JP2002302507A - Photocurable composition containing iodonium salt compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable composition which can use various cation- polymerizable compounds and can immediately and sufficiently be cured after irradiated. SOLUTION: This photocurable composition comprises (1) an anthracene derivative represented by formula (I) (R1 and R2 are each independently a 1 to 20C alkyl which may have one or more substituents; R3 and R4 are each independently a halogen, a 1 to 20C alkyl which may have one or more substituents, or a 1 to 20C alkoxy which may have one or more substituents), (2) a cation-polymerizable compound, and (3) a diaryliodonium salt represented by formula (II) (R5 is a 1 to 6C linear or branched alkyl; R6 is a 1 to 6C linear or branched alkyl; R7 is a 1 to 6C linear or branched alkyl; Y is a functional group selected from functional groups represented by formula (III)).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable composition, and more particularly, to a photocurable composition which generates an acid upon irradiation with an active energy ray such as light, an electron beam or an X-ray and cures in a short time. Composition. Since the cured product of the composition has excellent physical properties, paints, adhesives, photoresists, inks,
It is suitably used as a silicone release or the like.

[0002]

2. Description of the Related Art Polymerization of a cationically polymerizable compound with an active energy ray-sensitive cationic polymerization initiator is preferably effected by curability because it is not affected by oxygen, and has conventionally been carried out. It is known to use sensitizers to obtain sufficient curing characteristics for both pigment systems. It is known that a diaryliodonium salt is used as an active energy ray-sensitive cationic polymerization initiator, and an anthracene derivative is used as a sensitizer.

[0003] For example, JP-A-10-147608 discloses a compound selected from the group consisting of a polyaromatic compound having at least one aralkyloxy group, an optionally substituted aralkyloxy group, an alkoxy group, and a carbazole derivative. Compositions containing at least one compound having a UV spectral absorption at a wavelength longer than 330 nm as a sensitizer are described, and Examples are described as a combination of a photopolymerization initiator and a sensitizer. Describes a combination of 4,4-di-ter-butyl-diphenyliodonium = hexafluorophosphate and 2-ethyl-9,10-dimethoxyanthracene.

Japanese Patent Application Laid-Open No. 11-329552 discloses that, as essential constituents, (1) a cationically polymerizable organic substance, (2) an energy ray-sensitive cationic polymerization initiator, and (3) the following general formula:

Embedded image (Wherein, R is a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom or a halogen atom, and X is a hydrogen atom, a halogen atom, or a carbon atom which may contain an oxygen atom or a halogen atom. And a photopolymerizable composition containing an anthracene derivative represented by the following formula (1), and various onium salts are exemplified as an energy ray-sensitive cationic polymerization initiator. Sulfonium salts and iodonium salts are preferred, and the examples describe combinations with sulfonium salts such as 4,4'-bis (di (β-hydroxyethoxy) phenylsulfonio) phenylsulfide-bis-hexafluorophosphate. .

[0005]

However, Japanese Patent Application Laid-Open No.
The anthracene derivative exemplified in 147608 has a problem that it has low versatility due to low solubility in various cationically polymerizable compounds and has insufficient curing characteristics. Further, in JP-A-11-329552, only the cured state of the surface is measured as the curing characteristics after light irradiation, and there is a problem that it is insufficient to cure the inside of the resin immediately after light irradiation. The present invention
An object of the present invention is to provide a photocurable composition which can use various cationically polymerizable compounds and can be sufficiently cured immediately after irradiation.

The present inventors have conducted intensive studies to solve the above problems, and as a result, found that the above problems were solved by combining a diaryliodonium salt having a specific structure with an anthracene derivative having a specific structure, and completed the present invention. I came to.

That is, the present invention provides: [1] (1) Formula (I)

Embedded image (Wherein, R ₁ and R ₂ each independently represent a C1 to C20 alkyl group which may have a substituent, and R ₃ and R ₄ each independently represent a halogen atom or a substituent. Represents a C1 to C20 alkyl group which may have, a C1 to C20 alkoxy group which may have a substituent, and n and m each independently represent an integer of 0 or 1 to 4 , N and m are 2 or more, R ₃ or R ₄ may be the same or different, provided that when n and m are 0, R ₁ and R ₂ are each independently a substituent Represents a C4-C20 alkyl group which may have
Anthracene derivative represented by the formula (2), a cationically polymerizable compound, (3) a formula (II)

Embedded image (R ₅ represents a C1 to C6 linear or branched alkyl group, R ₆ represents a C1 to C6 linear or branched alkyl group, p represents an integer of 1 to 4, and p is 2 or more. Time R
₆ may be the same or different, and R ₇ has 1 carbon atom.
Represents a straight-chain or branched alkyl group of from 6 to 6;
And when q is 2 or more, R ₇ may be the same or different, and Y is a group represented by the formula (III)

Embedded image (Wherein R ₉ and R ₁₀ are each independently a hydrogen atom,
Represents a straight-chain or branched alkyl group of C6, a phenyl group or an aralkyl group, s represents an integer of 1 or 2,
When s is 2, R ₉ and R ₁₀ may be the same or different, and R ₈ and R ₁₁ are each independently a hydrogen atom,
It represents a C1-C12 linear or branched alkyl group which may have a substituent, a phenyl group which may have a substituent, and an aralkyl group which may have a substituent. And r is an integer of 1 to 5, and when r is 2 or more, Y may be the same or different, and X is non-nucleophilic. Represents an anion residue. The present invention relates to a photocurable composition containing a diaryliodonium salt represented by the formula (1).

[2] The diaryliodonium salt represented by the formula (II) is

Embedded image (R ₁₂ , R ₁₃ , and R ₁₄ each independently represent a C1 to C6 linear or branched alkyl group; R ₇ represents a linear or branched alkyl group having 1 to 6 carbon atoms; Represents an integer of 0 to 4, and when q is 2 or more, R ₇ may be the same or different, and Y is a group represented by the formula (III)

Embedded image (Wherein, R ₉ and R ₁₀ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group or an aralkyl group, s represents an integer of 1 or 2, When s is 2, R ₉ and R ₁₀ may be the same or different from each other, and R ₈ and R ₁₁ are each independently a hydrogen atom or a C1 to C12 linear group which may have a substituent. Or a branched alkyl group, a phenyl group which may have a substituent or an aralkyl group which may have a substituent.) Wherein r is 1 to 5 And when r is 2 or more, Y may be the same or different, and X represents a non-nucleophilic anionic residue. The present invention relates to the photocurable resin composition according to [1], which is a compound represented by the formula (1):

[3] The non-nucleophilic anion residue is Sb
F₆, AsF₆, PF₆, BF_Four Or (F_FiveC ₆)_FourNo B
Any one of [1] and [2],
The photocurable composition according to [4], wherein the photocurable composition further contains a pigment.
The photocurable composition according to any one of [1] to [3],
[5] The photocurable composition further comprises a radical polymerizable compound.
Any of [1] to [4], characterized by containing
The photocurable composition according to item 1.

[0010]

R ₅ in DETAILED DESCRIPTION OF THE INVENTION The formula used in the present invention (II) and formula _{(IV), R 6, R} 7, R 9, R 1 0, R 12,
Specifically the linear or branched alkyl group having C1~C6 of R _13, R _14, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec-
Examples thereof include a butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a t-pentyl group, a neopentyl group, an n-hexyl group, and an isohexyl group. The aralkyl group of R ₉ and R ₁₀ represents a benzyl group, a phenethyl group, or the like.

