375 A-35 372 A-71 372 (2)-1 383 (2)-6 383 (2)-8 408 (2)-9 410 (2)-11 411 (2)-12 413 C-1 388 C-3 357

[0425] (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 structures shown in the specific examples of the above-mentioned compounds.

[0426] C-1, C-3: Compounds with the following structures (comparative compounds)

[0427] [Chemical Formula 28]

[0428]

[0429] <Preparation of Photopolymerizable Compositions>

[0430] (Examples 1-50, Comparative Examples 1 and 2)

[0431] The photopolymerizable compositions of Examples 1-50 and Comparative Examples 1 and 2 were prepared by mixing the following components.

[0432] Ultraviolet absorber… 2.0 parts by weight

[0433] Polymerizing compound… 2.6 parts by weight

[0434] Resin... 12.9 parts by weight

[0435] Photopolymerization initiator… 2.5 parts by weight

[0436] Solvent (propylene glycol monomethyl ether acetate)... 40.0 parts by weight

[0437] Solvent (cyclopentanone)……40.0 parts by weight

[0438] Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd., methanol-modified polydimethylsiloxane at both ends, hydroxyl value 62 mgKOH / g)... 0.02 parts by weight

[0439] [Table 2]

[0440] Example 1 (1)-46 T-1 U-2 V-1 Example 2 (1)-5 T-1 U-2 V-1 Example 3 (1)-8 T-1 U-2 V-1 Example 4 (1)-11 T-1 U-2 V-1 Example 5 (1)-49 T-1 U-2 V-1 Example 6 (1)-52 T-1 U-2 V-1 Example 7 (1)-53 T-1 U-2 V-1 Example 8 (1)-59 T-1 U-2 V-1 Example 9 (1)-60 T-1 U-2 V-1 Example 10 (1)-61 T-1 U-2 V-1 Example 11 (1)-64 T-1 U-2 V-1 Example 12 (1)-65 T-1 U-2 V-1 Example 13 (1)-69 T-1 U-2 V-1 Example 14 A-1 T-1 U-2 V-1 Example 15 A-3 T-1 U-2 V-1 Example 16 A-26 T-1 U-2 V-1 Example 17 A-35 T-1 U-2 V-1 Example 18 A-71 T-1 U-2 V-1 Example 19 (2)-1 T-1 U-2 V-1 Example 20 (2)-6 T-1 U-2 V-1 Example 21 (2)-8 T-1 U-2 V-1 Example 22 (2)-9 T-1 U-2 V-1 Example 23 (2)-11 T-1 U-2 V-1 Example 24 (2)-12 T-1 U-2 V-1 Example 25 (1)-46 T-2 U-2 V-1 Example 26 (1)-46 T-3 U-2 V-1 Example 27 (1)-46 T-4 U-2 V-1 Example 28 (1)-46 T-1 U-1 V-1 Example 29 (1)-46 T-1 U-2 V-2 Example 30 (1)-46 T-1 U-2 V-3 Example 31 (1)-46 T-1 U-2 V-4 Example 32 (1)-46 T-1 U-2 V-5 Example 33 (1)-46 T-1 U-2 V-6 Example 34 (1)-46 T-1 U-2 V-7 Example 35 (1)-46 T-1 U-2 V-8 Example 36 (2)-8 T-1 U-2 V-2 Example 37 (1)-5 T-1 U-2 V-2 Example 38 (1)-5 T-1 U-2 V-5 Example 39 (1)-52 T-1 U-2 V-2 Example 40 (1)-52 T-1 U-2 V-5

[0441] [Table 3]

[0442]

[0443] (Example 51)

[0444] The photopolymerizable composition of Example 51 was prepared by mixing the following components.

[0445] Ultraviolet absorber (1)-46……2.0 parts by weight

[0446] Polymerizable compound T-2……0.5 parts by mass

[0447] Polymerizable compound T-4……1.5 parts by weight

[0448] Resin U-3……13.5 parts by weight

[0449] Photopolymerization initiator V-8…2.5 parts by weight

[0450] Solvent (toluene)……80.0 parts by weight

[0451] Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd., methanol-modified polydimethylsiloxane at both ends, hydroxyl value 62 mgKOH / g)... 0.02 parts by weight

[0452] (Example 52)

[0453] The photopolymerizable composition of Example 52 was prepared by mixing the following components.

