Compound, latent antioxidant, composition, cured product and method for producing cured product

Abstract

A compound represented by the following general formula (I-1). A composition comprising a compound represented by the following general formula (I-2) and a detached product from a photodetached group. (In the formula, A represents an atomic group having antioxidant ability, B represents a photodetached group, and k represents an integer of 1 to 10.) (In the formula, A represents an atomic group having antioxidant ability, and k represents an integer of 1 to 10.)

Description

Technical Field

[0001] The present invention relates to a compound which has little curing hindrance and can easily impart antioxidant ability to a cured product. Background Art

[0002] In order to improve the antioxidant ability and heat resistance of a curable composition, a method of adding an ultraviolet absorber or an antioxidant to a curing inhibitor to stabilize the composition is known (Patent Documents 1 to 3).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2011-048382

[0006] Patent document 2: US2016016919A1

[0007] Patent Document 3: Japanese Patent Application Publication No. 2015-108649 Summary of the invention

[0008] However, the antioxidants described in Patent Documents 1 to 3 have a problem in that they may inhibit the curing of the curable composition.

[0009] In order to solve such problems, the present inventors have found that phenolic antioxidants have the function of capturing free radicals that have a great influence on the degradation of polymers, and that when phenolic antioxidants are added to a polymerization system to achieve such a function, they usually act as so-called polymerization inhibitors and sometimes hinder curing.

[0010] As a means for solving the above-mentioned problems, there is known a latent additive in which the above-mentioned light absorbing function is inactivated in the polymerization system and can be activated after curing.

[0011] On the other hand, latent additives that can be activated after curing may require high-temperature heating for activation, and there is a demand for latent additives that can be activated more easily.

[0012] The present invention has been made in view of the above problems, and a main object of the present invention is to provide a compound which has little curing inhibition and can easily impart antioxidant ability to a cured product.

[0013] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that by using a photo-leaving group as a protecting group and protecting the phenolic hydroxyl group contained in the antioxidant with the photo-leaving group, it is easy to adjust the period when the antioxidant ability is manifested, thereby solving the above-mentioned problems and completing the present invention.

[0014] That is, the present invention provides a compound represented by the following general formula (I-1).

[0015] [Chemical formula 1]

[0016]

[0017] (wherein A represents an atomic group having antioxidant ability, B represents a photo-detached group, and k represents an integer of 1 to 10)

[0018] The present invention also provides a latent antioxidant comprising the compound represented by the above general formula (I-1).

[0019] The present invention also provides a composition comprising the compound represented by the above general formula (I-1).

[0020] The present invention also provides a cured product of a composition comprising a compound represented by the above general formula (I-1) and a polymerizable compound.

[0021] In addition, the present invention provides a method for producing a cured product, which comprises the following steps: a step of curing a composition containing a compound represented by the above-mentioned general formula (I-1) and a polymerizable compound to form a cured product; and a step of irradiating the above-mentioned cured product with light to release a photodetachable group contained in the compound represented by the above-mentioned general formula (I-1).

[0022] The present invention also provides a composition (hereinafter sometimes referred to as the "second composition") comprising a compound represented by the following general formula (I-2) (hereinafter sometimes referred to as "compound I-2") and a desorbed product derived from a photo-desorbed group (hereinafter sometimes referred to as "compound B'").

[0023] [Chemical formula 2]

[0024]

[0025] (In the formula, A represents an atomic group having antioxidant ability, and k represents an integer of 1 to 10.) DETAILED DESCRIPTION

[0026] The present invention relates to a compound, a latent antioxidant using the same, a composition, a cured product thereof, and a method for producing the cured product. These will be described in detail below.

[0027] A. Compounds

[0028] First, the compound of the present invention is described.

[0029] The compound of the present invention is represented by the following general formula (I-1) (hereinafter, the compound of the present invention is also referred to as compound I-1).

[0030] [Chemical formula 3]

[0031]

[0032] (In the formula, A represents an atomic group having antioxidant ability, B represents a photo-detached group, and k represents an integer of 1 to 10.)

[0033] The atomic group A of the compound I-1 of the present invention has an antioxidant activity. The compound I-1 of the present invention has a low antioxidant activity before the photoleaving group B is released, but after the photoleaving group B is released, the atomic group A exhibits an excellent antioxidant activity.

[0034] Therefore, when the compound I-1 before the photo-leaving radical B is released is added to a polymerization system, for example, the compound I-1 has a low ability to capture radicals generated by polymerization and is unlikely to inhibit the curing of the polymerization system.

[0035] In addition, the compound I-1 of the present invention is detached by photolysis by irradiation with light, showing excellent antioxidant ability. Therefore, by irradiating a cured product containing the compound I-1 with light, antioxidant ability can be easily imparted to the cured product. Since the compound I-1 does not need to be heated to demonstrate its antioxidant ability, it has the advantage that it is difficult to cause damage to the cured product and its surrounding components such as the substrate due to heating.

[0036] For the reasons described above, the compound I-1 has, for example, little curing inhibition and can easily impart antioxidant properties to a cured product.

[0037] Furthermore, since the compound I-1 has a photoleaving group B, for example, the dispersion stability in the composition can be easily adjusted.

[0038] Compound I-1 can be provided with excellent dispersibility in the composition by selecting the photo-leaving group B so as to improve the affinity with other components contained in the composition.

[0039] Therefore, the compound I-1 can impart excellent antioxidant ability to the composition and can also impart excellent dispersion stability during storage before use.

[0040] Hereinafter, the compound I-1 of the present invention will be described in detail.

[0041] 1. Photodetachment base B

[0042] The compound I-1 of the present invention has a photo-leaving group B.

[0043] The photo-detachable group in the present invention can be a group that can be detached from the compound I-1 by irradiating light of a specific wavelength. When the compound I-1 is irradiated with light of a specific wavelength, the photo-detachable group B is detached from the compound I-1 to generate a compound represented by the following general formula (I-2) containing a hydroxyl group and an atomic group A having antioxidant ability.

[0044] [Chemical formula 4]

[0045]

[0046] (In the formula, A represents an atomic group having antioxidant ability, and k represents an integer of 1 to 10.)

[0047] The wavelength of light by which the photo-detached group B is detached from the compound I-1 is, for example, in the wavelength region of ultraviolet light or visible light. Specifically, it can be set to light having a wavelength of 365 nm, more specifically, it can be set to light having a wavelength of 250 nm to 450 nm, and preferably, it can be set to light having a wavelength of 280 nm to 380 nm.

[0048] The cumulative amount of light irradiated to release the photo-detachable group B from the compound I-1 can be, for example, 1000 mJ / cm 2 Above and 10000mJ / cm 2 Below, preferably 1000mJ / cm 2 Above and 5000mJ / cm 2 Below, more preferably 2000mJ / cm 2 Above and 4000mJ / cm 2 The cumulative light intensity of the light irradiated for curing the composition containing the polymerizable compound etc. can be generally set to less than 1000 mJ / cm 2 Therefore, by making the integrated light amount within the above range, it is easy to apply to, for example, a photocurable composition.

[0049] It should be noted that the photo-leaved group B may be released as long as it can impart the desired antioxidant capacity. For example, the release rate of the photo-leaved group may be 50% or more, and particularly preferably 80% or more.

[0050] On the other hand, the cumulative light intensity for suppressing the photolysis of the compound I-1 can be set to less than 1000 mJ / cm as long as the desired curing inhibition effect can be obtained. 2 This is because it is easy to apply to a photocurable composition.

[0051] The suppression of photodetachment is sufficient as long as the desired curing inhibition effect can be obtained, and for example, the detachment rate of the photodetachable groups B can be less than 50%, and particularly preferably less than 20%, because it is easy to apply to the photocurable composition.

[0052] The above-mentioned cumulative light amount can be measured by preparing a 0.01 mass % acetonitrile solution of the compound I-1 and using the same method as the method for measuring the desorption rate described in the Examples.

[0053] As the photodetachable group B satisfying the above requirements, specifically, the groups represented by the following general formulae (B-1), (B-2), (B-3), (B-4), (B-5), (B-6), (B-7) and (B-8) can be cited. Particularly preferred are the groups represented by the following general formulae (B-1-a), (B-2-a), (B-3-a), (B-4), (B-5), (B-6), (B-7-a) (B-7-b) and (B-8-a), and preferably the group represented by the following general formula (B-1-a). This is because, by adopting these photodetachable groups, it is possible to easily detach from the compound I-1, and to easily impart antioxidant ability to the cured product. In addition, as the photodetachable group B satisfying the above requirements, specifically, the groups represented by the following general formulae (B-9) and (B-10) can also be cited.

[0054] [Chemical formula 5]

[0055]

[0056] [Chemical formula 6]

[0057]

[0058] (Where R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 each independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0059] R 12 , R 14 , R 17 , R 21 , R 22 , R 24 , R 25 , R 27 , R29 and R 30 each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0060] R 15 represents an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0061] R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 The methylene group in the alkyl group and arylalkyl group shown may be replaced by a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-, >P=O, -SS-, -SO2-, or a combination thereof.

[0062] R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0063] Multiple R 11 Each other, multiple R 13 Each other, multiple R 16 Each other, multiple R 18 Each other, multiple R 19 Each other, multiple R 20 Each other, multiple R 23 Each other, multiple R 26 Each other and multiple R 28 Sometimes they are bonded to each other to form a benzene ring or a naphthalene ring,

[0064] Multiple R 11 , R 12 , R13 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 , R 23 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 Sometimes they are the same, sometimes they are different.

[0065] b1, b2, b3, b6, b7, b8 and b9 each independently represent an integer of 0 to 4,

[0066] b4 and b5 each independently represent an integer of 0 to 5,

[0067] ** indicates the bonding position with the above AO-. )

[0068] [Chemical Formula 6A]

[0069]

[0070] (Where R 31 and R 40 each independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0071] R 32 , R 33 , R 41 , R 42 , R 43 , R 44 each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0072] R 31 , R 32 , R 33 , R 40 , R 41 , R 42 , R 43 and R 44The methylene groups in the alkyl and arylalkyl groups shown are sometimes replaced by carbon-carbon double bonds, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-, >P=O, -SS-, -SO2-, or combinations thereof.

[0073] The above-mentioned alkyl group, aryl group, arylalkyl group and heterocyclic ring-containing group may have a substituent.

[0074] c1 represents an integer from 0 to 5,

[0075] c2 represents an integer from 0 to 4,

[0076] ** indicates the bonding position with the above AO-. )

[0077] The above R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 40 , R 41 , R 42 , R 43 and R 44 (Hereinafter, these functional groups are sometimes collectively referred to as R 11 The alkyl group having 1 to 40 carbon atoms as represented by the group consisting of alkyl groups 1 to 40 carbon atoms (such as alkyl groups 1 to 40 carbon atoms) may be methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, 1-octyl, isooctyl, tert-octyl and adamantyl.

[0078] As the above R 11Examples of the aryl group having 6 to 20 carbon atoms represented by , include phenyl, naphthyl and anthracenyl.

[0079] As the above R 11 Examples of the arylalkyl group having 7 to 20 carbon atoms represented by , include benzyl, fluorenyl, indenyl and 9-fluorenylmethyl.

[0080] As the above R 11 The heterocyclic group having 2 to 20 carbon atoms represented by the above and the like can be exemplified by pyridyl, pyrimidinyl, pyridazinyl, piperidinyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, phenylthio, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidon-1-yl, 2-piperidon-1-yl, 2,4-dioxoimidazolidin-3-yl and 2,4-dioxooxazolidin-3-yl.

[0081] Examples of the alkyl group having 1 to 8 carbon atoms represented by R' include 11 The alkyl groups exemplified by alkyl groups such as ...

[0082] The above-mentioned alkyl group, aryl group, arylalkyl group and heterocyclic ring-containing group may have a substituent. Unless otherwise specified, the compound I-1 of the present invention includes a compound having no substituent and a compound having a substituent.

[0083] Examples of the substituent which may replace the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group include ethylenically unsaturated groups such as vinyl group, allyl group, acrylic group and methacrylic group; halogen atoms such as fluorine, chlorine, bromine and iodine; acyl groups such as acetyl group, 2-chloroacetyl group, propionyl group, octanoyl group, acryloyl group, methacryloyl group, phenylcarbonyl (benzoyl group), phthaloyl group, 4-trifluoromethylbenzoyl group, pivaloyl group, salicyl group, oxalyl group, stearoyl group, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group and carbamoyl group; acyloxy groups such as acetoxy group and benzoyloxy group; amino group, ethylamino group, dimethylamino group, diethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, chlorophenylamino group, toluidinyl group, anisidinyl group, N-methyl-anilino group, dimethylamino group, substituted amino groups such as phenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino and phenylsulfonylamino; sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, mercapto, imido, carbamoyl, sulfonylamide, phosphonic acid, phosphate or salts of carboxyl, sulfonic acid, phosphonic acid or phosphate.

[0084] In the present invention, when a hydrogen atom in a group is replaced by a substituent, the number of carbon atoms in the group is defined as the number of carbon atoms in the group after the replacement. For example, when a hydrogen atom in the above-mentioned alkyl group having 1 to 40 carbon atoms is replaced, the number of carbon atoms 1 to 40 refers to the number of carbon atoms after the hydrogen atom is replaced, not the number of carbon atoms before the hydrogen atom is replaced.

[0085] In the present invention, when the methylene group in the group is replaced by the above-mentioned divalent group, the number of carbon atoms in the group is defined as the number of carbon atoms in the group after the replacement. For example, in this specification, when the methylene group in the alkyl group having 1 to 40 carbon atoms is replaced by the above-mentioned divalent group, the "number of carbon atoms 1 to 40" refers to the number of carbon atoms after the methylene group is replaced, not the number of carbon atoms before the methylene group is replaced. Therefore, "-OC 40 H 81 ” corresponds to “an alkyl group having 40 carbon atoms (= an alkoxy group having 40 carbon atoms) in which the terminal methylene group is replaced by —O—”. Similarly, “—CO-OC 39 H 79” corresponds to “an alkyl group having 40 carbon atoms in which the terminal methylene group is replaced by -CO-O-”.

[0086] R 11 The methylene groups in the alkyl and arylalkyl groups used in the above are sometimes replaced by a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-, >P=O, -SS-, -SO2- or a combination thereof.

[0087] It should be noted that the combination of the above-mentioned methylene substitutions may be a combination under the condition that the oxygen atoms are not adjacent.

[0088] By R 11 In the alkyl group having 1 to 40 carbon atoms represented by , the terminal methylene group on the end side of the base may be replaced by -O- to form an alkoxy group. Examples of such alkoxy groups include alkoxy groups having 1 to 10 carbon atoms. Specifically, examples include methoxy, ethoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, tert-heptyloxy, 1-octyloxy, isooctyloxy, and tert-butoxy.

[0089] The above R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 It is preferably a group other than a hydroxyl group, for example, a halogen atom, a cyano group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. This is because by using a group other than a hydroxyl group, the photo-leaving group B becomes a group that is easily detached from the compound I-1, and the synthesis of the compound I-1 becomes easy.