R ₈ and R ₁₁ are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, sec -Represents an alkyl group having 1 to 12 carbon atoms such as a pentyl group, a t-pentyl group, a neopentyl group, an n-hexyl group, an isohexyl group, a heptyl group and an octyl group. And an aralkyl group which may have a substituent such as a phenyl group, a benzyl group, and a phenethyl group which may have a substituent. Examples of these substituents include halogen atoms such as chlorine, bromine and fluorine, alkyl groups having an ether bond, and hydroxy groups.

X is a non-nucleophilic anionic residue;
Preferred examples include bF ₆ , AsF ₆ , PF ₆ , BF ₄ or (F ₅ C ₆ ) ₄ B. Formula (II) and Formula (IV)
Representative examples of the iodonium salt compound represented by are shown below. Where X in the formula is SbF ₆ , AsF ₆ , PF ₆ , B
A non-nucleophilic anion residue such as F ₄ or (F ₅ C ₆ ) ₄ B is shown.

[0013]

Embedded image

The iodonium salt compound represented by the formula (II) can be produced, for example, according to the following reaction formula A or B (where M represents an alkali metal). The reaction of the compounds [a] and [b] with a sulfuric acid catalyst may be carried out, if necessary, in an organic solvent such as acetic acid or acetic anhydride at -20 ° C to room temperature.
Performed for hours to tens of hours. After the completion of the reaction, water is added to the reaction solution, followed by stirring. The precipitated compound is collected by filtration or extracted with an organic solvent to obtain the compound [c], and the target product [d] is obtained by a salt exchange reaction.

[0015]

Embedded image

The iodonium salt compound represented by the formula (IV) can be produced in the same manner. These iodonium salt compounds can be used as a photoacid generator, and as a photopolymerization initiator, a cationic polymerizable compound can be cured by irradiation with active energy rays such as light, an electron beam, and X-rays.
Light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps,
An ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp and the like are used. Further, it can be easily cured by a laser beam such as a semiconductor laser, an argon laser, a He-Cd laser, or an ionizing radiation such as an α-ray, a β-ray, a γ-ray, a neutron beam, an X-ray, and an accelerating electron beam. .

As the cationically polymerizable compound used in the present invention, any cationically polymerizable monomers, oligomers and polymers can be used irrespective of their types. Oxirane compounds such as cyclic epoxy compounds and oxetane compounds and vinyl ether compounds can be exemplified.

The cationically polymerizable compound used in the present invention will be more specifically described below. (A) As the vinyl compound, styrene compounds such as styrene, α-methylstyrene, p-methoxystyrene, pt-butoxystyrene, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and cyclohexyl vinyl ether Alkyl such as, 2-chloroethyl vinyl ether, 2-phenoxyethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, dodecyl vinyl ether, stearyl vinyl ether, and 2-acetoxyethyl vinyl ether Vinyl ether compound, allyl vinyl ether, 2-methacryloyloxyethylbi Ether, 2-acryl alkenyl vinyl ether compounds such as acryloyloxyethyl vinyl ether, phenyl vinyl ether, aryl vinyl ether compounds such as p- methoxyphenyl vinyl ether,
N-vinyl carbazole, cationically polymerizable nitrogen-containing compounds such as N-vinyl pyrrolidone, butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, hexanediol divinyl ether, Examples include polyfunctional vinyl compounds such as cyclohexanediol divinyl ether, cyclohexane dimethanol divinyl ether, 1,4-benzene dimethanol divinyl ether, hydroquinone divinyl ether, and sasolcinol divinyl ether.

(B) Epoxy compounds include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene Monooxide, 1,2-dodecylene oxide,
Monofunctional such as epichlorohydrin, 1,2-epoxydecane, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide monomer,
1,13-tetradecadienedoxide, limonenedoxide, 3,4-epoxycyclohexylmethyl-
(3,4-epoxycyclohexyl) carboxylate, di (3,4-epoxycyclohexyl) adipate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-, m-, p-cresol novolak type epoxy resin, phenol novolak And polyfunctional epoxy compounds such as polyepoxy resin and polyglycidyl ether of polyhydric alcohol.

(C) Bicycloorthoester compounds include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane and 1-ethyl-4
And compounds such as -hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane.

(D) As the spiro orthocarbonate compound, 1,5,7,11-tetraoxaspiro [5,
5] undecane, 3,9-dibenzyl-1,5,7,1
1-tetraoxaspiro [5,5] undecane, 1,
4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4,6-trioxaspiro [4,4] nonane,
Compounds such as 1,4,6-trioxaspiro [4,5] decane are exemplified. (E) As the oxetane compound, 3,3-dimethyloxetane, 3,3-bis (chloromethyl) oxetane,
2-hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-methoxymethyloxetane, 3-ethyl-3- (2-ethylhexoxymethyl)
Oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 1,4-bis [[(3-ethyl-3-oxetanyl) methoxy] methyl] benzene, 3-ethyl-3-
[[3- (triethoxysilyl) propoxy] methyl] oxetane, 3-ethyl-3-phenoxymethyloxetane,
Resorcinol bis (3-methyl-3-oxetanylethyl) ether, m-xylylenebis (3-ethyl-3
-Oxetanyl ethyl ether) and phenol novolak oxetane. These may be used alone or in combination of two or more.

The present invention is characterized in that an anthracene derivative represented by the formula (I) is used. R ₁ and R
₂ is each independently C1 which may have a substituent
Represents an ~C20 alkyl group, R ₃ and R ₄ are each independently, C1 to halogen atoms, which may have a substituent
C20 alkyl group, optionally substituted C1 to C1
20 represents an alkoxy group, n and m each independently represent an integer of 0 or 1 to 4, and when n and m are 2 or more, R ₃ or R ₄ is the same or different May be. However, when n and m are 0, R
₁ and R ₂ each independently represent a C4-C20 alkyl group which may have a substituent.

Examples of the substituent of the C1-C20 alkyl group or the alkoxy group include a halogen atom such as chlorine, bromine and fluorine, an alkyl group having an ether bond, a hydroxy group and an aryl group. Multiple bonds may be included in the alkyl chain.