[0454] Ultraviolet absorber (1)-46……2.0 parts by weight

[0455] Polymerizable compound T-6……10.5 parts by weight

[0456] Polymerizable compound T-1……5.0 parts by weight

[0457] Photopolymerization initiator V-1……2.2 parts by weight

[0458] Photopolymerization initiator V-5…0.3 parts by weight

[0459] Solvent (ethyl acetate)……40.0 parts by weight

[0460] Solvent (cyclopentanone)……40.0 parts by weight

[0461] Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd., methanol-modified polydimethylsiloxane at both ends, hydroxyl value 62 mgKOH / g)... 0.02 parts by weight

[0462] (Example 53)

[0463] The photopolymerizable composition of Example 53 was prepared by mixing the following components.

[0464] Ultraviolet absorber (1)-46……2.0 parts by weight

[0465] Polymerizable compound T-5……5.0 parts by weight

[0466] Polymerizable compound T-4……4.0 parts by weight

[0467] Resin U-1……6.5 parts by weight

[0468] Photopolymerization initiator V-1……2.0 parts by weight

[0469] Photopolymerization initiator V-6…0.5 parts by weight

[0470] Solvent (ethyl acetate)……40.0 parts by weight

[0471] Solvent (cyclopentanone)……40.0 parts by weight

[0472] Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd., methanol-modified polydimethylsiloxane at both ends, hydroxyl value 62 mgKOH / g)... 0.02 parts by weight

[0473] (Example 54)

[0474] The photopolymerizable composition of Example 54 was prepared by mixing the following components.

[0475] Ultraviolet absorber (1)-46……2.0 parts by weight

[0476] Polymerizable compound T-7……60 parts by weight

[0477] Polymerizable compound T-8…25 parts by weight

[0478] Polymerizable compound T-9…15 parts by weight

[0479] Photopolymerization initiator V-9…8.0 parts by weight

[0480] (Examples 55-59)

[0481] In Example 54, the photopolymerizable compositions of Examples 55 to 59 were prepared in the same manner as in Example 54, except that the ultraviolet absorber (1)-46 was replaced with equal amounts of ultraviolet absorber (1)-5, ultraviolet absorber (1)-52, ultraviolet absorber (1)-64, ultraviolet absorber A-71 or ultraviolet absorber (2)-8.

[0482] The detailed information of the raw materials recorded using the above abbreviations is as follows.

[0483] (UV absorber)

[0484] (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 structures shown in the specific examples of the above-mentioned compounds.

[0485] C-1, C-3: Compounds with the above structures (comparative compounds)

[0486] UV-1: Tinuvin 326 (manufactured by BASF)

[0487] (polymeric compounds)

[0488] T-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a compound having two or more olefinically unsaturated groups)

[0489] T-2: NK Ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd., a compound having two or more olefinically unsaturated groups)

[0490] T-3: Light Acrylate DCP-A (manufactured by KyoEisha Chemical Co., Ltd., a compound having two or more olefinically unsaturated groups)

[0491] T-4: Benzyl methacrylate

[0492] T-5: Beamset 577 (3-6 functional polyurethane acrylate, manufactured by ARAKAWA CHEMICAL INDUSTRIES, LTD.)

[0493] T-6: FA-512M (Dicyclopentenyloxyethyl methacrylate, manufactured by Showa Denko Materialsco., Ltd.)

[0494] T-7: CYCLOMER M100 (methyl 3,4-epoxycyclohexyl methacrylate, manufactured by Daicel Corporation)

[0495] T-8: OTX-221: (3-Ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, difunctional oxetane, manufactured by TOAGOSEI CO., LTD.)

[0496] T-9: Celoxide 2021P (3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, a difunctional epoxy resin, manufactured by Daicel Corporation)

[0497] (resin)

[0498] U-1: A 40% by mass solution of propylene glycol monomethyl ether acetate in a copolymer of benzyl methacrylate / methacrylic acid (75 / 25 [mass ratio]) (weight average molecular weight 12000).