[0090] The above R 11 and R 23 An alkoxy group is preferred because the photoleaving group B becomes a group that can be easily released from the compound I-1, and the synthesis of the compound I-1 becomes easy.

[0091] The above R 13 , R 18 , R19 , R 20 , R 26 and R 28 It is preferably an alkyl group having 1 to 40 carbon atoms. This is because the photoleaving group B becomes a group that is easily detached from the compound I-1, and the synthesis of the compound I-1 becomes easy.

[0092] Among them, the above R 16 It is particularly preferred that two adjacent R 16 The photoleaving group B is a group that is easily detached from the compound I-1, and the synthesis of the compound I-1 becomes easy.

[0093] The above R 18 and R 19 When the methylene group in the alkyl group and the arylalkyl group shown is replaced by -O-, the -O- replacing the methylene group may be contained in a manner that interrupts the alkyl group and the arylalkyl group, respectively, that is, the methylene group other than the terminal of the alkyl group and the arylalkyl group is replaced.

[0094] The above R 12 A hydrogen atom, a carboxyl group, or an alkyl group having 1 to 5 carbon atoms is preferred, and a hydrogen atom or a methyl group is particularly preferred.

[0095] The above R 14 , R 17 , R 21 , R 24 , R 25 , R 27 , R 29 and R 30 A hydrogen atom or an alkyl group having 1 to 40 carbon atoms is preferred, and a hydrogen atom is particularly preferred. This is because the photoleaving group B becomes a group that is easily detached from the compound I-1, and synthesis of the compound I-1 becomes easy.

[0096] The above R 15 and R 22 An alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group is particularly preferred because it can provide a compound that has little curing inhibition and can easily impart antioxidant properties to a cured product.

[0097] The above b1, b2, b3, b6, b7, b8 and b9 are each independently an integer of 0 to 4, and from the viewpoint of ease of synthesis, are preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 to 1, and particularly preferably 0. This is because a compound having little curing hindrance and capable of easily imparting antioxidant ability to a cured product can be provided.

[0098] The above b4 and b5 can each independently be an integer of 0 to 5, and from the viewpoint of ease of synthesis, an integer of 0 to 3 is preferred, an integer of 0 to 2 is more preferred, 0 to 1 is further preferred, and 0 is particularly preferred. This is because a compound having little curing hindrance and capable of easily imparting antioxidant properties to a cured product can be provided.

[0099] Regarding the type of photodetached group B contained in the compound I-1 of the present invention, when k is greater than 2, the type of photodetached group B is sometimes one type and sometimes two or more types relative to the compound I-1, but is preferably one type from the viewpoint of less curing hindrance, easy impartment of antioxidant ability to the cured product, and easy synthesis of the compound I-1.

[0100] The number k of the photo-detachable groups is an integer of 1 to 10, but is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3 from the viewpoint of less curing hindrance, easy impartment of antioxidant ability to the cured product, and ease of synthesis.

[0101] 2. Atomic groups with antioxidant capacity

[0102] The atomic group A is an atomic group having antioxidant ability.

[0103] The compound I-1 of the present invention is irradiated with light of a specific wavelength, so that the photodetachment group B is detached to generate a compound I-2 having a hydroxyl group. In the present invention, having an antioxidant ability means having a function of preventing or inhibiting the oxidation of a substance caused by heat, light, or other energy, such as exerting a free radical scavenging effect. In the present invention, the free radical scavenging effect means that the compound I-2 reacts with the chain carrier peroxy radical of the auto-oxidation to stop the oxidation. In the present invention, the atomic group having an antioxidant ability can be set as a group having an antioxidant ability or an aggregate of atoms having at least one group having an antioxidant ability.

[0104] Such an atomic group A may be the same as an atomic group generally used for an antioxidant having a phenolic hydroxyl group.

[0105] That is, the compound I-2 may be a compound generally used as an antioxidant having a phenolic hydroxyl group.

[0106] As the compound I-2, for example, phenolic antioxidants described in JP-A-6-179798, JP-A-11-71355, JP-A-2002-97224, and alkyl-substituted phenolic antioxidants described in JP-A-7-109380 can be used.

[0107] As the atomic group A having antioxidant ability, specifically, there can be mentioned an atomic group obtained by removing the above-mentioned BO- from a benzene ring in which a phenol structure is protected, i.e., a phenolic hydroxyl group is protected by the above-mentioned photo-leaving group B. More specifically, there can be mentioned an atomic group including a benzene ring to which the above-mentioned BO- is directly bonded, and an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, i.e., a first substituent. The above-mentioned first substituent is preferably directly bonded to the above-mentioned benzene ring, and more preferably, the bonding position of the above-mentioned first substituent on the benzene ring is ortho to the bonding position of the above-mentioned BO-. The atomic group A is preferably an atomic group in which the second substituent represented by a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms is further directly bonded to the benzene ring to which the first substituent is directly bonded, and more preferably the bonding position of the second substituent on the benzene ring is ortho to the bonding position of BO-. That is, the atomic group A is particularly preferably bonded to the bonding position of BO- in one ortho position and the second substituent in the other ortho position. This is because it is easy to prepare a compound with less curing hindrance and can easily impart antioxidant ability to the cured product.

[0108] Examples of the compound (I-1) of the present invention include compounds represented by the following general formula (A-1), (A-2) or (A-3).

[0109] [Chemical formula 7]

[0110]

[0111] (Where R 1 represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0112] R 2 , R 3 and R 4 each independently represents an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0113] R 1 , R 2 , R 3 and R 4The methylene group in the alkyl group and arylalkyl group used in the present invention may be replaced by a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-, >P=O, -SS-, -SO2-, or a combination thereof.

[0114] R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0115] Multiple R 1 Sometimes they are bonded to form a benzene ring or a naphthalene ring.

[0116] Multiple R 1 Sometimes the same, sometimes different,

[0117] m represents an integer from 1 to 10,

[0118] n represents an integer from 2 to 10,

[0119] a represents an integer from 0 to 2,

[0120] X 1 represents an m-valent bonding group,

[0121] X 2 represents an n-valent bonding group. )

[0122] As the above R 1 , R 2 , R 3 and R 4 The alkyl group having 1 to 40 carbon atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, the heterocyclic group having 2 to 20 carbon atoms and the alkyl group having 1 to 8 carbon atoms used in R' include those listed in the above "1. Photo-leaving group" as R 11 The groups exemplified by the above and R'.

[0123] The above R 1 It is preferably an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and is particularly preferably an alkyl group having 1 to 40 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms. This is because compound I-1 exhibits excellent antioxidant ability after the photo-leaving group B is released.

[0124] The above R 2 , R 3 and R 4An alkyl group having 1 to 40 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is particularly preferred, and a methyl group or a tert-butyl group is particularly preferred. This is because compound I-1 exhibits excellent antioxidant activity after the photo-leaving group B is released.

[0125] The above m is an integer of 1 to 10, and from the viewpoint of ease of synthesis, is preferably an integer of 1 to 6, particularly preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 4. This is because compound I-1 exhibits excellent antioxidant activity after the photocleavage group B is released.

[0126] The above n is an integer of 2 to 10, and from the viewpoint of ease of synthesis, is preferably an integer of 2 to 6, particularly preferably an integer of 2 to 5, particularly preferably an integer of 2 to 4, and particularly preferably an integer of 2 to 3. This is because compound I-1 exhibits excellent antioxidant ability after the photo-leaving group B is released.

[0127] The above-mentioned a is an integer of 0 to 2, and is preferably 0 to 1 from the viewpoint of the excellent antioxidant ability of the compound I-1 after the photocleavage group B is released and the ease of synthesis.

[0128] The compound I-1 represented by the above general formula (A-1) has X 1 The structure is formed by bonding a specific atom having a valence of m and m specific groups shown in the figure. The m specific groups may be the same as each other or different from each other.

[0129] The above X 1 It represents an m-valent bonding group.

[0130] As the above-mentioned bonding group X 1 , specifically, represents a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by (II-a) or (II-b) below, >C=O, >NR 53 、-OR 53 、-SR 53 、-NR 53 R 54 or an aliphatic hydrocarbon group having 1 to 120 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms having the same valence as m. 53 and R 54represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms, and the aliphatic hydrocarbon group, the hydrocarbon group containing an aromatic ring, and the heterocyclic group may also be represented by -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NH-CO-O-, -NR ’ The above aromatic ring or heterocyclic ring may be fused with other rings.

[0131] However, in X 1 When m is 3, X 1 is an oxygen atom or a sulfur atom, >C=O, -NH-CO-, -CO-NH- or >NR 53 In the case of m being 2, in X 1 For-OR 53 、-SR 53 or -NR 53 R 54 In the case of , m is 1 and X1 may form a ring together with the benzene ring.

[0132] [Chemical formula 8]

[0133]

[0134] (* means that the * portion is bonded to an adjacent group.)

[0135] Regarding the above bonding group X 1an aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same valence as m, wherein m is a univalent group, for example, an alkyl group such as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl and decyl; a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, pentyloxy group, isopentyloxy group, tert-pentyloxy group, hexyl group, cyclohexyl group, heptyl group, isoheptyl group, tert-heptyloxy group, n-octyloxy group, isooctyl group, Alkoxy groups such as tert-octyloxy, 2-ethylhexyloxy, nonyloxy and decyloxy; alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, pentylthio, isopentylthio, tert-pentylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio and 2-ethylhexylthio; alkenyl groups such as vinyl, 1-methylvinyl, 2-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, dicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl and tricosenyl; and groups in which these groups are substituted by substituents described below.

[0136] Regarding the above bonding group X 1 The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same valence as m as shown, as the group in which m is divalent, includes alkylene groups such as methylene, ethylene, propylene, butylene and butanediol; groups in which the methylene chains of the above alkylene groups are replaced by -O-, -S-, -CO-O-, -O-CO-; residues of diol groups such as ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol; residues of dithiol groups such as ethanedithiol, propylenethiol, butanediol, pentanediol and hexanediol; and groups in which these groups are substituted by substituents described below.

[0137] Regarding the above bonding group X 1 The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same valence as m as shown, as the group where m is trivalent, for example, alkylene groups such as propylidene and 1,1,3-butylpropylidene; and groups in which these groups are substituted with substituents described below.

[0138] Regarding the above bonding group X 1The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same valence number as m as shown, as the group where m is univalent, there can be mentioned arylalkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl and cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; arylthio groups such as phenylthio and naphthylthio; and groups in which these groups are substituted by substituents described below.

[0139] Regarding the above bonding group X 1 The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same valence number as m as shown, as the group where m is divalent, there can be mentioned arylene groups such as phenylene and naphthylene; residues of difunctional phenol groups such as catechol group and bisphenol group; 2,4,8,10-tetraoxaspiro[5,5]undecyl group; and groups in which these groups are substituted by substituents described below.

[0140] Regarding the above bonding group X 1 The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same valence as m as shown in the figure, wherein m is trivalent, includes phenyl-1,3,5-trimethylene and groups in which the group is substituted with a substituent described below.

[0141] Regarding the above bonding group X 1 The heterocyclic group having 2 to 35 carbon atoms and having the same valence as m as shown in the above formula (a), wherein m is a univalent group, includes pyridyl, pyrimidinyl, pyridazinyl, piperidinyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, phenylthio, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidon-1-yl, 2-piperidon-1-yl, 2,4-dioxoimidazolidin-3-yl, 2,4-dioxooxazolidin-3-yl and benzotriazolyl, and groups in which these groups are substituted with substituents described below.

[0142] Regarding the above bonding group X 1 The heterocyclic group having 2 to 35 carbon atoms and having the same valence as m as shown, as the group in which m is divalent, there can be mentioned divalent groups having a pyridine ring, pyrimidine ring, piperidine ring, piperazine ring, triazine ring, furan ring, thiophene ring and indole ring, and groups in which these groups are substituted with substituents described below.

[0143] As R 53 and R 54 Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms used in the method include the above-mentioned X 1The aliphatic hydrocarbon group having 1 to 120 carbon atoms used in the above or the group in which the aliphatic hydrocarbon group is substituted with a substituent described below, which is a group having 1 to 35 carbon atoms.

[0144] As R 53 and R 54 The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic group having 2 to 35 carbon atoms represented by 1 The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic ring-containing group having 2 to 35 carbon atoms, or a group in which these groups are substituted with a substituent described below.

[0145] Each functional group such as the above-mentioned aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group may have a substituent. Unless otherwise specified, the compound I-1 of the present invention includes compounds without a substituent and compounds with a substituent.

[0146] Examples of such substituents include aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic ring-containing groups. 11 The substituents substituted for the hydrogen atoms of the alkyl groups used in the above are the same as the substituents substituted for the hydrogen atoms of the alkyl groups used in the above.

[0147] When m is 2, the above X 1 The group represented by the following general formula (1) can be used.

[0148] When m is 3, the above X 1 The group represented by the following general formula (2) can be used.

[0149] When m is 4, the above X 1 A group represented by the following general formula (3) can be used.

[0150] When m is 5, the above X 1 A group represented by the following general formula (4) can be used.

[0151] When m is 6, the above X 1 A group represented by the following general formula (5) can be used.

[0152] [Chemical formula 9]

[0153] *—Z 1 —Y 1 —Z 2 -* (1)

[0154] (In the above general formula (1), Y 1 Indicates a single bond, -CR 55 R 56 -、-NR 57-, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms, or any substituent represented by the following (1-1) to (1-3), wherein the aliphatic hydrocarbon group, the hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, and the heterocyclic group containing 2 to 35 carbon atoms may be substituted with a bonding group of -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a combination thereof,

[0155] R 55 and R 56 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

[0156] Z 1 and Z 2 Each independently represents a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO2-, -SS-, -SO-, >NR 58 or >PR 58 ,

[0157] R 57 and R 58 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms,

[0158] * means that the * part is bonded to the adjacent group. )

[0159] [Chemical formula 10]

[0160]

[0161] (In the above formula, R 59 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms,

[0162] R 60 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom, wherein the alkyl group, alkoxy group, and alkenyl group may have a substituent, c1 is an integer of 0 to 5, and * means that the * portion is bonded to an adjacent group.

[0163] [Chemical formula 11]

[0164]

[0165] (* means that the * portion is bonded to an adjacent group.)

[0166] [Chemical formula 12]

[0167]

[0168] (In the above formula, R 61 and R 62 each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the methylene group in the alkyl group and the arylalkyl group may be replaced by an unsaturated bond, -O- or -S-,

[0169] R 61 There are also adjacent R 61 When they form a ring with each other,

[0170] c2 represents a number from 0 to 4,

[0171] c3 represents a number from 0 to 8,

[0172] c4 represents a number from 0 to 4,

[0173] c5 represents a number from 0 to 4,

[0174] The total number of c4 and c5 is 2 to 4.