An anthracene derivative represented by the formula (I)
Specifically, 9,10-diphenoxyanthracese
9,10-di-n-butoxyanthracene, 9.1
0-di-isobutoxyanthracene, 9,10-di-s
-Butoxyanthracene, 9,10-di-t-butoxy
Anthracene, 9,10-bis- (n-pentyloxy
C) anthracene, 9,10-bis- (isopentyl
Xy) anthracene, 9,10-bis- (1-methylbu
Tyloxy) anthracene, 9,10-bis- (t-pe
Nthyloxy) anthracene, 9,10-bis- (n-
Hexyloxy) anthracene, 9,10-bis- (A
Sohexyloxy) anthracene, 9,10-bis-
(N-heptyloxy) anthracene, 9,10-bis
-(N-octyloxy) anthracene, 9,10-bi
Su- (1-methylheptyloxy) anthracene, 9,
10-bis- (2-ethylhexyloxy) anthrace
9,10-bis- (n-nonyloxy) anthracene
9,10-bis- (n-decyloxy) anthracene
9,10-bis- (n-undecyloxy) ant
Helix, 9,10-bis- (n-dodecyloxy) anne
Toracene, 9,10-bis- (n-tridecyloxy)
Anthracene, 9,10-bis- (n-tetradecylo
Xy) anthracene, 9,10-bis- (n-pentade
Siloxy) anthracene, 9,10-bis- (n-f
Xadecyloxy) anthracene, 9,10-bis-
(N-heptadecyloxy) anthracene, 9,10-
Bis- (n-octadecyloxy) anthracene, 9,
10-bis- (cyclohexyloxy) anthracene,
9,10-bis- (2-phenoxyethoxy) anthra
Sen, 9,10-di- (benzyloxy) anthrace
1-chloro-9,10-diphenoxyanthracene
, 1-chloro-9,10-dimethoxyanthracene,
1-chloro-9,10-diethoxyanthracene, 1-
Chloro-9,10-di-n-propoxyanthracene,
1-chloro-9,10-di-isopropoxyanthracese
1-chloro-9,10-di-n-butoxyanthra
Sen, 1-chloro-9,10-di-isobutoxyant
Helix, 1-chloro-9,10-di-s-butoxyan
Toracene, 1-chloro-9,10-di-t-butoxya
Anthracene, 1-chloro-9,10-bis- (n-pen
Tyloxy) anthracene, 1-chloro-9,10-bi
S- (Isopentyloxy) anthracene, 1-chloro
-9,10-bis- (1-methylbutyloxy) ant
Helix, 1-chloro-9,10-bis- (t-pentyl
Oxy) anthracene, 1-chloro-9,10-bis-
(N-hexyloxy) anthracene, 1-chloro-
9,10-bis- (isohexyloxy) anthrace
1-chloro-9,10-bis- (n-heptyloxy
C) anthracene, 1-chloro-9,10-bis- (n
-Octyloxy) anthracene, 1-chloro-9,1
0-bis- (1-methylheptyloxy) anthrace
1-chloro-9,10-bis- (2-ethylhexyl
Loxy) anthracene, 1-chloro-9,10-bis
-(N-nonyloxy) anthracene, 1-chloro-
9,10-bis- (n-decyloxy) anthracene,
1-chloro-9,10-bis- (n-undecyloxy
C) anthracene, 1-chloro-9,10-bis- (n
-Dodecyloxy) anthracene, 1-chloro-9,1
0-bis- (n-tridecyloxy) anthracene, 1
-Chloro-9,10-bis- (n-tetradecyloxy
C) anthracene, 1-chloro-9,10-bis- (n
-Pentadecyloxy) anthracene, 1-chloro-
9,10-bis- (n-hexadecyloxy) anthra
Sen, 1-chloro-9,10-bis- (n-heptadeci
Loxy) anthracene, 1-chloro-9,10-bis
-(N-octadecyloxy) anthracene, 1-chloro
B-9,10-Bis- (cyclohexyloxy) ant
Helix, 1-chloro-9,10-bis- (2-phenoxy
Siethoxy) anthracene, 1-chloro-9,10-di
-(Benzyloxy) anthracene, 1,5-dichloro
-9,10-diphenoxyanthracene, 1,5-dic
Loro-9,10-dimethoxyanthracene, 1,5-di
Chloro-9,10-diethoxyanthracene, 1,5-
Dichloro-9,10-di-n-propoxyanthracese
, 1,5-dichloro-9,10-di-isopropoxy
Anthracene, 1,5-dichloro-9,10-di-n-
Butoxyanthracene, 1,5-dichloro-9,10-
Di-isobutoxyanthracene, 1,5-dichloro-
9,10-di-s-butoxyanthracene, 1,5-di
Chloro-9,10-di-t-butoxyanthracene,
1,5-dichloro-9,10-bis- (n-pentylthio
Xy) anthracene, 1,5-dichloro-9,10-bi
S- (Isopentyloxy) anthracene, 1,5-di
Chloro-9,10-bis- (1-methylbutyloxy)
Anthracene, 1,5-dichloro-9,10-bis-
(T-pentyloxy) anthracene, 1,5-dichloro
B-9,10-Bis- (n-hexyloxy) anthra
Sen, 1,5-dichloro-9,10-bis- (isohex
Siloxy) anthracene, 1,5-dichloro-9,1
0-bis- (n-heptyloxy) anthracene, 1,
5-dichloro-9,10-bis- (n-octyloxy
C) Anthracene, 1,5-dichloro-9,10-bis
-(1-methylheptyloxy) anthracene, 1,5
-Dichloro-9,10-bis- (2-ethylhexylio
Xy) anthracene, 1,5-dichloro-9,10-bi
S- (n-nonyloxy) anthracene, 1,5-dic
Loro-9,10-bis- (n-decyloxy) anthra
Sen, 1,5-dichloro-9,10-bis- (n-un
(Decyloxy) anthracene, 1,5-dichloro-9,
10-bis- (n-dodecyloxy) anthracene,
1,5-dichloro-9,10-bis- (n-tridecyl
Oxy) anthracene, 1,5-dichloro-9,10-
Bis- (n-tetradecyloxy) anthracene, 1,
5-dichloro-9,10-bis- (n-pentadecylthio
Xy) anthracene, 1,5-dichloro-9,10-bi
S- (n-hexadecyloxy) anthracene, 1,5
-Dichloro-9,10-bis- (n-heptadecyloxy
C) Anthracene, 1,5-dichloro-9,10-bis
-(N-octadecyloxy) anthracene, 1,5-
Dichloro-9,10-bis- (cyclohexyloxy)
Anthracene, 1,5-dichloro-9,10-bis-
(2-phenoxyethoxy) anthracene, 1,5-di
Chloro-9,10-di- (benzyloxy) anthrace
, 1,8-dichloro-9,10-diphenoxyant
Helix, 1,8-dichloro-9,10-dimethoxyan
Toracene, 1,8-dichloro-9,10-diethoxy
Anthracene, 1,8-dichloro-9,10-di-n-propyl
Lopoxyanthracene, 1,8-dichloro-9,10-
Di-isopropoxyanthracene, 1,8-dichloro-
9,10-di-n-butoxyanthracene, 1,8-di
Chloro-9,10-di-isobutoxyanthracene,
1,8-dichloro-9,10-di-s-butoxyant
Helix, 1,8-dichloro-9,10-di-t-butoki
Cyanthracene, 1,8-dichloro-9,10-bis-
(N-pentyloxy) anthracene, 1,8-dichloro
B-9,10-Bis- (isopentyloxy) anthra
Sen, 1,8-dichloro-9,10-bis- (1-methyl
Rubutyloxy) anthracene, 1,8-dichloro-
9,10-bis- (t-pentyloxy) anthrace
, 1,8-dichloro-9,10-bis- (n-hexyl
Loxy) anthracene, 1,8-dichloro-9,10
-Bis- (isohexyloxy) anthracene, 1,8
-Dichloro-9,10-bis- (n-heptyloxy)
Anthracene, 1,8-dichloro-9,10-bis-
(N-octyloxy) anthracene, 1,8-dichloro
B-9,10-Bis- (1-methylheptyloxy) a
Anthracene, 1,8-dichloro-9,10-bis- (2
-Ethylhexyloxy) anthracene, 1,8-dic
Rollo-9,10-bis- (n-nonyloxy) anthra
Sen, 1,8-dichloro-9,10-bis- (n-decyl
Loxy) anthracene, 1,8-dichloro-9,10
-Bis- (n-undecyloxy) anthracene, 1,
8-dichloro-9,10-bis- (n-dodecyloxy
C) anthracene, 1,8-dichloro-9,10-bis
-(N-tridecyloxy) anthracene, 1,8-di
Chloro-9,10-bis- (n-tetradecyloxy)
Anthracene, 1,8-dichloro-9,10-bis-
(N-pentadecyloxy) anthracene, 1,8-di
Chloro-9,10-bis- (n-hexadecyloxy)
Anthracene, 1,8-dichloro-9,10-bis-
(N-heptadecyloxy) anthracene, 1,8-di
Chloro-9,10-bis- (n-octadecyloxy)
Anthracene, 1,8-dichloro-9,10-bis-
(Cyclohexyloxy) anthracene, 1,8-dic
Rollo-9,10-bis- (2-phenoxyethoxy) a
Anthracene, 1,8-dichloro-9,10-di- (ben
(Zyloxy) anthracene, 2-chloromethyl-9,1
0-diphenoxyanthracene, 2-chloromethyl-
9,10-dimethoxyanthracene, 2-chloromethyl
-9,10-diethoxyanthracene, 2-chloromethyl
Ru-9,10-di-n-propoxyanthracene, 2-
Chloromethyl-9,10-di-isopropoxyanthra
Sen, 2-chloromethyl-9,10-di-n-butoxy
Anthracene, 2-chloromethyl-9,10-di-iso
Butoxyanthracene, 2-chloromethyl-9,10-