[0499] U-2: DianalBR-80 (manufactured by Mitsubishi Chemical Corporation)

[0500] U-3: ARTON RX4500 (manufactured by JSR Corporation, Tg140℃, cyclic polyolefin resin)

[0501] (Photopolymerization initiator)

[0502] V-1: Omnirad TPO (manufactured by IGM Res ins BV, photoradical polymerization initiator, acylphosphine compound)

[0503] V-2: Omnirad 2959 (manufactured by IGM Resins BV, photoradical polymerization initiator, hydroxyacetophenone compound)

[0504] V-3: 4,4'-bis(diethylamino)benzophenone (photoradical polymerization initiator, benzophenone compound)

[0505] V-4: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (o-Cl-HABI) (photoradical polymerization initiator, hexaarylbiimidazole compound)

[0506] V-5: IRGACURE-OXEO1 (manufactured by BASF, a photoradical polymerization initiator, an oxime compound)

[0507] V-6 Omnirad 907 (manufactured by TGM Resins BV, photoradical polymerization initiator, aminoacetophenone compound)

[0508] V-7 Omnirad 369 (manufactured by IGM Resins BV, photoradical polymerization initiator, aminoacetophenone compound)

[0509] V-8 Omnirad 819 (manufactured by IGM Resins BV, photoradical polymerization initiator, acylphosphine compound)

[0510] V-9: CPI-210S (manufactured by San-Apro Ltd., photocationic polymerization initiator, sulfonium salt)

[0511] Manufacturing of Ultraviolet Cut-off Filters

[0512] (Manufacturing Example 1)

[0513] The photopolymerizable compositions of Examples 1-59 were spin-coated onto a 50mm × 50mm glass substrate (1737, manufactured by Corning Incorporated Co., Ltd.) to a film thickness of 1.5μm, and dried at 100°C for 2 minutes to form a photopolymerizable composition layer. Subsequently, an i-ray stepper exposure apparatus (UX-1000SM-EH04, manufactured by USHIO INC.) was used at 1000mJ / cm². 2 The entire surface of the photopolymerizable composition layer is exposed to a certain amount of exposure. Then, using a hot plate, it is heated at 200°C for 8 minutes (followed by drying), thereby producing a UV cutoff filter (cured product).

[0514] Regarding the photopolymerizable compositions of Examples 1 to 59, the difference in transmittance at the maximum absorption wavelength (λmax) of the photopolymerizable composition layer before and after exposure (transmittance difference 1) and the difference in transmittance at the maximum absorption wavelength (λmax) of the photopolymerizable composition layer before and after drying (transmittance difference 2) are both less than 1%.

[0515] The difference in transmittance 1 = |Transmittance of the photopolymerizable composition layer before exposure at λmax - Transmittance of the photopolymerizable composition layer after exposure at λmax|

[0516] The difference in transmittance 2 = |Transmittance of the photopolymerizable composition layer before drying at λmax - Transmittance of the photopolymerizable composition layer after drying at λmax|

[0517] (Manufacturing Example 2)

[0518] In addition to using the photopolymerizable compositions of Comparative Examples 1 and 2 as photopolymerizable compositions, and adjusting the film thickness of the photopolymerizable composition layer so that the transmittance at the maximum absorption wavelength (λmax) of the photopolymerizable composition layer before exposure is 5 to 20%, an ultraviolet cut-off filter (cured product) was manufactured in the same manner as in Manufacturing Example 1.

[0519] <Evaluation>

[0520] [Evaluation of lightfastness]

[0521] The ultraviolet (UV) cutoff filter obtained above was subjected to a lightfastness test under condition 1, and the reduction in transmittance at the maximum absorption wavelength (λmax) was calculated. Specifically, after measuring the transmittance at the maximum absorption wavelength (λmax) of the UV cutoff filter, a lightfastness test was performed on the UV cutoff filter under condition 1. The transmittance at the maximum absorption wavelength (λmax) of the UV cutoff filter after the lightfastness test was measured, and the reduction in transmittance was calculated using the following formula.