[0175] * means that the * part is bonded to the adjacent group. )

[0176] [Chemical formula 13]

[0177]

[0178] (In the above general formula (2), Y 11 represents a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms,

[0179] Z 1 , Z 2 and Z 3 Each independently represents a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO2-, -SS-, -SO-, >NR 62 , PR 62 , an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms,

[0180] R 62represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms,

[0181] The aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic group having 2 to 35 carbon atoms may be substituted with a carbon-carbon double bond, -O-, -CO-, -O-CO-, -CO-O-, or -SO2-.

[0182] [Chemical formula 14]

[0183]

[0184] (In the above general formula (3), Y 12 represents a carbon atom or a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms, wherein the aliphatic hydrocarbon group, the hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or the heterocyclic group containing 2 to 35 carbon atoms may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z 1 ~Z 4 are each independently the same as Z in the above general formula (2) 1 ~Z 3 The same scope as the groups shown.)

[0185] [Chemical formula 15]

[0186]

[0187] (In the above general formula (4), Y 13 represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 30 carbon atoms, or a heterocyclic group containing 2 to 30 carbon atoms, wherein the aliphatic hydrocarbon group, the hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or the heterocyclic group containing 2 to 35 carbon atoms is sometimes substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, and Z 1 ~Z 5 are each independently the same as Z in the above general formula (2) 1 ~Z 3 The same scope as the groups shown.)

[0188] [Chemical formula 16]

[0189]

[0190] (In the above general formula (5), Y 14represents a single bond, a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms, wherein the aliphatic hydrocarbon group, the hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or the heterocyclic group containing 2 to 35 carbon atoms is sometimes substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, and Z 1 ~Z 6 are each independently the same as Z in the above general formula (7) 1 ~Z 3 The same scope as the groups shown.)

[0191] As Y in the group represented by the above general formula (1) 1 The divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Z includes methane, ethane, propane, isopropane, butane, sec-butane, tert-butane, isobutane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, isoheptane, tert-heptane, 1-methyloctane, isooctane, tert-octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane and the like. 1 and Z 2 These groups are sometimes interrupted by -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a combination thereof.

[0192] As Y in the group represented by the above general formula (1) 1 The divalent hydrocarbon group having 6 to 35 carbon atoms and containing an aromatic ring, such as phenylene, naphthylene, biphenylene, etc., is replaced by Z 1 and Z 2 Substituted divalent groups, etc.

[0193] As Y in the group represented by the above general formula (1) 1 The divalent heterocyclic group having 2 to 35 carbon atoms as represented by Z includes pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene, thiophene, tetrahydrothiophene and the like. 1 and Z 2 Substituted divalent group.

[0194] In the group represented by the above general formula (1), Y 1 The aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group shown may be further substituted with a halogen atom, a cyano group, a nitro group or an alkoxy group having 1 to 8 carbon atoms.

[0195] Each functional group such as the above-mentioned aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group may have a substituent, but unless otherwise specified, it may be an unsubstituted group or a substituted group.

[0196] Examples of the substituents for such aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic groups include those in which R 11 The substituents substituted for the hydrogen atoms of the alkyl groups used in the above are the same as the substituents substituted for the hydrogen atoms of the alkyl groups used in the above.

[0197] As R in the group represented by the above general formula (1) 55 and R 56 Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, 1-octyl, isooctyl and tert-octyl.

[0198] As R in the group represented by the above general formula (1) 55 and R 56 Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, and cinnamyl.

[0199] In the group represented by the above general formula (1), R 57 and R 58 The aliphatic hydrocarbon group having 1 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or the heterocyclic group having 2 to 35 carbon atoms represented by 53 and R 54 The groups exemplified are the same groups.

[0200] As R in the group represented by the above general formula (1-1) 59 Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl and the like, and groups in which these groups are substituted with alkyl groups having 1 to 10 carbon atoms or alkoxy groups having 1 to 10 carbon atoms.

[0201] As the group represented by the above general formula (1-1), R 60 The alkyl group having 1 to 10 carbon atoms represented by R includes the group consisting of 11 The alkyl groups exemplified by the alkyl groups represented by the above and the like are alkyl groups having 1 to 10 carbon atoms.

[0202] As the group represented by the above general formula (1-1), R 60The alkoxy group having 1 to 10 carbon atoms represented by the above-mentioned "1. Photo-leaving group B" as represented by R 11 The alkoxy groups exemplified by the alkoxy groups represented by the following are alkoxy groups having 1 to 10 carbon atoms.

[0203] Examples of the alkenyl group having 2 to 10 carbon atoms in the group represented by the general formula (1-1) include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl and 2-octenyl.

[0204] The phenyl group, alkyl group, alkoxy group and alkenyl group in the general formula (1-1) may have a substituent. Examples of such a substituent include 1 The substituents are the same as those exemplified as the substituents for replacing a hydrogen atom of the alkyl group or the like used in the above description.

[0205] The above R 60 The alkyl group, alkoxy group and alkenyl group in the group may be substituted with a halogen atom, for example, and the substitution position is not limited.

[0206] As R in the group represented by the above general formula (1-3) 61 and R 62 The alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the arylalkyl group having 7 to 20 carbon atoms shown in the figure include those mentioned as R in the above-mentioned "1. Photo-leaving group B" 11 The groups satisfying the prescribed number of carbon atoms among the examples shown above are groups having the same carbon number as those listed above.

[0207] As R in the group represented by the above general formula (1-3) 61 and R 62 The aryloxy radical having 6 to 20 carbon atoms represented by the above-mentioned radical includes phenoxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 4-vinylphenyloxy, 3-isopropylphenyloxy, 4-isopropylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyloxy, 4-(2-ethylhexyl)phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, Phenyloxy, 2,5-dimethylphenyloxy, 2,6-dimethylphenyloxy, 3,4-dimethylphenyloxy, 3,5-dimethylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di-tert-butylphenyloxy, 2,4-di-tert-pentylphenyloxy, 2,5-tert-pentylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy and ferrocenyloxy, and groups obtained by substituting these groups with halogen atoms.

[0208] As R in the group represented by the above general formula (1-3)61 and R 62 The arylthio group having 6 to 20 carbon atoms shown in the above-mentioned group includes a group in which the oxygen atom of the aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom is replaced with a sulfur atom.

[0209] As R in the group represented by the above general formula (1-3) 61 and R 62 Examples of the arylalkenyl group having 8 to 20 carbon atoms include groups in which the oxygen atom of an aryloxy group having 6 to 20 carbon atoms which may be substituted with the above-mentioned halogen atom is replaced with an alkenyl group such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, or 2-octenyl.

[0210] As R in the group represented by the above general formula (1-3) 61 and R 62 Examples of the heterocyclic group having 2 to 20 carbon atoms include pyridyl, pyrazinyl, piperidinyl, piperazinyl, pyrimidinyl, pyridazinyl, triazinyl, hexahydrotriazinyl, furanyl, tetrahydrofuranyl, chromanyl, xanthene, thienyl and thiofuranyl, and groups in which these groups are substituted by halogen atoms.

[0211] In the group represented by the above general formula (1-3), R 61 and R 62 Each functional group such as the aryloxy group, arylthio group, arylalkenyl group, and heterocyclic group shown may have a substituent, but unless otherwise specified, it may be an unsubstituted group having no substituent or a group having a substituent.

[0212] As the substituent for replacing the hydrogen atom of the aryloxy group, arylthio group, arylalkenyl group, heterocyclic group, etc., it can be set as 11 The same applies to the substituents replacing the hydrogen atoms of the alkyl groups used in the above.

[0213] As the group represented by the above general formula (2), Y 11 The trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms represented by the formula (1) may be 1 The aliphatic hydrocarbon group exemplified in the description of 1 , Z 2 and Z 3 Substituted trivalent groups, these groups may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO2-, -NH-, or a group composed of a combination of these.

[0214] As the group represented by the above general formula (2), Y 11The trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by X in the above general formula (1) is exemplified by 1 The aromatic ring-containing hydrocarbon groups exemplified in the description of 1 , Z 2 and Z 3 A substituted trivalent group.

[0215] As the group represented by the above general formula (2), Y 11 The trivalent heterocyclic group having 2 to 35 carbon atoms represented by 1 The heterocyclic group exemplified in the description of 1 , Z 2 and Z 3 A substituted trivalent group.

[0216] In the group represented by the above general formula (2), Z 1 , Z 2 and Z 3 and R 62 The aliphatic hydrocarbon group having 1 to 35 carbon atoms, the hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or the heterocyclic group containing 2 to 35 carbon atoms can be set as the above R 53 and R 54 The contents of the examples are the same.

[0217] As Y in the group represented by the above general formula (3) 12 The tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by 1 The aliphatic hydrocarbon group exemplified in the description of 1 , Z 2 , Z 3 and Z 4 Substituted tetravalent groups: These groups may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a group composed of a combination of these groups.

[0218] As the group represented by the above general formula (3), Y 12 The tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by X in the above general formula (1) is 1 The aromatic ring-containing hydrocarbon groups exemplified in the description of 1 , Z 2 , Z 3 and Z 4 A substituted tetravalent group.

[0219] As the group represented by the above general formula (3), Y 12 The tetravalent heterocyclic group having 2 to 35 carbon atoms represented by1 The heterocyclic group exemplified in the description of 1 , Z 2 , Z 3 and Z 4 A substituted tetravalent group.

[0220] As Y in the group represented by the above general formula (4) 13 The pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms used in the formula (1) may be X 1 The aliphatic hydrocarbon group exemplified in the description of 1 , Z 2 , Z 3 , Z 4 and Z 5 Substituted pentavalent groups, these groups are sometimes substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO2-, -NH-, or a group composed of a combination of these.

[0221] Examples of the pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms in the group represented by the general formula (4) include X in the general formula (1): 1 The aromatic ring-containing hydrocarbon groups exemplified in the description of 1 , Z 2 , Z 3 , Z 4 and Z 5 A substituted pentavalent group.

[0222] Examples of the pentavalent heterocyclic group having 2 to 35 carbon atoms in the group represented by the general formula (4) include X in the general formula (1): 1 The heterocyclic group exemplified in the description of 1 , Z 2 , Z 3 , Z 4 and Z 5 A substituted pentavalent group.

[0223] As Y in the above general formula (5) 14 The hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by 1 The aliphatic hydrocarbon group exemplified in the description of 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 Substituted hexavalent groups, these groups are sometimes substituted with -O-, -S-, -CO-, -COO-, -OCO-, -SO2-, -NH-, or a group composed of a combination of these.

[0224] As Y in the above general formula (5) 14 The hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by 1 The aromatic ring-containing hydrocarbon groups exemplified in the description of 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 A substituted hexavalent group.

[0225] As Y in the above general formula (5) 14 The hexavalent heterocyclic group having 2 to 35 carbon atoms represented by 1 The heterocyclic group exemplified in the description of 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 A substituted hexavalent group.

[0226] The above bonding group X 1 When m is 2, it is preferably any substituent represented by the following general formulae (1-4), (1-5), and (1-6-a) to (1-6-e).

[0227] The above bonding group X 1 When m is 3, it is preferably a group selected from the following Group 1.

[0228] The above bonding group X 1 When m is 4, it is preferably a group selected from the following Group 2.

[0229] The above bonding group X 1 When m is 5, it is preferably a group selected from the following Group 3.

[0230] The above bonding group X 1 When m is 6, it is preferably a group selected from the following Group 4.

[0231] This is because these substituents can serve as groups that enable Compound I-1 to exhibit excellent antioxidant activity after the photoleaving group B is released, and the raw materials can be easily obtained and produced.

[0232] [Chemical formula 17]

[0233]

[0234] (In the above general formula (1-4), Y 1 and Y 5 Each independently represents an alkylene group having 1 to 4 carbon atoms, and Y2 and Y 4 Each independently represents an oxygen atom or -NR 113 -, R 113 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Y 3 Indicates -CR 114 R 115 -、-NR 116 -, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a substituent represented by the following general formula (1-7), wherein the aliphatic hydrocarbon group, the hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, and the heterocyclic group containing 6 to 35 carbon atoms may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and R 114 and R 115 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and R 116 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms.

[0235] [Chemical formula 18]

[0236]

[0237] (In the above general formula (1-5), Y 6 and Y 8 Each independently represents -NR 117 - or an alkylene group having 1 to 4 carbon atoms which may be substituted by an oxygen atom, Y 7 Indicates direct bonding, -O-, -S-, -SO2-, -CR 118 R 119 - or any substituent represented by the above general formula (1-1) to (1-3), R 117 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, R 118 and R 119 Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted by a halogen atom.

[0238] [Chemical formula 19]

[0239]

[0240] (In the above general formulas (1-6-a) to (1-6-e), R 31 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms.

[0241] [Chemical formula 20]

[0242]

[0243] (In the above general formula (1-7), Y 9 and Y 10 Each independently represents an alkylene group having 1 to 4 carbon atoms. )

[0244] [Chemical formula 21]

[0245] <Group 1>

[0246]

[0247] (Where R 32 is the same as R in the above general formula (2) 62 The same group, when there are two or more in the group, may be the same or different, Z 11 Represents Z 1 ~Z 3 The same scope as the groups shown.)

[0248] [Chemical formula 22]

[0249] <Group 2>

[0250]

[0251] (In the above formula, R 32 is the same as R in the above general formula (2) 62 The same group, when there are two or more in the group, may be the same or different, Z 11 Represents Z 1 ~Z 3 The same scope as the groups shown.)

[0252] [Chemical formula 23]

[0253] <Group 3>

[0254]

[0255] (In the above formula, Z 10 , Z 11 , Z 12 , Z 13 and Z 14 Represents Z 1 ~Z 3 The same scope as the groups shown.)

[0256] [Chemical formula 24]

[0257] <Group 4>

[0258]

[0259] (In the above formula, Z 10 , Z 11 , Z 12 , Z 13 and Z 14 Represents Z 1 ~Z 3 The same scope as the groups shown.)

[0260] Y used as a substituent in the above-mentioned general formulas (1-4) to (1-7) 1 , Y 5 , Y 6 , Y 8 , Y 9 and Y 10 Examples of the alkylene group having 1 to 4 carbon atoms include methylene, ethylene, propylene, isopropylene, and butylene.

[0261] As the above R 113 and R 117 The aliphatic hydrocarbon group having 1 to 20 carbon atoms used in the above-mentioned bonding group X is exemplified by 1 The aliphatic hydrocarbon group having 1 to 120 carbon atoms used in the present invention is a group having the prescribed number of carbon atoms among the examples of the group having a valence of 1, wherein m is a group having a valence of 1.

[0262] As mentioned above Y 3 The divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms and the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by 1 The contents of the examples are the same.

[0263] As the above R 114 , R 115 , R 118 and R 119 The alkyl group having 1 to 8 carbon atoms used in 114 and R 115 The aryl group having 6 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms used in the present invention may be combined with the above R 55 and R 56 The contents of the examples are the same.

[0264] As the above R 116 and R 31 The aliphatic hydrocarbon group having 1 to 35 carbon atoms, the hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, and the heterocyclic group containing 2 to 35 carbon atoms used may be combined with the above R 53 and R 54 The contents of the examples are the same.