Di-s-butoxyanthracene, 2-chloromethyl-
9,10-di-t-butoxyanthracene, 2-chloro
Methyl-9,10-bis- (n-pentyloxy) an
Toracene, 2-chloromethyl-9,10-bis- (iso
Pentyloxy) anthracene, 2-chloromethyl-
9,10-bis- (1-methylbutyloxy) anthra
Sen, 2-chloromethyl-9,10-bis- (t-pen
Tyloxy) anthracene, 2-chloromethyl-9,1
0-bis- (n-hexyloxy) anthracene, 2-
Chloromethyl-9,10-bis- (isohexyloxy
C) anthracene, 2-chloromethyl-9,10-bis
-(N-heptyloxy) anthracene, 2-chloromethine
Cyl-9,10-bis- (n-octyloxy) ant
Helix, 2-chloromethyl-9,10-bis- (1-meth
Tylheptyloxy) anthracene, 2-chloromethyl
-9,10-bis- (2-ethylhexyloxy) anne
Toracene, 2-chloromethyl-9,10-bis- (n-
Nonyloxy) anthracene, 2-chloromethyl-9,
10-bis- (n-decyloxy) anthracene, 2-
Chloromethyl-9,10-bis- (n-undecyloxy
C) anthracene, 2-chloromethyl-9,10-bis
-(N-dodecyloxy) anthracene, 2-chloromethine
Cyl-9,10-bis- (n-tridecyloxy) an
Toracene, 2-chloromethyl-9,10-bis- (n-
Tetradecyloxy) anthracene, 2-chloromethyl
-9,10-bis- (n-pentadecyloxy) ant
Helix, 2-chloromethyl-9,10-bis- (n-f
Xadecyloxy) anthracene, 2-chloromethyl-
9,10-bis- (n-heptadecyloxy) anthra
Sen, 2-chloromethyl-9,10-bis- (n-octane
Tadecyloxy) anthracene, 2-chloromethyl-
9,10-bis- (cyclohexyloxy) anthrace
2-chloromethyl-9,10-bis- (2-pheno
(Xyethoxy) anthracene, 2-chloromethyl-9,
10-di- (benzyloxy) anthracene, 2-chloro
B-9,10-Diphenoxyanthracene, 2-chloro
-9,10-dimethoxyanthracene, 2-chloro-
9,10-diethoxyanthracene, 2-chloro-9,
10-di-n-propoxyanthracene, 2-chloro-
9,10-di-isopropoxyanthracene, 2-chloro
B-9,10-Di-n-butoxyanthracene, 2-c
Loro-9,10-di-isobutoxyanthracene, 2-
Chloro-9,10-di-s-butoxyanthracene, 2
-Chloro-9,10-di-t-butoxyanthracene,
2-chloro-9,10-bis- (n-pentyloxy)
Anthracene, 2-chloro-9,10-bis- (isope
Nthyloxy) anthracene, 2-chloro-9,10-
Bis- (1-methylbutyloxy) anthracene, 2-
Chloro-9,10-bis- (t-pentyloxy) an
Toracene, 2-chloro-9,10-bis- (n-hexyl
Ruoxy) anthracene, 2-chloro-9,10-bis
-(Isohexyloxy) anthracene, 2-chloro-
9,10-bis- (n-heptyloxy) anthrace
2-chloro-9,10-bis- (n-octyloxy
C) anthracene, 2-chloro-9,10-bis- (1
-Methylheptyloxy) anthracene, 2-chloro-
9,10-bis- (2-ethylhexyloxy) ant
Helix, 2-chloro-9,10-bis- (n-nonylo
Xy) anthracene, 2-chloro-9,10-bis-
(N-decyloxy) anthracene, 2-chloro-9,
10-bis- (n-undecyloxy) anthracene,
2-chloro-9,10-bis- (n-dodecyloxy)
Anthracene, 2-chloro-9,10-bis- (n-to
Ridecyloxy) anthracene, 2-chloro-9,10
-Bis- (n-tetradecyloxy) anthracene, 2
-Chloro-9,10-bis- (n-pentadecyloxy
C) anthracene, 2-chloro-9,10-bis- (n
-Hexadecyloxy) anthracene, 2-chloro-
9,10-bis- (n-heptadecyloxy) anthra
Sen, 2-chloro-9,10-bis- (n-octadecyl
Ruoxy) anthracene, 2-chloro-9,10-bis
-(Cyclohexyloxy) anthracene, 2-chloro
-9,10-bis- (2-phenoxyethoxy) ant
Helix, 2-chloro-9,10-di- (benzyloxy
C) Anthracene, 2-ethyl-9,10-diphenoxy
Cyanthracene, 2-ethyl-9,10-dimethoxya
Anthracene, 2-ethyl-9,10-diethoxyant
Helix, 2-ethyl-9,10-di-n-propoxya
Anthracene, 2-ethyl-9,10-di-isopropoxy
Cyanthracene, 2-ethyl-9,10-di-n-but
Xianthracene, 2-ethyl-9,10-di-isobu
Toxianthracene, 2-ethyl-9,10-di-s-
Butoxyanthracene, 2-ethyl-9,10-di-t
-Butoxyanthracene, 2-ethyl-9,10-bis
-(N-pentyloxy) anthracene, 2-ethyl-
9,10-bis- (isopentyloxy) anthrace
2-ethyl-9,10-bis- (1-methylbutyl
Oxy) anthracene, 2-ethyl-9,10-bis-
(T-pentyloxy) anthracene, 2-ethyl-
9,10-bis- (n-hexyloxy) anthrace
, 2-ethyl-9,10-bis- (isohexyloxy
C) anthracene, 2-ethyl-9,10-bis- (n
-Heptyloxy) anthracene, 2-ethyl-9,1
0-bis- (n-octyloxy) anthracene, 2-
Ethyl-9,10-bis- (1-methylheptyloxy
C) anthracene, 2-ethyl-9,10-bis- (2
-Ethylhexyloxy) anthracene, 2-ethyl-
9,10-bis- (n-nonyloxy) anthracene,
2-ethyl-9,10-bis- (n-decyloxy) a
Anthracene, 2-ethyl-9,10-bis- (n-un
(Decyloxy) anthracene, 2-ethyl-9,10-
Bis- (n-dodecyloxy) anthracene, 2-ethyl
-9,10-bis- (n-tridecyloxy) ant
Helix, 2-ethyl-9,10-bis- (n-tetrade
Siloxy) anthracene, 2-ethyl-9,10-bi
S- (n-pentadecyloxy) anthracene, 2-d
Cyl-9,10-bis- (n-hexadecyloxy) a
Anthracene, 2-ethyl-9,10-bis- (n-heptane
Tadecyloxy) anthracene, 2-ethyl-9,10
-Bis- (n-octadecyloxy) anthracene, 2
-Ethyl-9,10-bis- (cyclohexyloxy)
Anthracene, 2-ethyl-9,10-bis- (2-
Enoxyethoxy) anthracene, 2-ethyl-9,1
0-di- (benzyloxy) anthracene, 2-methyl
-9,10-diphenoxyanthracene, 2-methyl-
9,10-dimethoxyanthracene, 2-methyl-9,
10-diethoxyanthracene, 2-methyl-9,10
-Di-n-propoxyanthracene, 2-methyl-9,
10-di-isopropoxyanthracene, 2-methyl-
9,10-di-n-butoxyanthracene, 2-methyl
-9,10-di-isobutoxyanthracene, 2-methyl
-9,10-di-s-butoxyanthracene, 2-meth
Cyl-9,10-di-t-butoxyanthracene, 2-
Methyl-9,10-bis- (n-pentyloxy) an
Toracene, 2-methyl-9,10-bis- (isopentene
Ruoxy) anthracene, 2-methyl-9,10-bis
-(1-methylbutyloxy) anthracene, 2-methyl
Ru-9,10-bis- (t-pentyloxy) anthra
Sen, 2-methyl-9,10-bis- (n-hexyl
Xy) anthracene, 2-methyl-9,10-bis-
(Isohexyloxy) anthracene, 2-methyl-
9,10-bis- (n-heptyloxy) anthrace
, 2-methyl-9,10-bis- (n-octyloxy
C) anthracene, 2-methyl-9,10-bis- (1
-Methylheptyloxy) anthracene, 2-methyl-
9,10-bis- (2-ethylhexyloxy) ant
Helix, 2-methyl-9,10-bis- (n-nonylo
Xy) anthracene, 2-methyl-9,10-bis-
(N-decyloxy) anthracene, 2-methyl-9,
10-bis- (n-undecyloxy) anthracene,
2-methyl-9,10-bis- (n-dodecyloxy)
Anthracene, 2-methyl-9,10-bis- (n-to
Ridecyloxy) anthracene, 2-methyl-9,10
-Bis- (n-tetradecyloxy) anthracene, 2
-Methyl-9,10-bis- (n-pentadecyloxy
C) anthracene, 2-methyl-9,10-bis- (n
-Hexadecyloxy) anthracene, 2-methyl-
9,10-bis- (n-heptadecyloxy) anthra
Sen, 2-methyl-9,10-bis- (n-octadecyl
Ruoxy) anthracene, 2-methyl-9,10-bis
-(Cyclohexyloxy) anthracene, 2-methyl
-9,10-bis- (2-phenoxyethoxy) ant
Helix, 2-methyl-9,10-di- (benzyloxy
C) anthracene, 2-t-butyl-9,10-dife
Noxianthracene, 2-t-butyl-9,10-dimension
Toxianthracene, 2-t-butyl-9,10-die
Toxianthracene, 2-t-butyl-9,10-di-
n-propoxyanthracene, 2-t-butyl-9,1
0-di-isopropoxyanthracene, 2-t-butyl
-9,10-di-n-butoxyanthracene, 2-t-
Butyl-9,10-di-isobutoxyanthracene, 2
-T-butyl-9,10-di-s-butoxyanthracese
2-t-butyl-9,10-di-t-butoxyan