[0522] The degree of reduction in transmittance (%) = (transmittance of the UV cutoff filter at λmax after the lightfastness test) - (transmittance of the UV cutoff filter at λmax before the lightfastness test)

[0523] (Condition 1)

[0524] Apparatus: Xenon lamp weathering tester (Suga Test Instruments Co., Ltd.: XL75)

[0525] Illuminance: 90klx

[0526] Test duration: 50 hours

[0527] Environment: 23℃, relative humidity 50%

[0528] Furthermore, the degree of color change of the ultraviolet cutoff filter after the lightfastness test was visually confirmed, and the presence or absence of coloration was evaluated according to the following criteria.

[0529] A: Uncolored

[0530] B: It has a small amount of coloring, but it is at a practical level.

[0531] [Evaluation of solvent resistance]

[0532] The ultraviolet cutoff filter obtained above was immersed in propylene glycol monomethyl ether acetate (PGMEA) for 10 minutes, the absorbance retention rate was calculated, and the solvent resistance was evaluated according to the following criteria.

[0533] Absorbance retention rate (%) = (Absorbance at λmax of the UV cutoff filter after immersion in PGMEA / Absorbance at λmax of the UV cutoff filter before immersion in PGMEA) × 100

[0534] A: The absorbance retention rate is over 85%.

[0535] B: The absorbance retention rate is above 70% and below 85%.

[0536] C: Absorbance retention rate is less than 70%.

[0537] [Table 4]

[0538]

[0539] [Table 5]

[0540]

[0541] As shown in the table above, Examples 1 to 59 exhibit both high levels of lightfastness and solvent resistance.

[0542] The photopolymerizable composition of the embodiments can be used in various components constituting a liquid crystal display device or an organic electroluminescent display device.

Claims

1. A photopolymerizable composition comprising: The compound represented by formula (1); Polymer compounds; and Photopolymerization initiator, In equation (1), R 1 R 2 Each of these groups independently represents a hydrogen atom, alkyl, aryl, acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, or a group containing an alkene unsaturated bond. R 3 and R 4 One of them is a hydrogen atom, and the other is a halogen atom, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylamino, aniline, acylamino, alkylsulfonamide, arylsulfonamide, alkylthio, arylthio, or a group containing an alkene unsaturated bond. Y 1 Y 2 Each group can be represented independently as an electron-withdrawing group. Y 1 and Y 2 They can be bonded arbitrarily to form rings. R 1 and R 3 They can be bonded arbitrarily to form rings. R 2 and R 4 They can be bonded arbitrarily to form a ring.

2. The photopolymerizable composition according to claim 1, wherein, The compound represented by formula (1) is the compound represented by formula (3) below. In equation (3), R 1 R 2 Each of these groups independently represents a hydrogen atom, alkyl, aryl, acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, or a group containing an alkene unsaturated bond. R 3 and R 4 One of them is a hydrogen atom, and the other is a halogen atom, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylamino, aniline, acylamino, alkylsulfonamide, arylsulfonamide, alkylthio, arylthio, or a group containing an alkene unsaturated bond. R 5 R 6 Each can be used independently to represent a hydrogen atom or a substituent. R 1 and R 3 They can be bonded arbitrarily to form rings. R 2 and R 4 They can be bonded arbitrarily to form rings. R 5 and R 6 They can be bonded arbitrarily to form a ring.

3. The photopolymerizable composition according to claim 1 or 2, wherein, The polymerizable compound is a compound having two or more groups containing olefinic unsaturated bonds.

4. The photopolymerizable composition according to claim 1 or 2, wherein, The photopolymerization initiator is at least one selected from acetophenone compounds, acylphosphine compounds, and benzophenone compounds.

5. The photopolymerizable composition according to claim 1 or 2, further comprising a resin.

6. The photopolymerizable composition according to claim 5, wherein, The resin contains an alkali-soluble resin.

7. The photopolymerizable composition according to claim 5, wherein, The resin is selected from at least one of (meth)acrylic resins, polystyrene resins, polyester resins, polyurethane resins, polysulfide urethane resins, polyimide resins, epoxy resins, polycarbonate resins, cyclic olefin resins, and acylated cellulose resins.

8. The photopolymerizable composition according to claim 1 or 2, wherein it is an adhesive or bonding agent.

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

10. An optical component comprising the cured material of claim 9.

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