[0265] Each functional group such as the above-mentioned aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group may have a substituent, but unless otherwise specified, the functional group may be unsubstituted or have a substituent.

[0266] As such aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, heterocyclic ring-containing groups and other substituents, R 11 The same applies to the substituents replacing the hydrogen atoms of the alkyl groups used in the above.

[0267] In addition, the above-mentioned bonding group X 1 When m is 2, an aliphatic hydrocarbon group having 1 to 10 carbon atoms may be preferably used, and an aliphatic hydrocarbon group having 1 to 6 carbon atoms is particularly preferred. This is because a compound with little curing hindrance can be obtained, and antioxidant ability can be easily imparted to the cured product, and further, the preparation of compound I-1 is easy.

[0268] When m is 1, the bonding group X is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 120 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. This is because compound I-1 exhibits excellent antioxidant ability after the photo-leaving group B is released, and compound I-1 is easy to produce.

[0269] As the above-mentioned bonding group X 1 The bonding position to the benzene ring can be any position that can be bonded to the benzene ring, for example, the bonding position relative to the above-mentioned BO- can be the ortho position or the para position, and can be the para position. This is because compound I-1 exerts excellent antioxidant ability after the photo-detachable group B is detached.

[0270] The above X 1 When m=1, preferably a hydrogen atom or 1 Same group.

[0271] The compound I-1 represented by the general formula (A-2) or (A-3) has a bonded 2 The structure of a specific atom having a valence of n and n specific groups is shown. The n specific groups may be the same as or different from each other.

[0272] The above X 2 Can be combined with the above X 1 The same applies to the bonding group in which m is 2 or more among the bonding groups used in .

[0273] As the above-mentioned bonding group X 2 The bonding position with the benzene ring can be set to the same position as the above X 1 same.

[0274] The above X 2 When n=1, it is preferably a hydrogen atom or1 Same group.

[0275] The atomic group A may contain a phenolic hydroxyl group, that is, the compound I-1 may contain a phenolic hydroxyl group not protected by the photoleaving group B. The number of phenolic hydroxyl groups is preferably 2 or less, more preferably 0. This is because the compound I-1 is a compound with little curing hindrance.

[0276] 3. Compounds

[0277] The compound of the present invention can be any compound represented by the general formula (I-1), preferably a compound represented by the general formula (A-1), the general formula (A-2) or (A-3), and as the photodetached group B, preferably includes a group represented by the general formula (B-1-a). This is because the synthesis is easy and the photodetachment is easy. In addition, this is because it is easy to impart antioxidant ability to the cured product. In addition, this is because compound I-1 is the general formula (A-1), (A-2) or (A-3), so it is possible to stably capture free radicals by the detachment of the photodetached group B.

[0278] Specific examples of the compound I-1 include the following compounds.

[0279] [Chemical formula 25]

[0280]

[0281] [Chemical formula 26]

[0282]

[0283] [Chemical formula 27]

[0284]

[0285] [Chemical formula 28]

[0286]

[0287] [Chemical formula 29]

[0288]

[0289] [Chemical formula 30]

[0290]

[0291] [Chemical formula is 31]

[0292]

[0293] [Chemical formula 32]

[0294]

[0295] [Chemical formula 33]

[0296]

[0297] [Chemical formula 34]

[0298]

[0299] [Chemical formula 35]

[0300]

[0301] [Chemical formula 36]

[0302]

[0303] [Chemical formula 37]

[0304]

[0305] [Chemical formula 38]

[0306]

[0307] [Chemical formula 39]

[0308]

[0309] [Chemical formula 40]

[0310]

[0311] The molecular weight of the compound I-1 can be set according to the application of the compound I-1 and the like.

[0312] The molecular weight may be, for example, 250 or more and 5000 or less, 300 or more and 2500 or less, or 350 or more and 1500 or less.

[0313] In addition, when compound I-1 is a polymer containing a repeating structure as its structure, the above molecular weight can be a molecular weight represented by a weight average molecular weight (Mw).

[0314] Hereinafter, the weight average molecular weight (Mw) can be determined as a standard polystyrene conversion value by gel permeation chromatography (GPC).

[0315] The weight average molecular weight Mw is obtained by, for example, using HLC-8120GPC manufactured by TOSOH Co., Ltd., setting the elution solvent to N-methylpyrrolidone added with 0.01 mol / L lithium bromide, setting the calibration curve to polystyrene standards of Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (the above are Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by TOSOH Co., Ltd.), and setting the measurement column to TSK-GEL ALPHA-M×2 (manufactured by TOSOH Co., Ltd.). In addition, the measurement temperature can be set to 40°C, and the flow rate can be set to 1.0 mL / min.

[0316] The method for producing the above-mentioned compound I-1 is not particularly limited as long as it is a method that can obtain the desired structure. For example, it can be obtained by reacting a phenolic compound produced by the method described in the gazettes of Japanese Patent Application No. 57-111375, Japanese Patent Application No. 3-173843, Japanese Patent Application No. 6-128195, Japanese Patent Application No. 7-206771, Japanese Patent Application No. 7-252191, and Japanese Patent Application No. 2004-501128 with an alkyl halide or the like.

[0317] The compound I-1 is inactive before light irradiation, but upon light irradiation, the photo-leaving group is detached to generate a compound I-2 having a hydroxyl group. The compound I-2 exhibits an antioxidant activity.

[0318] As the use of such compound I-1, preferably, it is used for the purpose of requiring the antioxidant activity to be exerted by light irradiation, and examples thereof include antioxidants added to compositions.

[0319] In addition, the compound I-1 generates a compound I-2 having a hydroxyl group by light irradiation. Examples of uses of the compound I-1 include antioxidants that require high dispersion stability.

[0320] B. Latent antioxidants

[0321] Next, the latent antioxidant of the present invention will be described.

[0322] The latent antioxidant of the present invention comprises the compound I-1 of the present invention.

[0323] According to the latent antioxidant of the present invention, for example, it has little curing inhibition and can easily impart antioxidant ability to a cured product.

[0324] The content of the compound I-1 in the latent antioxidant of the present invention can be appropriately set according to the application of the latent antioxidant and the like.

[0325] The latent antioxidant of the present invention may contain 100 parts by mass of the compound I-1 in 100 parts by mass of the latent antioxidant, that is, the latent antioxidant may consist of only the compound I-1.

[0326] In addition, the latent antioxidant of the present invention sometimes contains other ingredients in addition to compound I-1. When the latent antioxidant of the present invention contains other ingredients, the content of compound I-1 in 100 parts by mass of the latent antioxidant can be set to, for example, more than 20 parts by mass and less than 99 parts by mass, preferably more than 25 parts by mass and less than 99 parts by mass, more preferably more than 50 parts by mass and less than 99 parts by mass, and particularly preferably more than 80 parts by mass and less than 99 parts by mass. This is because the effect of less curing hindrance can be more effectively exerted.

[0327] The latent antioxidant may contain only one type of compound I-1 or two or more types of compound I-1. When the latent antioxidant contains several types of compound I-1, the number of types may be, for example, two or more and five or less.

[0328] It should be noted that the above-mentioned compound I-1 may be the same as that described in the section "A. Compound", and thus the description here is omitted.

[0329] Examples of the other components include those described in the section "2. Other components" of "C. Composition" described later.

[0330] The latent antioxidant may contain a resin component such as a polymer having no polymerizable group as another component.

[0331] The latent antioxidant may be in the form of powder or granules.

[0332] In the case of a pelletized form, as a method for producing the latent antioxidant, for example, a method in which the compound I-1 and a resin component are mixed using an extruder or the like and then molded into a pelletized form can be used.

[0333] C. Composition

[0334] Next, the composition of the present invention will be described.

[0335] The composition of the present invention comprises the compound I-1 of the present invention.

[0336] According to the composition of the present invention, for example, a cured product having less curing hindrance and excellent antioxidant ability can be obtained. In addition, the composition of the present invention can easily impart photosensitivity and can easily impart antioxidant ability to the cured product. Hereinafter, each component contained in the composition of the present invention is described.

[0337] 1. Compounds

[0338] The content of the compound I-1 in the composition of the present invention is not particularly limited as long as it is an amount that can impart a desired antioxidant activity or the like to the composition.

[0339] The above content can be, for example, 0.01 to 20 parts by mass, preferably 0.05 to 5 parts by mass, in 100 parts by mass of the solid content of the composition. This is because it is easy to prepare a composition with little curing hindrance and can easily impart antioxidant ability to the cured product.

[0340] In addition, the solid content refers to a component including all components except the solvent.

[0341] In addition, in the present invention, the content is based on mass unless otherwise specified.

[0342] The content of the compound I-1 varies depending on the content of the solvent, etc., and can be set to, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition, and is particularly preferably 0.005 parts by mass or more and 10 parts by mass or less. This is because it is easy to prepare a composition with little curing hindrance and can easily impart antioxidant ability to the cured product.

[0343] The compound I-1 contained in the composition may be of one kind or two or more kinds. For example, the number of the compound I-1 may be two or more and five or less.

[0344] It should be noted that the above-mentioned compound I-1 may be the same as that described in the section "A. Compound", and thus the description here is omitted.

[0345] 2. Other ingredients

[0346] The above composition may contain other components besides the above compound I-1 depending on its use and the like.

[0347] As said other component, a resin component is mentioned, for example.

[0348] This is because, by including the resin component, for example, curability and the like can be easily imparted to the composition.

[0349] In addition, as the other component, it is preferred that a polymerization initiator be contained together with the resin component. This is because the composition can be easily provided with curing properties, for example, by containing the resin component, the polymerization initiator, etc. as other components.

[0350] (1) Resin component

[0351] The resin component may be a component capable of retaining the compound I-1 and may be appropriately set according to the application of the composition, and examples thereof include polymerizable compounds having a polymerizable group and polymers having no polymerizable group.

[0352] By containing a polymerizable compound as the resin component, the composition can be used as, for example, a photocurable composition, a thermosetting composition, or the like.

[0353] (a) Polymerizable compounds

[0354] The above-mentioned polymerizable compound is a compound having a polymerizable group.

[0355] In addition, the polymerizable compound is usually used together with a polymerization initiator.

[0356] Such polymerizable compounds vary depending on the type of polymerizable group, that is, the type of polymerization reaction, and examples thereof include radical polymerizable compounds, cation polymerizable compounds, and anion polymerizable compounds.

[0357] From the viewpoint of effectively exhibiting the effect of reducing the inhibition of curing, the polymerizable compound preferably contains a radical polymerizable compound.

[0358] (i) Radically polymerizable compounds

[0359] The radical polymerizable compound may have at least one radical polymerizable group, and may have two or more radical polymerizable groups.

[0360] The above-mentioned radical polymerizable compound is usually used together with a radical polymerization initiator.

[0361] Examples of the radically polymerizable group include ethylenically unsaturated double bond groups such as a (meth)acryloyl group and a vinyl group.

[0362] In addition, (meth)acryloyl is used for the meaning including acryloyl and methacryloyl. In addition, (meth)acrylate is used for the meaning including acrylate and methacrylate.

[0363] The radical polymerizable compound may be a compound having an acid value or a compound not having an acid value.

[0364] As a compound which has an acid value, the compound which has a carboxyl group etc. are mentioned, for example.

[0365] The composition contains a compound having an acid value as a radical polymerizable compound, so that the solubility of the light-irradiated portion in an alkaline developer is reduced. Therefore, the composition can be used as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation. More specifically, the composition contains a compound having an acid value, so that the composition can be used as a negative composition.

[0366] As the alkali developer, an alkali developer generally used as an alkali developer, such as a tetramethylammonium hydroxide (TMAH) aqueous solution or a potassium hydroxide aqueous solution, can be used.

[0367] As for the above-mentioned free radical polymerizable compound, for example, as a compound having an ethylenically unsaturated double bond group and having an acid value, there can be mentioned: (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, nadic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], and ω-carboxy polycaprolactone mono(meth)acrylate, a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends; hydroxyethyl (meth)acrylate maleate, hydroxypropyl (meth)acrylate maleate, dicyclopentadiene maleate, or a polyfunctional (meth)acrylate having one carboxyl group and two or more (meth)acryloyl groups. unsaturated monobasic acids; phenol and / or cresol novolac epoxy resins, novolac epoxy resins having a biphenyl skeleton or a naphthalene skeleton, novolac epoxy compounds such as bisphenol A novolac epoxy compounds and dicyclopentadiene novolac epoxy compounds, polyphenylmethane epoxy resins having a multifunctional epoxy group, a resin obtained by reacting an unsaturated monobasic acid with an epoxy group of an epoxy resin such as an epoxy compound represented by the following general formula (III), a resin obtained by reacting an unsaturated monobasic acid with an epoxy group of an epoxy resin such as an epoxy compound represented by the following general formula (III) and then reacting a polybasic acid anhydride, a reaction product of a hydroxyl-containing multifunctional acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate with a dibasic acid anhydride such as succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride, i.e., a multifunctional acrylate having an acid value, etc.

[0368] [Chemical formula 41]

[0369]

[0370] (Where X 41represents a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO2-, -SS-, -SO-, -CO-, -OCO-, or a substituent as shown in (1-1) to (1-3) above,

[0371] R 41 , R 42 , R 43 and R 44 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom,

[0372] d is an integer from 0 to 10. )

[0373] Examples of the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 8 carbon atoms, and the alkenyl group having 2 to 5 carbon atoms include those mentioned as R in the above-mentioned "A. Compound" 11 Among the exemplified groups, those satisfying the prescribed number of carbon atoms.

[0374] Examples of the alkylidene group having 1 to 4 carbon atoms include a methylene group, an ethylidene group, a propylidene group, and a butylidene group.

[0375] Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

[0376] The above-mentioned alkyl groups, alkoxy groups, alkenyl groups, alkylidene groups, alicyclic hydrocarbon groups, etc. may have a substituent, but unless otherwise specified, these groups are unsubstituted or have a substituent.

[0377] As the substituent replacing the hydrogen atom of such an alkyl group, alkoxy group, alkenyl group, alkylidene group, alicyclic hydrocarbon group, etc., it is possible to set 11 The same applies to the substituents replacing the hydrogen atoms of the alkyl groups used in the above.