Toracene, 2-t-butyl-9,10-bis- (n-pe
(Nthyloxy) anthracene, 2-tert-butyl-9,1
0-bis- (isopentyloxy) anthracene, 2-
t-butyl-9,10-bis- (1-methylbutyloxy
C) Anthracene, 2-t-butyl-9,10-bis-
(T-pentyloxy) anthracene, 2-t-butyl
-9,10-bis- (n-hexyloxy) anthracene
2-t-butyl-9,10-bis- (isohexyl
Oxy) anthracene, 2-t-butyl-9,10-bi
S- (n-heptyloxy) anthracene, 2-t-butyl
Cyl-9,10-bis- (n-octyloxy) ant
Helix, 2-t-butyl-9,10-bis- (1-methyl
Ruheptyloxy) anthracene, 2-t-butyl-
9,10-bis- (2-ethylhexyloxy) ant
Helix, 2-t-butyl-9,10-bis- (n-noni
Loxy) anthracene, 2-t-butyl-9,10-
Bis- (n-decyloxy) anthracene, 2-t-butyl
Cyl-9,10-bis- (n-undecyloxy) an
Toracene, 2-t-butyl-9,10-bis- (n-do
(Decyloxy) anthracene, 2-t-butyl-9,1
0-bis- (n-tridecyloxy) anthracene, 2
-T-butyl-9,10-bis- (n-tetradecylthio
Xy) anthracene, 2-t-butyl-9,10-bis
-(N-pentadecyloxy) anthracene, 2-t-
Butyl-9,10-bis- (n-hexadecyloxy)
Anthracene, 2-t-butyl-9,10-bis- (n
-Heptadecyloxy) anthracene, 2-t-butyl
-9,10-bis- (n-octadecyloxy) ant
Helix, 2-t-butyl-9,10-bis- (cyclo
Xyloxy) anthracene, 2-tert-butyl-9,1
0-bis- (2-phenoxyethoxy) anthracene,
2-tert-butyl-9,10-di- (benzyloxy) a
Anthracene, 1,4,9,10-tetraphenoxy-
5,6-dichloroanthracene, 1,4,9,10-te
Tramethoxy-5,6-dichloroanthracene, 1,
4,9,10-tetraethoxy-5,6-dichloroan
Toracene, 1,4,9,10-tetra-n-propoxy
-5,6-dichloroanthracene, 1,4,9,10-
Tetra-isopropoxy-5,6-dichloroanthrace
1,4,9,10-tetra-n-butoxy-5,6
-Dichloroanthracene, 1,4,9,10-tetra-
Isobutoxy-5,6-dichloroanthracene, 1,
4,9,10-tetra-s-butoxy-5,6-dichloro
Loanthracene, 1,4,9,10-tetra-t-but
Xy-5,6-dichloroanthracene, 1,4,9,1
0-tetrakis- (n-pentyloxy) -5,6-di
Chloroanthracene, 1,4,9,10-tetrakis-
(Isopentyloxy) -5,6-dichloroanthrace
1,4,9,10-tetrakis- (1-methylbutyi)
Ruoxy) -5,6-dichloroanthracene, 1,4
9,10-tetrakis- (t-pentyloxy) -5,
6-dichloroanthracene, 1,4,9,10-tetra
Kis- (n-hexyloxy) -5,6-dichloroan
Toracene, 1,4,9,10-tetrakis- (isohex
Siloxy) -5,6-dichloroanthracene, 1,
4,9,10-tetrakis- (n-heptyloxy)-
5,6-dichloroanthracene, 1,4,9,10-te
Trakis- (n-octyloxy) -5,6-dichloro
Anthracene, 1,4,9,10-tetrakis- (1-
Methylheptyloxy) -5,6-dichloroanthrace
1,4,9,10-tetrakis- (2-ethylhexane)
Siloxy) -5,6-dichloroanthracene, 1,
4,9,10-tetrakis- (n-nonyloxy)-
5,6-dichloroanthracene, 1,4,9,10-te
Trakis- (n-decyloxy) -5,6-dichloroa
Anthracene, 1,4,9,10-tetrakis- (n-U
Ndecyloxy) -5,6-dichloroanthracene,
1,4,9,10-tetrakis- (n-dodecyloxy
B) -5,6-dichloroanthracene, 1,4,9,1
0-tetrakis- (n-tridecyloxy) -5,6-
Dichloroanthracene, 1,4,9,10-tetrakis
-(N-tetradecyloxy) -5,6-dichloroan
Toracene, 1,4,9,10-tetrakis- (n-pen
Tadecyloxy) -5,6-dichloroanthracene,
1,4,9,10-tetrakis- (n-hexadecylthio)
Xy) -5,6-dichloroanthracene, 1,4,9,
10-tetrakis- (n-heptadecyloxy) -5,
6-dichloroanthracene, 1,4,9,10-tetra
Kis- (n-octadecyloxy) -5,6-dichloro
Anthracene, 1,4,9,10-tetrakis- (sic
Rohexyloxy) -5,6-dichloroanthracene,
1,4,9,10-tetrakis- (2-phenoxyeth
Xy) -5,6-dichloroanthracene, 1,4,9,
10-tetrakis- (benzyloxy) -5,6-dic
Loloanthracene, 1,4,9,10-tetraphenoki
C-6,7-dichloroanthracene, 1,4,9,10
-Tetramethoxy-6,7-dichloroanthracene,
1,4,9,10-tetraethoxy-6,7-dichloro
Anthracene, 1,4,9,10-tetra-n-propo
Xy-6,7-dichloroanthracene, 1,4,9,1
0-tetra-isopropoxy-6,7-dichloroant
Helix, 1,4,9,10-tetra-n-butoxy-
6,7-dichloroanthracene, 1,4,9,10-te
Tra-isobutoxy-6,7-dichloroanthracene,
1,4,9,10-tetra-s-butoxy-6,7-di
Chloroanthracene, 1,4,9,10-tetra-t-
Butoxy-6,7-dichloroanthracene, 1,4
9,10-tetrakis- (n-pentyloxy) -6,6
7-dichloroanthracene, 1,4,9,10-tetra
Kis- (isopentyloxy) -6,7-dichloroan
Toracene, 1,4,9,10-tetrakis- (1-methyl
Rubutyloxy) -6,7-dichloroanthracene,
1,4,9,10-tetrakis- (t-pentyloxy
B) -6,7-dichloroanthracene, 1,4,9,1
0-tetrakis- (n-hexyloxy) -6,7-di
Chloroanthracene, 1,4,9,10-tetrakis-
(Isohexyloxy) -6,7-dichloroanthrace
1,4,9,10-tetrakis- (n-heptylthio)
Xy) -6,7-dichloroanthracene, 1,4,9,
10-tetrakis- (n-octyloxy) -6,7-
Dichloroanthracene, 1,4,9,10-tetrakis
-(1-methylheptyloxy) -6,7-dichloroa
Anthracene, 1,4,9,10-tetrakis- (2-E
Tylhexyloxy) -6,7-dichloroanthrace
1,4,9,10-tetrakis- (n-nonyloxy
B) -6,7-dichloroanthracene, 1,4,9,1
0-tetrakis- (n-decyloxy) -6,7-dic
Loloanthracene, 1,4,9,10-tetrakis-
(N-undecyloxy) -6,7-dichloroanthra
Sen, 1,4,9,10-tetrakis- (n-dodecyl)
Oxy) -6,7-dichloroanthracene, 1,4
9,10-tetrakis- (n-tridecyloxy)-
6,7-dichloroanthracene, 1,4,9,10-te
Trakis- (n-tetradecyloxy) -6,7-dic
Loloanthracene, 1,4,9,10-tetrakis-
(N-pentadecyloxy) -6,7-dichloroant
Helix, 1,4,9,10-tetrakis- (n-hexa
(Decyloxy) -6,7-dichloroanthracene, 1,
4,9,10-tetrakis- (n-heptadecyloxy
B) -6,7-dichloroanthracene, 1,4,9,1
0-tetrakis- (n-octadecyloxy) -6,7
-Dichloroanthracene, 1,4,9,10-tetraki
S- (cyclohexyloxy) -6,7-dichloroan
Toracene, 1,4,9,10-tetrakis- (2-fe
Noxyethoxy) -6,7-dichloroanthracene,
1,4,9,10-tetrakis- (benzyloxy)-
6,7-dichloroanthracene, 1,2,9,10-te
Traphenoxyanthracene, 1,2,9,10-tet
Lamethoxyanthracene, 1,2,9,10-tetraet
Toxianthracene, 1,2,9,10-tetra-n-
Propoxyanthracene, 1,2,9,10-tetra-
Isopropoxyanthracene, 1,2,9,10-tet
Ra-n-butoxyanthracene, 1,2,9,10-te
Tora-isobutoxyanthracene, 1,2,9,10-
Tetra-s-butoxyanthracene, 1,2,9,10
-Tetra-t-butoxyanthracene, 1,2,9,1
0-tetrakis- (n-pentyloxy) anthrace
1,2,9,10-tetrakis- (isopentyl
Xy) anthracene, 1,2,9,10-tetrakis-
(1-methylbutyloxy) anthracene, 1,2,2
9,10-tetrakis- (t-pentyloxy) ant
Helix, 1,2,9,10-tetrakis- (n-hexyl
Ruoxy) anthracene, 1,2,9,10-tetraki
S- (isohexyloxy) anthracene, 1,2,2
9,10-tetrakis- (n-heptyloxy) ant
Helix, 1,2,9,10-tetrakis- (n-octy
Ruoxy) anthracene, 1,2,9,10-tetraki
Su- (1-methylheptyloxy) anthracene, 1,
2,9,10-tetrakis- (2-ethylhexyloxy
C) Anthracene, 1,2,9,10-tetrakis-
(N-nonyloxy) anthracene, 1,2,9,10
-Tetrakis- (n-decyloxy) anthracene,
1,2,9,10-tetrakis- (n-undecyloxy
C) Anthracene, 1,2,9,10-tetrakis-
(N-dodecyloxy) anthracene, 1,2,9,1
0-tetrakis- (n-tridecyloxy) anthrace
1,2,9,10-tetrakis- (n-tetradeci-
Ruoxy) anthracene, 1,2,9,10-tetraki
Su- (n-pentadecyloxy) anthracene, 1,