[0378] As for the above-mentioned free radical polymerizable compound, for example, as a compound having an ethylenically unsaturated double bond group and having no acid value, there can be mentioned: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, the following compounds No. A1 to No. A4, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylamino (meth)acrylate. methyl ester, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate Esters of unsaturated monobasic acids such as (meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dihydroxymethyl di(meth)acrylate, tri[(meth)acryloylethyl] isocyanurate, polyester (meth)acrylate oligomers, and polyols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride , tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methylnadic anhydride and other unsaturated polybasic acid anhydrides; (meth)acrylamide, methylenebis(meth)acrylamide, diethylenetriaminetri(meth)acrylamide, xylenebis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl(meth)acrylamide and other unsaturated monobasic acid and polyamine amides; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, allyl nitrile and the like;Unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; indene, 1 -methylindene and other indenes; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene, etc.; macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain such as polystyrene, poly(methyl)acrylate, poly(meth)acrylate n-butyl ester, polysiloxane, etc.; (meth)acrylonitrile, ethylene, propylene, butylene, vinyl chloride, vinyl acetate and other vinyl compounds, as well as macromonomers such as polymethyl methacrylate macromonomer, polystyrene macromonomer, monomethacrylate of tricyclodecane skeleton, N-phenylmaleimide, copolymers of methacryloyloxymethyl-3-ethyloxetane and (meth)acrylic acid, and Karenz manufactured by Showa Denko K.K. Copolymers of (meth) acrylic acid obtained by reacting isocyanate compounds having unsaturated bonds such as MOI and AOI with them, vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphonate, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl monomers containing hydroxyl groups and vinyl carbamate compounds of polyisocyanate compounds, vinyl monomers containing hydroxyl groups and vinyl epoxy compounds of polyepoxide compounds, reaction products of polyfunctional acrylates containing hydroxyl groups such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate with polyfunctional isocyanates such as toluene diisocyanate and hexamethylene diisocyanate, etc.;

[0379] [Chemical formula 42]

[0380] Compound No.A1

[0381]

[0382] [Chemical formula 43]

[0383] Compound No.A2

[0384]

[0385] [Chemical formula 44]

[0386] Compound No.A3

[0387]

[0388] [Chemical formula 45]

[0389] Compound No.A4

[0390]

[0391] The radical polymerizable compounds may be used alone or in combination of two or more thereof. In addition, the radical polymerizable compounds may be used in combination of a compound having an ethylenically unsaturated double bond group and having an acid value and a compound having an ethylenically unsaturated double bond group and having no acid value.

[0392] When two or more radical polymerizable compounds are used as a mixture, they may be copolymerized in advance and used as a copolymer.

[0393] The content of the radical polymerizable compound can be appropriately set according to the purpose of the composition, for example, it can be set to 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, preferably 10 parts by mass or more and 90 parts by mass or less, and particularly preferably 40 parts by mass or more and 80 parts by mass or less. This is because by making the above content within the above range, for example, the above composition can be used as a negative composition with excellent sensitivity. In addition, this is because it is possible to provide a composition with little curing hindrance and capable of easily imparting antioxidant ability to the cured product.

[0394] The content of the polymerizable compound is preferably 1 part by mass or more and 99 parts by mass or less, preferably 50 parts by mass or more and 99.9 parts by mass or less, particularly preferably 80 parts by mass or more and 99.7 parts by mass or less, and more preferably 90 parts by mass or more and 99.5 parts by mass or less, in 100 parts by mass of the total of compound I-1 and the polymerizable compound. This is because by setting the content within the above range, the curing hindrance of the composition is small, and a composition that can easily impart antioxidant ability to a cured product can be provided.

[0395] In addition, the content of the compound I-1 and the radical polymerizable compound can be appropriately set according to the purpose of the composition, for example, it can be set to 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, preferably 10 parts by mass or more and 90 parts by mass or less, and particularly preferably 40 parts by mass or more and 80 parts by mass or less. This is because by making the above content within the above range, for example, the above composition can be used as a negative composition with excellent sensitivity. In addition, this is because it is possible to provide a composition with little curing hindrance and which can easily impart antioxidant ability to the cured product.

[0396] (ii) Cationic polymerizable compounds and anionic polymerizable compounds

[0397] The cationically polymerizable compound may have at least one polymerizable group capable of cation polymerization.

[0398] The above-mentioned cationically polymerizable compound is usually used together with a cationic polymerization initiator.

[0399] Examples of the polymerizable group capable of cation polymerization include cyclic ether groups such as an epoxy group and an oxetanyl group, and a vinyl ether group.

[0400] That is, examples of the cationically polymerizable compound include cyclic ether compounds such as epoxy compounds and oxetane compounds, and vinyl ether compounds.

[0401] Examples of the epoxy compound include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, phenyl-2-methyl glycidyl ether, hexadecyl glycidyl ether, stearyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, methacrylate glycidyl ether, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, 4-phenylphenol glycidyl ether, Glycidyl ethers such as oily ether, cresyl glycidyl ether, dibromocresyl glycidyl ether, decyl glycidyl ether, methoxy polyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetrakis(glycidyloxyphenyl)ethane and pentaerythritol tetraglycidyl ether; glycidyl acetate, glycidyl stearate esters such as glycidyl esters; 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, ethylenebis(3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-cyclohexyl Oxycyclohexylmethyl 6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4-epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadiene diepoxide, 3,4-epoxy-6-methylcyclohexylcarboxylate, α-pinene oxide, styrene oxide, cyclohexene oxide, cyclopentene oxide and other epoxycycloalkyl compounds and N-glycidylphthalimide, etc.

[0402] In addition, as the above-mentioned epoxy compound, epoxidized polyolefin can also be used. Epoxidized polyolefin refers to a polyolefin modified with an epoxy-containing monomer to introduce an epoxy group. It can be produced by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy-containing monomer, and other monomers as required by any of copolymerization and grafting methods. Ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy-containing monomer and other monomers can be polymerized separately or with multiple other monomers. In addition, it can also be obtained by epoxidizing the double bonds of non-conjugated polybutadiene having a hydroxyl group at the end by a peracetic acid method, and a substance having a hydroxyl group in the molecule can also be used. In addition, the hydroxyl group can also be urethanized with isocyanate, and an epoxy compound containing a primary hydroxyl group is reacted therein to introduce an epoxy group.

[0403] Examples of the ethylene or C3-20 α-olefins include ethylene, propylene, butene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene and isoprene.

[0404] Examples of the epoxy group-containing monomer include glycidyl esters of α,β-unsaturated acids, vinylbenzyl glycidyl ether, and allyl glycidyl ether. Specific examples of glycidyl esters of α,β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, and glycidyl methacrylate is particularly preferred.

[0405] Examples of the other monomers include unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, nadic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], ω-carboxy polycaprolactone mono(meth)acrylate, hydroxyethyl(meth)acrylate / maleate, hydroxypropyl(meth)acrylate, and other polymers having carboxyl groups and hydroxyl groups at both ends. unsaturated polybasic acids such as ester maleate, dicyclopentadiene maleate, and polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate Ester, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate Esters of unsaturated monobasic acids and polyols or polyphenols such as esters of unsaturated monobasic acids and polyols or polyphenols such as esters of unsaturated monobasic acids, ...Anhydrides of unsaturated polybasic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride and methylnadic anhydride; unsaturated monoacrylic acids such as (meth)acrylamide, methylenebis(meth)acrylamide, diethylenetriaminetri(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl(meth)acrylamide Amides of primary acids and polyamines; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl nitrile; unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylnaphthalene; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether and isobutyl vinyl ether; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; indene and 1-methylindene and other indenes; macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain such as polystyrene, poly(methyl)acrylate, poly(n-butyl)(meth)acrylate and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphonate, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbamide azoles, vinyl pyrrolidone, vinyl pyridine, vinyl monomers containing hydroxyl groups and vinyl carbamate compounds of polyisocyanate compounds, vinyl monomers containing hydroxyl groups and vinyl epoxy compounds of polyepoxide compounds, polyfunctional acrylates containing hydroxyl groups such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate; reaction products of polyfunctional isocyanates such as toluene diisocyanate and hexamethylene diisocyanate; reaction products of polyfunctional acrylates containing hydroxyl groups such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate with dibasic acid anhydrides such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride, i.e. polyfunctional acrylates having acid values. ;

[0406] As the above-mentioned epoxidized polyolefin, commercially available products can also be used, for example, EPOLEAD PB3600, EPOLEAD PB4700 (manufactured by Daicel); BF-1000, FC-3000 (manufactured by ADEKA); BONDFAST 2C, BONDFAST E, BONDFAST CG5001, BONDFAST CG5004, BONDFAST 2B, BONDFAST 7B, BONDFAST7L, BONDFAST 7M, BONDFAST VC40 (manufactured by Sumitomo Chemical Co., Ltd.); JP-100, JP-200 (manufactured by Nippon Soda Co., Ltd.); Poly bd R-45HT, Poly bd R-15HT (manufactured by Idemitsu Kosan Co., Ltd.) and Ricon 657 (manufactured by Arkema Co., Ltd.) can be used.

[0407] As the epoxy compound, a compound having a Cardo skeleton is more preferably used from the viewpoint of good heat resistance.

[0408] Examples of the oxetane compound include 3,7-bis(3-oxetanyl)-5-oxo-nonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl)propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetrakis(3-ethyl-3-oxetanylmethyl)ether, Ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane and 3-ethyl-3-(chloromethyl)oxetane, etc.

[0409] Examples of the vinyl ether compound include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,6-cyclohexanedimethanol divinyl ether.

[0410] The anionic polymerizable compound may have one or more anionic polymerizable groups.

[0411] The above-mentioned anionic polymerizable compound is usually used together with an anionic polymerization initiator.

[0412] Examples of the polymerizable group capable of anionic polymerization include an epoxy group, a lactone group, and a (meth)acryloyl group.

[0413] That is, examples of the anionic polymerizable compound include epoxy compounds, lactone compounds, and compounds having a (meth)acryloyl group.

[0414] Examples of the lactone compound include β-propiolactone and ε-caprolactone.

[0415] In addition, as the epoxy compound, the epoxy compounds exemplified as the above-mentioned cationically polymerizable compound can be used. In addition, as the compound having a (meth)acryloyl group, the compounds exemplified as the above-mentioned radically polymerizable compound can be used.

[0416] The above-mentioned cationically polymerizable compounds and anionically polymerizable compounds may be used alone or in combination of two or more.

[0417] (b) Polymer

[0418] The weight average molecular weight (Mw) of the polymer can be appropriately set depending on the application of the composition, and can be, for example, 1,500 or more, or 1,500 or more and 300,000 or less.

[0419] In addition, the above-mentioned polymer does not have a polymerizable group.

[0420] Such a polymer may contain any repeating structure, and examples thereof include photosensitive resins having photosensitivity and non-photosensitive resins having no photosensitivity.

[0421] The above composition can be used as a photosensitive composition by containing a photosensitive resin as a resin component, for example.

[0422] (i) Photosensitive resin

[0423] The photosensitive resin has photosensitivity, and examples thereof include positive-type resins that change in a direction in which solubility in a developer increases due to cleavage of chemical bonds such as ester groups or acetal groups by the action of an acid when used together with an acid generator.

[0424] The composition contains a positive resin as a resin component, so that the solubility of the light-irradiated portion in an alkaline developer is increased.

[0425] Therefore, the composition can be used as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation, for example, and more specifically, can be used as a positive composition.

[0426] As the positive-type resin, a resin obtained by partially substituting a high molecular weight polymer with an acid-labile group having an alkali dissolution control capability can be used.

[0427] Examples of the above-mentioned high molecular polymer include polyhydroxystyrene and its derivatives; polyacrylic acid and its derivatives; polymethacrylic acid and its derivatives; copolymers of two or more selected from hydroxystyrene, acrylic acid, methacrylic acid and their derivatives; copolymers of two or more selected from hydroxystyrene, styrene and their derivatives; copolymers of three or more selected from cycloolefins and their derivatives, maleic anhydride, and acrylic acid and its derivatives; copolymers of three or more selected from cycloolefins and their derivatives, maleimide, and acrylic acid and its derivatives; polynorbornene; one or more high molecular polymers selected from the group consisting of metathesis ring-opening polymers, etc.

[0428] Examples of the acid-labile group introduced into the high molecular weight polymer include tertiary alkyl groups, trialkylsilyl groups, oxoalkyl groups, aryl-substituted alkyl groups, heterocyclic groups such as tetrahydropyran-2-yl groups, tertiary alkylcarbonyl groups, tertiary alkylcarbonylalkyl groups, and alkoxycarbonyl groups.

[0429] Specific examples of the positive-type resin may be the same as those described in, for example, Japanese Patent Application Laid-Open No. 2003-192665, claim 3 of Japanese Patent Application Laid-Open No. 2004-323704, Japanese Patent Application Laid-Open No. 10-10733, and the like.

[0430] As the acid generator used together with the positive type resin, a known acid generator can be used. Specific examples of the acid generator include photocationic polymerization initiators and thermal cationic polymerization initiators described below.

[0431] (ii) Non-photosensitive resin

[0432] The above-mentioned non-photosensitive resin only needs to be non-photosensitive, and examples thereof include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, epoxy resin, etc.

[0433] As the non-photosensitive resin, for example, a polymer of the polymerizable compound may be used.

[0434] (iii) Polymer

[0435] The weight average molecular weight (Mw) of the polymer can be appropriately set depending on the application of the composition, and can be, for example, 1,500 or more, or 1,500 or more and 300,000 or less.

[0436] (c) Resin component

[0437] The content of the resin component can be appropriately set according to the purpose of the composition, for example, in 100 parts by mass of the solid content of the composition, it can be set to 1 part by mass to 99 parts by mass, preferably 10 parts by mass or more and 90 parts by mass or less, and particularly preferably 20 parts by mass or more and 80 parts by mass or less. This is because by making the content within the above range, the composition can, for example, stably maintain the compound I-1.

[0438] The content of the resin component can be appropriately set according to the purpose of the composition, for example, in 100 parts by mass of the composition, it can be set to be 1 part by mass or more and 99 parts by mass or less, preferably 10 parts by mass or more and 90 parts by mass or less, and particularly preferably 40 parts by mass or more and 80 parts by mass or less. This is because by making the above content within the above range, for example, the composition can be used as a negative composition with excellent sensitivity. In addition, this is because it is possible to provide a composition with little curing hindrance and capable of easily imparting antioxidant ability to the cured product.

[0439] The content of the resin component varies depending on the purpose of the composition, but is preferably 1 part by mass or more and 99.9 parts by mass or less, preferably 50 parts by mass or more and 99.7 parts by mass or less, particularly preferably 80 parts by mass or more and 99.5 parts by mass or less, and more preferably 90 parts by mass or more and 98 parts by mass or less, in a total of 100 parts by mass of the compound I-1 and the resin component. This is because by making the above content within the above range, the above composition can provide a composition that can easily impart antioxidant ability to the cured product.

[0440] In addition, as the content of the above-mentioned compound I-1 and the resin component, it can be appropriately set according to the purpose of the composition, for example, it can be set to 1 mass part or more and 99 mass parts or less in 100 mass parts of the composition, preferably 10 mass parts or more and 90 mass parts or less, and particularly preferably 40 mass parts or more and 80 mass parts or less. This is because by making the above-mentioned content the above-mentioned range, for example, the above-mentioned composition can be used as a negative composition with excellent sensitivity. In addition, this is because it is possible to provide a composition with little curing hindrance and can easily impart antioxidant ability to the cured product.

[0441] The type of the above-mentioned resin component may be only one type, or may be a combination of two or more types.

[0442] The resin component may be, for example, a resin component containing only one of a polymerizable compound and a polymer, or a resin component containing both of them.

[0443] When the resin component contains both a polymerizable compound and a polymer, the content of the polymerizable compound can be appropriately set according to the purpose of the composition, for example, 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the total of the polymerizable compound and the polymer.

[0444] (2) Polymerization initiator

[0445] The above-mentioned polymerization initiator is contained as a curable component and is usually used together with a polymerizable compound or the like.

[0446] The polymerization initiator may be any polymerization initiator that can polymerize the polymerizable compound, and examples thereof include photopolymerization initiators that can polymerize the polymerizable compound by irradiation with light and thermal polymerization initiators that can polymerize the polymerizable compound by heating.

[0447] (a) Photopolymerization initiator

[0448] The photopolymerization initiator may be any photopolymerization initiator that can polymerize a polymerizable compound by being irradiated with light, and examples thereof include photoradical polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators.

[0449] From the viewpoint of effectively exhibiting the effect of the composition being a material with little curing inhibition, the photopolymerization initiator preferably contains a photoradical polymerization initiator.

[0450] The photoradical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and a conventionally known compound can be used.

[0451] As the photoradical polymerization initiator, for example, acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, oxime ester compounds and the like can be exemplified as preferred photoradical polymerization initiators.

[0452] Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylideneacetophenone, 1 -Hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, etc.

[0453] Examples of the benzyl-based compound include benzyl and the like.

[0454] Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

[0455] Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0456] Examples of the oxime compound include compounds represented by the following general formula (IV).

[0457] [Chemical formula 46]

[0458]

[0459] (Where R 71 and R 72 each independently represents a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0460] R 73 and R 74 Each independently represents a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 75 , OR 76 , SR 77 NR 78 R 79 , COR 80 、SOR 81 、SO2R 82or CONR 83 R 84 , R 73 and R 74 Sometimes they bond to each other to form a ring,

[0461] R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 and R 84 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0462] X 3 Represents oxygen atoms, sulfur atoms, selenium atoms, CR 85 R 86 、CO、NR 87 or PR 88 ,

[0463] X 4 represents a single bond or CO,

[0464] R 85 , R 86 , R 87 and R 88 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, wherein the methylene group in the alkyl group or arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or a heterocyclic group, or may be substituted with -O-,

[0465] R 73 and R 74 Sometimes they independently form a ring with any adjacent benzene ring.

[0466] e1 represents an integer from 0 to 4,

[0467] e2 represents an integer from 0 to 5. )

[0468] As R in the above general formula (IV) 71 , R 72 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 85 , R 86 , R87 and R 88 The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms and the substituents thereof used in the above-mentioned "1. Photo-leaving group B" as R 11 The group having the specified number of carbon atoms in the above-mentioned examples is a group having the specified number of carbon atoms.

[0469] Examples of the oxime compounds include ethyl ketone-1-[9-ethyl-6-(2-methylbenzoyl-9H-carbazole-3-yl]-1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazole-3-yl]-octane-1-one oxime-O-acetate. Carbazole-based oxime ester compounds having a carbazole structure such as ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazole-3-yl]-1-(O-acetyl oxime), and ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime).

[0470] As the oxime compound, for example, an indole oxime ester compound having an indole structure may be used.

[0471] Examples of the indole oxime ester compound include oxime ester compounds represented by the following general formula (V) described in International Publication No. 2017 / 051680.

[0472] [Chemical formula 47]

[0473]

[0474] (Where R 201 and R 202 Each independently represents R 211 , OR 211 , COR 211 , SR211 ,CONR 212 R 213 or CN,

[0475] R 211 , R 212 and R 213 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0476] R 211 , R 212 and R 213 The hydrogen atoms of the groups shown are sometimes further represented by R 221 , OR 221 , COR 221 , SR 221 NR 222 R 223 ,CONR 222 R 223 NR 222 OR 223 , NCOR 222 OCOR 223 NR 222 COR 221 ,OCOR 221 、COOR 221 SCOR 221 , OCSR 221 、COSR 221 ,CSOR 221 , hydroxyl, nitro, CN, halogen atoms, or COOR 221 replace,

[0477] R 221 , R 222 and R 223 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0478] R 221 , R 222 and R 223 The hydrogen atoms of the groups shown are sometimes further substituted by hydroxyl, nitro, CN, halogen atoms, hydroxyl or carboxyl groups,

[0479] R 211 , R 212 , R 213 , R 221 , R 222 and R 223The methylene group of the alkylene portion of the group shown may be replaced by -O-, -S-, -COO-, -OCO-, -OCOO-, -CONR 224 -、-NR 224 -、-NR 224 CO-、-NR 224 COO-、-OCONR 224 -, -SCO-, -COS-, -OCS- or -SCOO- replacement,

[0480] R 224 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0481] R 211 , R 212 , R 213 , R 221 , R 222 , R 223 and R 224 The alkyl portion of the group shown may have a branched side chain or may be a cyclic alkyl group.

[0482] R 203 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and R 203 The alkyl portion of the group shown may have a branched side chain or may be a cyclic alkyl group. 203 With R 207 and R 203 With R 208 Sometimes they form a ring together.

[0483] R 203 The hydrogen atoms of the groups shown are sometimes further replaced by R 221 , OR 221 , COR 221 , SR 221 NR 222 R 223 ,CONR 222 R 223 NR 222 OR 223 , NCOR 222 OCOR 223 NR 222 COR 221 ,OCOR 221 、COOR 221 SCOR 221 , OCSR 221 、COSR221 ,CSOR 221 , hydroxyl, nitro, CN, halogen atoms, or COOR 221 replace,

[0484] R 204 , R 205 , R 206 and R 207 Each independently represents R 211 , OR 211 , SR 211 , COR 214 ,CONR 215 R 216 NR 212 COR 211 ,OCOR 211 、COOR 214 SCOR 211 , OCSR 211 、COSR 214 ,CSOR 211 , hydroxyl, CN or halogen atom, R 204 With R 205 , R 205 With R 206 and R 206 With R 207 Sometimes they form a ring together.

[0485] R 204 , R 205 , R 206 and R 207 The hydrogen atoms of the groups shown are sometimes further replaced by R 221 , OR 221 , COR 221 , SR 221 NR 222 R 223 ,CONR 222 R 223 NR 222 OR 223 , NCOR 222 OCOR 223 NR 222 COR 221 ,OCOR 221 、COOR 221 SCOR 221 , OCSR 221 、COSR 221 ,CSOR 221 , hydroxyl, nitro, CN, halogen atom or COOR 221 replace,

[0486] R214 , R 215 and R 216 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

[0487] R 214 , R 215 and R 216 The alkyl portion of the group shown may have a branched side chain or may be a cyclic alkyl group.

[0488] R 208 Represents R 211 , OR 211 , SR 211 , COR 211 ,CONR 212 R 213 NR 212 COR 211 ,OCOR 211 、COOR 211 SCOR 211 , OCSR 211 、COSR 211 ,CSOR 211 , hydroxyl, CN or halogen atoms,

[0489] n1 represents 0 or 1. )

[0490] As R in the above general formula (V) 203 , R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 221 , R 222 , R 223 and R 224 The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms used in the above-mentioned "1. Photo-leaving group B" as R 11 The group having the specified number of carbon atoms in the above-mentioned examples is a group having the specified number of carbon atoms.

[0491] Examples of other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and titanocene compounds such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyrrolyl-1-yl)]titanium and the like.

[0492] Examples of commercially available radical polymerization initiators include Adeka optomer N-1414, N-1717, N-1919, Adeka Arkls NCI-831, NCI-930 (manufactured by ADEKA), IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, OXE 03, OXE 04, IRGACURE 784 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-314, and TR-PBG-327 (manufactured by Tronly).

[0493] These photoradical polymerization initiators can be used alone or in combination of two or more depending on the desired performance.

[0494] The content of the photo-radical polymerization initiator may be any content as long as it can impart the desired curability and photosensitivity, and may be, for example, 0.001 to 20 parts by mass, preferably 0.1 to 30 parts by mass, and preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the polymerizable compound. This is because the above content provides excellent curability, etc. of the composition, and also excellent dispersibility, etc.

[0495] As the above-mentioned photocationic polymerization initiator, there is no particular limitation as long as it is a compound that can release a substance that initiates cationic polymerization by light irradiation, and existing compounds can be used, preferably an onium salt that releases a Lewis acid by irradiation with energy rays, that is, a double salt or a derivative thereof. As a representative compound of the compound, a salt of a cation and an anion represented by the following general formula can be cited.

[0496] [A1] r+ [B1] r-

[0497] The above cation [A1] r+ Onium is preferred, and its structure can be represented by the following general formula, for example.

[0498] [(R 101 ) f1 Q] r+

[0499] Furthermore, here, R 101 is an organic group having 1 to 60 carbon atoms and sometimes containing several atoms other than carbon atoms. f1 is any integer from 1 to 5. e R 58 Each is independent, sometimes the same, sometimes different. In addition, R 101At least one of the above-mentioned organic groups is preferably an aromatic ring. For example, phenyl groups which may be substituted by alkyl groups, alkoxy groups, hydroxyl groups, hydroxyalkoxy groups, halogen atoms, benzyl groups, thiophenoxy groups, 4-benzoylphenylthio groups, 2-chloro-4-benzoylphenylthio groups, etc. may be mentioned. Q is an atom or an atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. In addition, when the cation [A1] r+ When the atomic valence of Q in is set to q, the relationship r=f1-q needs to hold (where N=N is treated as an atomic valence of 0).

[0500] In addition, anion [B1] r- Preferably, it is a halide complex, and its structure can be represented by the following general formula: f2 ] r- express.

[0501] In addition, here, L is a metal or semimetal (Metalloid) serving as the central atom of the halide complex, such as B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn and Co.

[0502] X f2 is a halogen atom, or a phenyl group which may be substituted by a halogen atom or an alkoxy group. f2 is an integer of 3-7.

[0503] In addition, anion [B1] r- When the atomic valence of L in is p, the relationship r=f2-p needs to hold.

[0504] As the anion of the above general formula [LX f2 ] r- Specific examples include tetrakis(pentafluorophenyl)borate, tetrakis(3,5-difluoro-4-methoxyphenyl)borate, tetrafluoroborate (BF4) - 、Hexafluorophosphate (PF6) - 、Hexafluoroantimonate (SbF6) - 、Hexafluoroarsenate (AsF6) - , and hexachloroantimonate (SbCl6) - wait.

[0505] In addition, anion [B1] r- Anions having a structure represented by the following general formula can also be preferably used.

[0506] [LX f2-1 (OH)] r-

[0507] L, X, and f2 are the same as those described above. In addition, as other anions that can be used, perchlorate ion (ClO4) can be cited. - , trifluoromethylsulfite ion (CF3SO3) - 、Fluorosulfonate ion (FSO3) - , toluenesulfonate anion, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexafluorooctanesulfonate, tetraarylborates, and tetrakis(pentafluorophenyl)borate, etc.

[0508] In the present invention, among such onium salts, the following aromatic onium salts (M) to (O) are particularly effective and preferred. These may be used alone or in combination of two or more.

[0509] (M) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate.

[0510] Diaryliodonium salts such as (N)diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate and tricumyliodonium tetrakis(pentafluorophenyl)borate.

[0511] (O) Sulfonium salts of sulfonium cations represented by the following Group I or Group II and hexafluoroantimonate ions, tetrakis(pentafluorophenyl)borate ions, and the like.

[0512] [Chemical formula 48]

[0513] <Group I>

[0514]

[0515] [Chemical formula 49]

[0516] <Group II>

[0517]

[0518] In addition, other preferred substances include iron-aromatic complexes such as (η5-2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl)benzene]-iron-hexafluorophosphate; aluminum complexes such as tri(acetylacetonate)aluminum, tri(ethylacetone acetate)aluminum, tri(salicylicaldehyde)aluminum; mixtures of silanols such as triphenylsilanol, etc.

[0519] As the above-mentioned photocationic polymerization initiator, a commercially available product can also be used, for example, IRUGACURE 261 (manufactured by BASF), Adeka optomer SP-150, SP-151, SP-152, SP-170, SP-171, SP-172 (manufactured by ADEKA), UVE-1014 (manufactured by General Electronics), CD-1012 (manufactured by Sartomer), CI-2064, CI-2481 (manufactured by Nippon Soda Co., Ltd.), Uvacure 1590, 1591 (Daicel UCB), CYRACURE UVI-6990 (manufactured by Union Carbide), BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103 and NDS-103 (manufactured by Midori Chemical Co., Ltd.) and the like can be mentioned.

[0520] Among them, aromatic iodonium salts, aromatic sulfonium salts, and iron-arene complexes are preferably used from the perspective of practicality and sensitivity.

[0521] As the photo-ion polymerization initiator, an initiator that generates a base by utilizing light can be used, and a known initiator can be used as the photo-ion polymerization initiator.

[0522] Examples of the photoanionic polymerization initiator include acetophenone O-aroyloxime and nifedipine.

[0523] (b) Thermal polymerization initiator

[0524] The thermal polymerization initiator may be any thermal polymerization initiator that can polymerize a polymerizable compound by heating, and examples thereof include thermal radical polymerization initiators, thermal cationic polymerization initiators, and thermal anionic polymerization initiators.

[0525] From the viewpoint of effectively exhibiting the effect of reducing the inhibition of curing, the thermal polymerization initiator preferably contains a thermal radical polymerization initiator.

[0526] As the thermal radical polymerization initiator, an initiator that generates radicals by heating can be used, and a known initiator can be used as the thermal radical polymerization initiator.

[0527] As the thermal radical polymerization initiator, for example, an azo compound, a peroxide, a persulfate, etc. can be exemplified as a preferred initiator.

[0528] Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methylisobutyronitrile), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane).

[0529] Examples of the peroxide include benzoyl peroxide, di-tert-butylbenzoyl peroxide, tert-butyl peroxypivalate, and di(4-tert-butylcyclohexyl)peroxydicarbonate.

[0530] Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

[0531] As the thermal cationic polymerization initiator, an initiator that generates a cationic species or a Lewis acid by heating can be used, and a known initiator can be used as the thermal cationic polymerization initiator.

[0532] Specific examples of the thermal cationic polymerization initiator include sulfonium salts, thiophenium salts, tetrahydrothiophenium salts, benzyl ammonium, pyridinium salts, and hydrazinium salts; polyalkyl polyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; Amines; polyepoxy addition modified products produced by reacting the above polyamines with various epoxy resins such as glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether or glycidyl esters of carboxylic acids by conventional methods; amidated modified products produced by reacting the above organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid by conventional methods; Mannich modified products produced by reacting the above-mentioned polyamines with aldehydes such as formaldehyde and phenols having at least one hydroformylation reactive site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol and resorcinol; polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylglutaric acid, 2-methylsuberic acid, aliphatic dicarboxylic acids such as 3,8-dimethyldecane dioic acid, 3,7-dimethyldecane dioic acid, hydrogenated dimer acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; tricarboxylic acids such as trimers of trimellitic acid, trimesic acid and castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid, etc.; anhydrides of dicyandiamide, imidazoles, carboxylates, sulfonates and amine imides, etc.