2,9,10-tetrakis- (n-hexadecyloxy
C) anthracene, 1,2,9,10-tetrakis-
(N-heptadecyloxy) anthracene, 1,2,2
9,10-tetrakis- (n-octadecyloxy) a
Anthracene, 1,2,9,10-tetrakis- (cyclo
Hexyloxy) anthracene, 1,2,9,10-te
Trakis- (2-phenoxyethoxy) anthracene,
1,2,9,10-tetrakis- (benzyloxy) a
Anthracene, 1,4,9,10-tetraphenoxyan
Toracene, 1,4,9,10-tetramethoxyanthra
Sen, 1,4,9,10-tetraethoxyanthrace
, 1,4,9,10-tetra-n-propoxyant
Helix, 1,4,9,10-tetra-isopropoxya
Anthracene, 1,4,9,10-tetra-n-butoxy
Anthracene, 1,4,9,10-tetra-isobutoki
Cyanthracene, 1,4,9,10-tetra-s-buto
Xianthracene, 1,4,9,10-tetra-t-butyl
Toxianthracene, 1,4,9,10-tetrakis-
(N-pentyloxy) anthracene, 1,4,9,1
0-tetrakis- (isopentyloxy) anthrace
1,4,9,10-tetrakis- (1-methylbutyi)
Ruoxy) anthracene, 1,4,9,10-tetraki
Su- (t-pentyloxy) anthracene, 1,4,
9,10-tetrakis- (n-hexyloxy) ant
Helix, 1,4,9,10-tetrakis- (isohexyl
Ruoxy) anthracene, 1,4,9,10-tetraki
S- (n-heptyloxy) anthracene, 1,4,
9,10-tetrakis- (n-octyloxy) ant
Helix, 1,4,9,10-tetrakis- (1-methyl
Heptyloxy) anthracene, 1,4,9,10-te
Trakis- (2-ethylhexyloxy) anthrace
1,4,9,10-tetrakis- (n-nonyloxy
C) anthracene, 1,4,9,10-tetrakis-
(N-decyloxy) anthracene, 1,4,9,10
-Tetrakis- (n-undecyloxy) anthracene
1,4,9,10-tetrakis- (n-dodecylamine)
Xy) anthracene, 1,4,9,10-tetrakis-
(N-tridecyloxy) anthracene, 1,4,9,
10-tetrakis- (n-tetradecyloxy) ant
Helix, 1,4,9,10-tetrakis- (n-pentane
(Decyloxy) anthracene, 1,4,9,10-tet
Lakis- (n-hexadecyloxy) anthracene,
1,4,9,10-tetrakis- (n-heptadecylthio)
Xy) anthracene, 1,4,9,10-tetrakis-
(N-octadecyloxy) anthracene, 1,4,
9,10-tetrakis- (cyclohexyloxy) anne
Toracene, 1,4,9,10-tetrakis- (2-fe
Noxyethoxy) anthracene, 1,4,9,10-te
Thrakis- (benzyloxy) anthracene, 1,5
9,10-tetraphenoxyanthracene, 1,5
9,10-tetramethoxyanthracene, 1,5,9,
10-tetraethoxyanthracene, 1,5,9,10
-Tetra-n-propoxyanthracene, 1,5,9,
10-tetra-isopropoxyanthracene, 1,5
9,10-tetra-n-butoxyanthracene, 1,
5,9,10-tetra-isobutoxyanthracene,
1,5,9,10-tetra-s-butoxyanthrace
, 1,5,9,10-tetra-t-butoxyanthra
Sen, 1,5,9,10-tetrakis- (n-pentyl
Oxy) anthracene, 1,5,9,10-tetrakis
-(Isopentyloxy) anthracene, 1,5,9,
10-tetrakis- (1-methylbutyloxy) ant
Helix, 1,5,9,10-tetrakis- (t-pliers
Ruoxy) anthracene, 1,5,9,10-tetraki
S- (n-hexyloxy) anthracene, 1,5
9,10-tetrakis- (isohexyloxy) ant
Helix, 1,5,9,10-tetrakis- (n-hepti
Ruoxy) anthracene, 1,5,9,10-tetraki
S- (n-octyloxy) anthracene, 1,5
9,10-tetrakis- (1-methylheptyloxy)
Anthracene, 1,5,9,10-tetrakis- (2-
Ethylhexyloxy) anthracene, 1,5,9,1
0-tetrakis- (n-nonyloxy) anthracene,
1,5,9,10-tetrakis- (n-decyloxy)
Anthracene, 1,5,9,10-tetrakis- (n-
Undecyloxy) anthracene, 1,5,9,10-
Tetrakis- (n-dodecyloxy) anthracene,
1,5,9,10-tetrakis- (n-tridecyloxy
C) anthracene, 1,5,9,10-tetrakis-
(N-tetradecyloxy) anthracene, 1,5
9,10-tetrakis- (n-pentadecyloxy) a
Anthracene, 1,5,9,10-tetrakis- (n-f
Xadecyloxy) anthracene, 1,5,9,10-
Tetrakis- (n-heptadecyloxy) anthrace
1,5,9,10-tetrakis- (n-octadecyl
Ruoxy) anthracene, 1,5,9,10-tetraki
S- (cyclohexyloxy) anthracene, 1,5
9,10-tetrakis- (2-phenoxyethoxy) a
Anthracene, 1,5,9,10-tetrakis- (benzy
Loxy) anthracene, 1,8,9,10-tetraf
Enoxyanthracene, 1,8,9,10-tetramethate
Xianthracene, 1,8,9,10-tetraethoxy
Anthracene, 1,8,9,10-tetra-n-propo
Xianthracene, 1,8,9,10-tetra-isop
Lopoxyanthracene, 1,8,9,10-tetra-n
-Butoxyanthracene, 1,8,9,10-tetra-
Isobutoxyanthracene, 1,8,9,10-tetra
-S-butoxyanthracene, 1,8,9,10-tet
Tert-butoxyanthracene, 1,8,9,10-te
Thrakis- (n-pentyloxy) anthracene, 1,
8,9,10-tetrakis- (isopentyloxy) a
Anthracene, 1,8,9,10-tetrakis- (1-meth
Butylbutyloxy) anthracene, 1,8,9,10-
Tetrakis- (t-pentyloxy) anthracene,
1,8,9,10-tetrakis- (n-hexyloxy
C) anthracene, 1,8,9,10-tetrakis-
(Isohexyloxy) anthracene, 1,8,9,1
0-tetrakis- (n-heptyloxy) anthrace
1,8,9,10-tetrakis- (n-octylthio)
Xy) anthracene, 1,8,9,10-tetrakis-
(1-methylheptyloxy) anthracene, 1,8,
9,10-tetrakis- (2-ethylhexyloxy)
Anthracene, 1,8,9,10-tetrakis- (n-
Nonyloxy) anthracene, 1,8,9,10-tet
Lakis- (n-decyloxy) anthracene, 1,8,
9,10-tetrakis- (n-undecyloxy) an
Toracene, 1,8,9,10-tetrakis- (n-dode
Siloxy) anthracene, 1,8,9,10-tetra
Kiss- (n-tridecyloxy) anthracene, 1,
8,9,10-tetrakis- (n-tetradecyloxy
C) anthracene, 1,8,9,10-tetrakis-
(N-pentadecyloxy) anthracene, 1,8,
9,10-tetrakis- (n-hexadecyloxy) a
Anthracene, 1,8,9,10-tetrakis- (n-f
(Ptadecyloxy) anthracene, 1,8,9,10-
Tetrakis- (n-octadecyloxy) anthrace
1,8,9,10-tetrakis- (cyclohexyl)
Oxy) anthracene, 1,8,9,10-tetrakis
-(2-phenoxyethoxy) anthracene, 1,8,
9,10-tetrakis- (benzyloxy) anthrace
2,6,9,10-tetraphenoxyanthracene
2,6,9,10-tetramethoxyanthracene,
2,6,9,10-tetraethoxyanthracene, 2,
6,9,10-tetra-n-propoxyanthracene,
2,6,9,10-tetra-isopropoxyanthracese
2,6,9,10-tetra-n-butoxyanthra
Sen, 2,6,9,10-tetra-isobutoxyant
Helix, 2,6,9,10-tetra-s-butoxyan
Toracene, 2,6,9,10-tetra-t-butoxya
Anthracene, 2,6,9,10-tetrakis- (n-pe
(Nthyloxy) anthracene, 2,6,9,10-tet
Lakis- (isopentyloxy) anthracene, 2,
6,9,10-tetrakis- (1-methylbutyloxy
C) anthracene, 2,6,9,10-tetrakis-
(T-pentyloxy) anthracene, 2,6,9,1
0-tetrakis- (n-hexyloxy) anthrace
2,6,9,10-tetrakis- (isohexylio
Xy) anthracene, 2,6,9,10-tetrakis-
(N-heptyloxy) anthracene, 2,6,9,1
0-tetrakis- (n-octyloxy) anthrace
2,6,9,10-tetrakis- (1-methylhepta
Tyloxy) anthracene, 2,6,9,10-tetra
Kiss- (2-ethylhexyloxy) anthracene,
2,6,9,10-tetrakis- (n-nonyloxy)
Anthracene, 2,6,9,10-tetrakis- (n-
(Decyloxy) anthracene, 2,6,9,10-tet
Lakis- (n-undecyloxy) anthracene, 2,
6,9,10-tetrakis- (n-dodecyloxy) a
Anthracene, 2,6,9,10-tetrakis- (n-to
Ridecyloxy) anthracene, 2,6,9,10-te
Trakis- (n-tetradecyloxy) anthracene,
2,6,9,10-tetrakis- (n-pentadecylthio)
Xy) anthracene, 2,6,9,10-tetrakis-
(N-hexadecyloxy) anthracene, 2,6
9,10-tetrakis- (n-heptadecyloxy) a
Anthracene, 2,6,9,10-tetrakis- (n-o
Cutadecyloxy) anthracene, 2,6,9,10-
Tetrakis- (cyclohexyloxy) anthracene,
2,6,9,10-tetrakis- (2-phenoxyeth
Xy) anthracene, 2,6,9,10-tetrakis-
(Benzyloxy) anthracene and the like.

The above-mentioned anthracene derivative and a known sensitizer can be used in combination. Known sensitizers include the Journal of Polymer Sc
issue: Polymer Chemistry E
division, Vol. Dyes such as acridine orange, acridine yellow, and benzoflavin, and coumarin derivatives described in US Pat.
Redox system in combination with photo radical generator, 4-
Methoxyphenol, 4-benzyloxyphenol,
Phenol derivatives such as 4-methoxy-2- (t-butyl) phenol, hydroquinone, 4-methoxy-1-naphthol, 2-hydroxydibenzofuran, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-
Methoxynaphthalene, 1-hydroxyphenanthrene,
Glycidyl-1-naphthyl ether, 2- (2-naphthoxy) ethyl vinyl ether, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-
Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dimethoxynaphthalene, 1,1′-thiobis (2-naphthol), 1,1′-bi-2-naphthol, 1,5-naphthyldiglycidyl ether, , 7-
Di (2-vinyloxyethyl) naphthyl ether, 4-
Condensation of methoxy-1-naphthol, ESN-175 (epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) or a series thereof, an epoxy compound obtained by reacting a naphthol derivative with epichlorohydrin, a mixture of a naphthol derivative and a phenol derivative, and formalin Compounds, epoxy compounds obtained by reacting them with epichlorohydrin, condensates of naphthol derivatives with formalin, 1,4-dimethoxychrysene,
1,4-diethoxychrysene, 1,4-dipropoxychrysene, 1,4-dibenzyloxychrysene, 1,4-
Chrysene derivatives such as di-α-methylbenzyloxychrysene, 9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-ethoxyphenanthrene, 9-benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene, 9,10-diethoxyphenanthrene,
9,10-dipropoxyphenanthrene, 9,10-dibenzyloxyphenanthrene, 9,10-di-α-methylbenzyloxyphenanthrene, 9-hydroxy-
10-methoxyphenanthrene, 9-hydroxy-10
Phenanthrene derivatives such as ethoxyphenanthrene,
Examples thereof include (thio) xanthone derivatives such as xanthone, thioxanthone and 2,4-diethylthioxanthone, and carbazole derivatives such as carbazole, N-vinylcarbazole and N-ethylcarbazole. In addition, thioxanthones, which are generally known as sensitizers of iodonium salt compounds, and various dye derivatives can be used in combination.