[0533] As the thermal cationic polymerization initiator, commercially available products may be used, for example, Adeka option CP-77, Adeka opton CP-66 (manufactured by ADEKA Corporation), CI-2639, CI-2624 (manufactured by Nippon Soda Co., Ltd.), SanEid SI-60L, SanEid SI-80L, SanEid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), etc.

[0534] As the thermal anionic polymerization initiator, an initiator that generates a base by heat can be used, and a known initiator can be used as the thermal anionic polymerization initiator.

[0535] Specific examples of the anionic polymerization initiator include aliphatic amine compounds, aromatic amine compounds, secondary or tertiary amine compounds, imidazole compounds, polythiol compounds, boron trifluoride-amine complexes, dicyanamide, and organic acid hydrazides.

[0536] (c) Content of polymerization initiator

[0537] The content of the polymerization initiator can be any content as long as it can impart the desired curability and photosensitivity, and for example, can be 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the solid content. This is because the above content can provide excellent curability, etc. of the composition, and also excellent dispersibility, etc.

[0538] The content of the polymerization initiator may be any content as long as it can impart the desired curability and photosensitivity, and may be, for example, 0.001 to 20 parts by mass, preferably 0.1 to 30 parts by mass, and preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the polymerizable compound. This is because the above content provides excellent curability, etc. of the composition, and also excellent dispersibility, etc.

[0539] (3) Others

[0540] As the other components, in addition to the resin component and the polymerization initiator, a colorant, a solvent, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, etc. may be contained as necessary.

[0541] In addition to these, the above-mentioned other components may also use, as needed, thermal polymerization inhibitors such as anisole, hydroquinone, catechol, tert-butylcatechol, and phenothiazine; plasticizers; adhesion promoters; fillers; defoamers; leveling agents; surface conditioners; antioxidants such as phenolic antioxidants, phosphite antioxidants, and thioether antioxidants other than the compounds shown in the above-mentioned compound I-1; ultraviolet absorbers; dispersing aids; anti-agglomeration agents; catalysts; effect promoters; cross-linking agents; thickeners and other additives.

[0542] (a) Colorants

[0543] The colorant may be any colorant capable of imparting desired coloration to the composition or a cured product thereof, and examples thereof include dyes and pigments.

[0544] As dyes, compounds having absorption at 380 to 1200 nm can be used, for example, azo compounds, anthraquinone compounds, indigo compounds, triarylmethane compounds, xanthene compounds, alizarin compounds, acridine compounds, stilbene compounds, thiazole compounds, naphthol compounds, quinoline compounds, nitro compounds, indamine compounds, oxazine compounds, phthalocyanine compounds, cyanine compounds, diimmonium compounds, cyanovinyl compounds, dicyanostyrene compounds, rhodamine compounds, perylene compounds, polyene naphtholactams (polyene naphthalene lactams), and the like. The present invention also includes dyes such as naphtholactam compounds, coumarin compounds, squarylium compounds, crotonyl compounds, spiropyran compounds, spirooxazine compounds, merocyanine compounds, oxonol compounds, styryl compounds, pyrylium compounds, rhodanine compounds, oxazolone compounds, phthalimide compounds, cinnoline compounds, naphthoquinone compounds, azaanthraquinone compounds, porphyrin compounds, azaporphyrin compounds, pyrrolemethine compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, azine compounds, azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinoneimine compounds, iridium complex compounds, europium complex compounds, etc., and these can also be used in combination.

[0545] As the pigment, inorganic pigments or organic pigments can be used, for example, nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindolinone compounds, quinacridone compounds, anthranthrene dione compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids; metal complex compounds of azo dyes and cyanine dyes; color lakes Pigments; carbon black obtained by a furnace method, a channel method, or a thermal method, or carbon black such as acetylene black, ketjen black, or lamp black; a pigment obtained by adjusting and coating the above carbon black with an epoxy resin; a pigment obtained by pre-dispersing the above carbon black in a solvent with a resin so that it adsorbs 20 to 200 mg / g of the resin; a pigment obtained by subjecting the above carbon black to an acidic or alkaline surface treatment; carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less; a total oxygen content calculated from CO and CO2 in the volatile components at 950°C relative to 100 m 2 Carbon black having a surface area of ​​9 mg or more; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese series, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cyan blue, chrome green, emerald green, lead sulfate, chrome yellow, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, synthetic iron black, umber and other inorganic pigments or organic pigments. These pigments can be used alone or in combination.

[0546] As the inorganic pigment or organic pigment, commercially available pigments may be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179 , 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71 ; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 1 52, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

[0547] The content of the colorant may be 0.01 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the solid content of the composition.

[0548] The content of the colorant can be 0.01 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition.

[0549] (b) Solvent

[0550] The solvent may be any solvent capable of dissolving or dispersing the above components, and examples thereof include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, ethyl acetate, Ester solvents such as cyclohexyl ester, ethyl lactate, dimethyl succinate, Texanol, etc.; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, diacetone alcohol, etc.; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl Ether ester solvents such as oxyethyl propionate, 1-tert-butoxy-2-propanol, 3-methoxybutyl acetate, and cyclohexanol acetate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; mineral spirits, Swasol #310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso #100 (Exxon Chemical Co., Ltd.); paraffin-based solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, 1,2-dichloroethane, etc.; halogenated aliphatic hydrocarbon-based solvents such as chlorobenzene; carbitol-based solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. These solvents can be used as a mixed solvent of one or more.

[0551] The content of the solvent varies depending on the application of the composition, but can be 1 part by mass or more and 99 parts by mass or less, preferably 10 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the composition, because it is easy to improve coating properties.

[0552] (c) Chain transfer agents and sensitizers

[0553] The chain transfer agent and sensitizer may be substances that can adjust the sensitivity of the composition, and sulfur-containing compounds are generally used. Examples thereof include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, and the like. Acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) and other mercapto groups. Compounds, disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid and other iodinated alkyl compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol di (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, the following compound No. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, and Karenz manufactured by Showa Denko K.K. MT BD1, PE1, NR 1 wait.

[0554] [Chemical formula 50]

[0555] Compound No.C1

[0556]

[0557] (d) Surfactant

[0558] As the above-mentioned surfactant, a surfactant that can improve the dispersion stability, coating properties, etc. of the composition can be used, and surfactants such as fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, cationic surfactants such as higher amine halides and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants and the like can be used, and they can be used in combination.

[0559] (e) Silane coupling agent

[0560] The silane coupling agent is a silane compound having a reactive group chemically bonded to an inorganic material such as glass and a reactive group chemically bonded to an organic material such as a synthetic resin, and can be used to improve the adhesion of the composition or its cured product. As the silane coupling agent, for example, silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and preferably KBE-9007, KBM-502, KBE-403 and other silane coupling agents having an isocyanate group, a methacryloyl group, or an epoxy group can be used.

[0561] (f) Melamine compounds

[0562] As the above-mentioned melamine compound, a compound capable of improving curability can be used, for example, a compound in which all or part (at least 2) of the active methylol groups (CH2OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea are alkyl-etherified. Here, as the alkyl group constituting the alkyl ether, a methyl group, an ethyl group or a butyl group can be mentioned, which are sometimes the same as each other and sometimes different from each other. In addition, the methylol groups that are not alkyl-etherified sometimes self-condense within one molecule, and can also condense between two molecules, resulting in the formation of an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, etc. can be used. Among them, alkyl-etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred.

[0563] 3. Composition

[0564] The viscosity of the composition may be, for example, 200 mPa·s or less, or 1 mPa·s or more and 200 mPa·s or less, from the viewpoint of obtaining a composition having coating properties. This is because the composition has excellent coating properties.

[0565] The above viscosity is measured according to JIS Z 8803:2011 using a rotational viscometer (e.g., Anton Paar, Physica MCR 3 In addition, in this specification, the process and measurement which do not specify the temperature may be performed at 25°C.

[0566] The method for producing the composition may be any method as long as the components can be blended in desired contents, and may be a method of adding and mixing the components simultaneously or a method of adding and mixing the components sequentially.

[0567] The above composition can be used for thermosetting paint, photocurable paint or varnish, thermosetting adhesive, photocurable adhesive, printed substrate, or color filter in liquid crystal display panel of color display such as color TV, PC monitor, portable information terminal, digital camera, color filter of CCD image sensor, photo spacer, black columnar spacer, electrode material for plasma display panel, touch panel, touch sensor, powder coating, printing ink, printing plate, adhesive, dental composition, photo-molding resin, gel coating, photoresist for electronics, plating resist, etching resist, both liquid and dry film, solder resist, for the production of color filter for various display applications or in the production process of plasma display panel, electroluminescent display device and LCD The present invention can be used for various purposes, including resists for forming structures, compositions for encapsulating electrical and electronic components, solder resists, magnetic recording materials, micromechanical components, waveguides, optical switches, masks for plating, etching masks, color test systems, glass fiber cable coatings, templates for screen printing, materials for producing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials used in the formation of dielectric layers in the sequential lamination of printed circuit boards, photoresist materials or protective films for 3D mounting, and the like, and the uses are not particularly limited.

[0568] D. Cured product

[0569] Next, the cured product of the present invention will be described.

[0570] The cured product of the present invention is a cured product of a composition, wherein the composition contains the compound and a polymerizable compound.

[0571] According to the present invention, since the above-mentioned composition is used, curing is easy and antioxidant ability and the like can be easily imparted.

[0572] The cured product of the present invention uses the above-mentioned composition.

[0573] Hereinafter, the cured product of the present invention will be described in detail.

[0574] The above composition contains the above compound I-1 and a polymerizable compound.

[0575] Furthermore, the composition may contain components other than the compound I-1 and the polymerizable compound.

[0576] The contents of each component of such a composition may be the same as those described in the section "2. Other components" of the above-mentioned "C. Composition".

[0577] The compound I-1 contained in the composition may be before or after the photocleavage group B is released in the cured product, but is preferably after release because the cured product has excellent antioxidant properties.

[0578] The cured product generally contains a polymer of a polymerizable compound.

[0579] The residual amount of the polymerizable compound contained in the cured product is appropriately set depending on the application of the cured product, and is, for example, 10 parts by mass or less, and preferably 1 part by mass or less, based on 100 parts by mass of the cured product.

[0580] The solidified product may be a solidified product substantially containing no solvent.

[0581] The content of the solvent contained in the solidified material may be, for example, 1 part by mass or less, or 0.5 part by mass or less, based on 100 parts by mass of the solidified material.

[0582] The elastic modulus of the cured product is usually higher than that of the composition, and can be set to 10 -3 M or more, and can be 10 MPa or more. This is because the above-mentioned cured product can stably retain the compound I-1 and the like by setting the elastic modulus to the above-mentioned value.

[0583] The upper limit of the elastic modulus can be appropriately set according to the application of the cured product, for example, 10 6 Below MPa.

[0584] In addition, below, elastic modulus means a compression elastic modulus, and it can be measured at 23 degreeC according to JIS K7181.

[0585] As the measurement sample, for example, a cubic test piece with a side length of 6 mm may be prepared or cut out, and the measurement may be performed under the condition of a test speed of 1±0.2 mm / min in accordance with JIS K7181.

[0586] The method for producing the cured product may be any method as long as the composition can be cured, and for example, the method may be the same as described in the section "F. Method for producing cured product" described later.

[0587] The uses and the like of the cured product may be the same as those described in the above section "C. Composition".

[0588] E. Composition

[0589] Next, the second composition of the present invention will be described.

[0590] The second composition of the present invention is characterized by comprising a compound represented by the following general formula (I-2) and a desorbed product derived from a photo-desorbed group.

[0591] [Chemical formula 51]

[0592]

[0593] (In the formula, A represents an atomic group having antioxidant ability, and k represents an integer of 1 to 10.)

[0594] According to the present invention, the second composition can be easily formed using the above composition, for example. In addition, the second composition can easily impart antioxidant ability and the like.

[0595] The second composition of the present invention comprises compound I-2 and compound B'.

[0596] Hereinafter, the second composition of the present invention will be described in detail.

[0597] 1. Compound I-2

[0598] The above-mentioned compound I-2 exerts antioxidant ability.

[0599] The compound I-2 is a compound in which the BO- in the compound I-1 is substituted with an -OH group.

[0600] The contents of such compound I-1 may be the same as those described in the above section "A. Compound", and thus the description here is omitted.

[0601] The content of the compound I-2 in the composition may be any content as long as it can impart the desired antioxidant activity, and may be, for example, the same as the content of the compound I-1 in the solid component described in the above section "C. Composition".

[0602] 2. Compound B'

[0603] The compound B' is a product derived from a photo-detached group.

[0604] The photo-leaving group may be any group that can bond to the phenolic hydroxyl group as a protecting group, and may be the same as described in "1. Photo-leaving group B" of the above "A. Compound".

[0605] Such a compound B' may be any compound as long as it is a compound that can be obtained by detaching the photo-detachable group from the phenolic hydroxyl group.

[0606] It should be noted that the photo-leaving group B after being released from the phenolic hydroxyl group is generally highly reactive and can obtain various structures.

[0607] As the above-mentioned compound B', when the photodetached group B is a group represented by the above-mentioned general formula (B-1-a), (B-2), (B-3), (B-4), (B-5), (B-6), (B-7), etc., for example, it can include compounds represented by the following general formulas (B-111-a), (B-112), (B-113), (B-114), (B-115), (B-116), (B-117), etc.

[0608] [Chemical formula 52]

[0609]

[0610] Regarding R contained in the above compound B' 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 As well as b1, b2, b3, b4, b5, b6, b7 and b8, they may be the same as those described in the above-mentioned section "A. Compounds", and therefore, their description is omitted here.

[0611] The compound B' may be of one kind or a combination of two or more kinds.

[0612] The compound B' may contain one source of the photo-leaving group B, or may contain two or more sources of the photo-leaving group B.

[0613] 3. Others

[0614] The second composition contains compound I-2 and compound B', but usually contains other components.

[0615] Examples of such other components include those described in the section "2. Other components" of the above-mentioned "C. Composition".

[0616] The other components preferably include a resin component, and particularly preferably include a polymer having no polymerizable group, such as a polymer containing a polymerizable compound. This is because the second composition can effectively exert the effect of easily imparting antioxidant ability to the cured product, for example.

[0617] In addition, the type of the resin component may be only one kind, or two or more kinds may be used in combination.

[0618] The second composition may be a composition containing a solvent, a polymerizable compound, etc. and having coating properties. The viscosity in this case may be the same as described in the above section "C. Composition".

[0619] When the second composition is a cured product of a polymer containing a polymerizable compound, the elastic modulus of the second composition may be the same as described in the above section "D. Cured product".

[0620] The uses and the like of the second composition may be the same as those described in the above section "D. Cured product".

[0621] The method for producing the second composition may be any method as long as it is capable of producing a composition containing the above components, and for example, a method of irradiating a composition containing the above compound I-1 or a cured product of the composition with light can be used.

[0622] In addition, about the manufacturing method of the hardened|cured material of a composition, the method of light irradiation, etc., the method similar to the content described in the later-mentioned "F. Manufacturing method of hardened|cured material" can be used.

[0623] F. Method for producing a cured product

[0624] Next, the method for producing the cured product of the present invention will be described.

[0625] The method for producing a cured product of the present invention comprises the steps of curing a composition containing the compound I-1 of the present invention and a polymerizable compound to form a cured product, and irradiating the cured product with light to release a photo-detachable group B contained in the compound.

[0626] According to the method for producing a cured product of the present invention, the composition can be easily cured, and a cured product having excellent antioxidant ability and the like can be easily produced.

[0627] The production method of the present invention includes a step of forming a solidified product and a step of releasing the solidified product. Each step will be described in detail below.

[0628] 1. Process of forming a solidified product

[0629] The step of forming the cured product is a step of forming a cured product of the composition.

[0630] The method for forming a cured product of the composition in this step may be any method as long as it can form a cured product having a desired hardness, and the method varies depending on the components contained in the composition.

[0631] Regarding the curing method, for example, when the composition contains a polymerizable compound and a photopolymerization initiator as a polymerization initiator, a method of irradiating the composition with light to polymerize the polymerizable compounds can be used.

[0632] The light irradiated to the composition may include light having a wavelength of 300 nm to 450 nm.

[0633] Examples of the light source for the light irradiation include ultrahigh pressure mercury, mercury vapor arc, carbon arc, xenon arc and the like.

[0634] Laser light may be used as the irradiation light. As the laser light, laser light including light having a wavelength of 340 to 430 nm may be used.

[0635] As a laser light source, a light source that emits light in the visible to infrared region, such as an argon ion laser, a helium-neon laser, a YAG laser, and a semiconductor laser, may be used.

[0636] When using these lasers, the composition may contain a sensitizing dye that absorbs light in the visible to infrared region.

[0637] The total amount of light irradiated is preferably an amount that can suppress the detachment of the photodetachable groups B, and can be, for example, less than 1000 mJ / cm 2 , can be set to 800mJ / cm 2 Below, can be set to 500mJ / cm 2 the following.

[0638] Regarding the curing method, for example, when the composition contains a polymerizable compound and a thermal polymerization initiator as a polymerization initiator, a method of heating the composition to polymerize the polymerizable compounds can be used.

[0639] The heating temperature may be any heating temperature at which the composition can be stably cured, and may be 60° C. or higher, and preferably 100° C. or higher and 300° C. or lower.

[0640] In addition, the heating temperature can be set to the temperature of the coating film surface of the composition.

[0641] The heating time may be about 10 seconds to about 3 hours.

[0642] The above-mentioned curing method may include only one type or two or more types.

[0643] The composition used in this step contains the above-mentioned compound I-1 and a polymerizable compound.

[0644] Furthermore, the composition may contain other components besides the compound I-1 and the polymerizable compound.

[0645] The contents of each component of such a composition may be the same as those described in the section "2. Other components" of the above-mentioned "C. Composition", and thus the description here is omitted.

[0646] 2. Separation process

[0647] The above-mentioned elimination step is a step of eliminating the photoeliminating group B contained in the above-mentioned compound I-1.

[0648] The method for releasing the photo-releasing group B contained in the compound I-1 may be any method as long as the cured product is irradiated with light.

[0649] The light irradiated to the cured product and the total light amount thereof are not particularly limited as long as they are light capable of releasing the photo-releasing group B and the total light amount thereof, and may be the same as those described in the above section "1. Photo-releasing group B".

[0650] It should be noted that the light source for light irradiation can be appropriately selected according to the wavelength of the light to be irradiated, and can be, for example, the same as described in the above-mentioned section “1. Step of forming a cured product”.

[0651] The temperature of the cured product in this step can be appropriately set according to the heat resistance of the cured product and the substrate supporting the cured product, and is preferably 200°C or less, preferably 0°C or more and 150°C or less, and particularly preferably 0°C or more and 100°C or less. This is because the above temperature is in the above range, which facilitates the detachment of the photodetachable group B. In addition, as a result, for example, damage to the cured product and its surrounding members such as the substrate due to heating can be reduced.

[0652] It should be noted that the temperature of the solidified material may be the temperature of the surface of the solidified material.

[0653] 3. Other processes

[0654] The above-mentioned production method includes a step of forming a cured product and a step of releasing the cured product, but may include other steps as necessary.

[0655] Examples of the other steps include a step of applying the composition on a substrate.

[0656] As a method for applying the composition, a known method such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing methods, and dipping can be used.

[0657] The substrate can be appropriately selected depending on the application of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, and plastics.

[0658] Furthermore, after the cured product is formed on a substrate, it may be peeled off from the substrate before use, or it may be transferred from the substrate to another adherend before use.

[0659] 4. Others

[0660] The cured product produced by the above production method and its uses may be the same as those described in the above section "D. Cured product".

[0661] The present invention is not limited to the above-described embodiments. The above-described embodiments are illustrative, and any form having substantially the same configuration and achieving the same function and effect as the technical concept described in the claims of the present invention is included in the technical scope of the present invention.

[0662] Example

[0663] Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples.

[0664] Various measurements were performed according to the following methods.

[0665] [Example 1]

[0666] Mix 0.003 mol of the phenol compound in the following process 1, 0.0062 mol of potassium carbonate and 10 g of DMF, add 0.0075 mol of o-nitrobenzyl chloride dropwise at room temperature under a nitrogen atmosphere, stir for 10 hours, and obtain compound I-1-161 represented by the following general formula (I-1-161) corresponding to compound I-1 through the following reaction. Add 50 g of ethyl acetate and 50 g of ion exchange water to the reaction solution for oil-water separation. After drying the organic layer with anhydrous sodium sulfate, distill off the solvent and separate it with a silica column (hexane: ethyl acetate = 9: 1). After separation, wash with methanol, and dry the obtained white solid under reduced pressure at 40°C for 2 hours to obtain the target product. H-NMR confirmed that the obtained white solid was the target product.

[0667] [Chemical formula 53]

[0668] Process 1

[0669]

[0670] Table 1

[0671]

[0672] [evaluate]

[0673] A 0.01 mass % acetonitrile solution of compound I-1 (compound I-1-161) was prepared and placed in a 1 cm square quartz cell. An ultra-high pressure mercury lamp UL750 (manufactured by HOYA) was adjusted to 20 mW / cm 2 , irradiate the quartz cell filled with solution with 100mJ / cm 2 、3000mJ / cm 2 、10000mJ / cm 2 amount of light.

[0674] The irradiated liquid was analyzed by high performance liquid chromatography (HPLC), and the desorption rate was calculated according to the following formula. The results are shown in Table 2 below.

[0675] In the analysis based on HPLC, when the peak at 230 nm derived from compound 1-1 completely disappeared, calculation was performed assuming that 100% of the peak disappeared.

[0676] Desorption rate (%) = phenol compound (compound I-2) / phenol compound (compound I-2) + compound I-1) × 100

[0677] Table 2

[0678] <![CDATA[Exposure dose (mJ / cm 2 )]]> Detachment rate (%) 100 4.4 3000 84.6 10000 100

[0679] It can be confirmed from Table 2 that the photo-detachable group B of compound I-1 is detached by light irradiation.

[0680] As a result, it was confirmed that the compound I-1 can impart antioxidant ability to the cured product by light irradiation.

[0681] In addition, it was confirmed that the phenolic hydroxyl group of compound I-1 was protected by the photoleaving group B before light irradiation, and curing inhibition could be suppressed.

[0682] [Example 2 and Comparative Examples 1 and 2]

[0683] The components shown in Table 3 below were mixed in the ratios shown in Table 3 to obtain compositions of Example 2 and Comparative Examples 1 and 2. The symbols in Table 3 represent the following compounds. The numerical values ​​in the table represent parts by mass.

[0684] A-1: Free radical polymerizable compound (NKoligo EA-1020 (bisphenol A epoxy acrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0685] A-2: Radically polymerizable compound (KAYARAD DPHA (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.)

[0686] B-1: IRGACURE 907 manufactured by BASF (free radical polymerization initiator)

[0687] C-1: Silane coupling agent KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.

[0688] D-1:2-Butanone (solvent)

[0689] E-1: a compound represented by the following formula (1) (antioxidant)

[0690] F-1: Compound I-1-161 (Compound I-1)

[0691] [Chemical formula 54]

[0692]

[0693] The curability and heat resistance of the obtained compositions of Example 2 and Comparative Examples 1 and 2 were evaluated by the following methods.

[0694] [Curing properties]

[0695] The compositions of Example 2 and Comparative Examples 1 and 2 were coated on a PET film with a thickness of about 3 μm using a bar coater. Then, after prebaking at 80°C for 3 minutes, an ultra-high pressure mercury lamp (UL750) was used as a light source for exposure (20 mW / cm 2 ). It should be noted that the exposure was performed with an exposure light amount of 500 mJ / cm 2 At this time, in order to be able to measure the photosensitivity, a negative film made in a way that the transmittance is reduced in stages was used (a step tablet in which the optical density of 0.05 is set as the first stage and the optical density increases by 0.15 for each stage). Next, using isopropyl alcohol (IPA), it was washed and developed for 10 seconds at 25°C, and then dried at 80°C for 30 minutes. Then, the photosensitivity was evaluated by measuring the number of stages of the step tablet of the cured product formed on the PET film. The results are shown in Table 4 below. The higher the number of stages of the step tablet, the higher the photosensitivity.

[0696] [Heat resistance]

[0697] The compositions of Example 2 and Comparative Examples 1 and 2 were respectively coated on a glass substrate using a spin coater. Then, after prebaking at 80°C for 3 minutes, an ultra-high pressure mercury lamp (UL750) was used as a light source for exposure (20 mW / cm 2 ). It should be noted that the exposure was performed with an exposure light amount of 100 mJ / cm 2 Then irradiate with 3000mJ / cm 2 Next, a heat resistance test was performed by heat-treating the evaluation sample at 200° C. for 2 hours in an oven.

[0698] The difference in transmittance (%) at a wavelength of 430 nm before and after the heat resistance test of the evaluation sample was measured ((transmittance (%) before the heat resistance test - transmittance (%) before the heat resistance test)), and the heat resistance was evaluated according to the following criteria. The results are shown in Table 3 below.

[0699] ○: The transmittance difference (%) is less than 1% with respect to the transmittance before the heat resistance test.

[0700] ×: The transmittance difference (%) is 1% or more relative to the transmittance before the heat resistance test.

[0701] When the heat resistance evaluation is "○", it means that the cured product is excellent in heat resistance.

[0702] Table 3

[0703] Example 2 Comparative Example 1 Comparative Example 2 A-1 50 50 50 A-2 50 50 50 B-1 5 5 5 C-1 1 1 1 D-1 50 50 50 E-1 1 F-1 1 Curing 18 18 14 Heat resistance ○ × ○

[0704] As shown in Table 3, the composition of Example 2 containing Compound I-1 has better heat resistance than the composition of Comparative Example 1 not containing an antioxidant. In addition, the composition of Example 2 has better curing properties than the composition of Comparative Example 2 containing an antioxidant. It can be seen that according to the present invention, a composition with less curing hindrance and excellent antioxidant ability can be obtained.

[0705] Industrial Applicability

[0706] According to the compound of the present invention, it is possible to provide a compound which has little curing hindrance and can easily impart antioxidant ability to a cured product.

[0707] According to the latent antioxidant of the present invention, there is little hindrance to curing, and antioxidant ability and the like can be easily imparted to the cured product.

[0708] According to the composition of the present invention, for example, it is possible to provide a composition which has little curing hindrance and can produce a cured product having excellent antioxidant ability.

[0709] According to the cured product of the present invention, a cured product having excellent antioxidant ability can be provided.

[0710] According to the production method of the present invention, a cured product having excellent antioxidant ability can be produced without causing curing inhibition.

[0711] According to the second composition of the present invention, it is possible to provide a composition that does not cause curing inhibition and can provide a cured product having excellent antioxidant ability.

Claims

1. A compound represented by the following general formula (A-3): In the formula, R 1 represents an alkyl group having 1 to 5 carbon atoms, Multiple R 1 Can be the same or different. B represents a photodetachable group represented by the following general formula (B-1-a), n represents an integer from 2 to 3, a represents an integer from 0 to 2, When n is 2, X 2 represents a group represented by the following general formula (1), when n is 3, X 2 represents a group represented by the following general formula (2), In the formula, R 11 represents an alkyl group having 1 to 40 carbon atoms, R 12 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Multiple R 11 , R 12 They can be the same or different. b1 represents an integer from 0 to 4, ** represents the bonding position to -O- in the general formula (A-3), *-Z 1 —Y 1 —Z 2 * (1) In the above general formula (1), Y 1 Indicates that methane, ethane, propane, butane, or isobutane is Z 1 and Z 2 Substituted divalent groups, Z 1 and Z 2 Each independently represents a direct bond, * means that the * part is bonded to the adjacent group. In the above general formula (2), Y 11 Indicates that propane, butane, or isobutane is Z 1 , Z 2 and Z 3 Substituted trivalent groups, Z 1 , Z 2 and Z 3 Each independently represents a direct bond.

2. A latent antioxidant comprising the compound according to claim 1.

3. A composition comprising the compound according to claim 1 and a polymerizable compound. A cured product, which is a cured product of the composition according to claim 3.

5. A method for producing a solidified product, comprising the following steps: A step of curing a composition comprising the compound according to claim 1 and a polymerizable compound to form a cured product; and and irradiating the cured product with light to release the photo-release group contained in the compound.

6. A composition comprising a compound represented by the following general formula (A-3) and a desorbed product derived from a photo-desorbed group, The photodetachable group is a group represented by the following general formula (B-1-a): In the formula, R 1 represents an alkyl group having 1 to 5 carbon atoms, Multiple R 1 Can be the same or different. B represents a hydrogen atom, n represents an integer from 2 to 3, a represents an integer from 0 to 2, When n is 2, X 2 represents a group represented by the following general formula (1), when n is 3, X 2 represents a group represented by the following general formula (2), In the formula, R 11 represents an alkyl group having 1 to 40 carbon atoms, R 12 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Multiple R 11 , R 12 They can be the same or different. b1 represents an integer from 0 to 4, ** represents the bonding position with -O- in the general formula (A-3), *—Z 1 —Y 1 —Z 2 —* (1) In the above general formula (1), Y 1 Indicates that methane, ethane, propane, butane, or isobutane is Z 1 and Z 2 Substituted divalent groups, Z 1 and Z 2 Each independently represents a direct bond, * means that the * part is bonded to the adjacent group. In the above general formula (2), Y 11 Indicates that propane, butane, or isobutane is Z 1 , Z 2 and Z 3 Substituted trivalent groups, Z 1 , Z 2 and Z 3 Each independently represents a direct bond.

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