In the present invention, the mixing ratio of the iodonium salt compound represented by the formula (II) or (IV) and the cation polymerizable compound is based on 100 parts of the cation polymerizable compound (parts by weight, hereinafter the same). , Iodonium salt compound 0.0
The content is preferably 1 to 20 parts, more preferably 0.1 to 10 parts. If the amount of the iodonium salt compound is small, the curability of the cationically polymerizable compound is reduced, and if it is excessive, the properties of the cured product are reduced.

On the other hand, the mixing ratio of the anthracene derivative represented by the formula (I) and the cationically polymerizable compound is preferably 0.001 to 10 parts, more preferably 0.01 to 5 parts, per 100 parts of the cationically polymerizable compound. Parts. When the amount of the anthracene derivative is small, the photoreactivity of the iodonium salt compound used as a photopolymerization initiator decreases, and when the amount is excessive, the properties of the cured product deteriorate.

When the photocurable composition of the present invention contains a pigment, it is used for inks and photoresists. As the pigment used in the present invention, carbon black, acetylene black, run black, black pigments such as aniline black, graphite, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, Yellow pigments such as naphthol yellow S, Hanza yellow G, Hanza yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake, red mouth lead, molybdenum orange,
Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Indus Ren Brilliant Orange R
Orange pigments such as K, benzidine orange G, and indus len brilliant orange GK, red bengal, cadmium red, lead red, cadmium mercury sulfide, permanent red 4
Red pigments such as R, Risor Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake Purple pigment, navy blue, cobalt blue, etc.
Alkaline blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated phthalocyanine blue, blue pigments such as fast sky blue, induslen blue BC, chrome green, chromium oxide, pigment green B, malachite green lake, Examples include green pigments such as Null Yellow Green G, white pigments such as zinc white, titanium dioxide, antimony white, and zinc sulfide, and extender pigments such as barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. be able to.

In order to control the physical properties and curability of the cured product of the photocurable composition according to the present invention, a radical polymerizable compound can be used. As the radical polymerizable compound used in the present invention, any monomers, oligomers and polymers having radical polymerizability can be used regardless of the kind thereof. As the radical polymerizable monomer, monofunctional or polyfunctional acrylate or methacrylate monomer, etc., as the radical polymerizable oligomer, epoxy acrylate, epoxy methacrylate, polyester acrylate, polyester methacrylate, polyether acrylate, polyether methacrylate, polyurethane acrylate, Polyurethane methacrylate, polybutadiene acrylate, polybutadiene methacrylate, and the like, and radical polymerizable polymers include polyester, polybutadiene, and polyether. , Urethane, each acrylates such as epoxy, the methacrylate compounds, can be exemplified unsaturated polyesters. Examples of the radical polymerizable reactive diluent include acrylate monomers such as acrylic acid and ethyl acrylate, methacrylate monomers such as methacrylic acid and methyl methacrylate, and styrene.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[0032]

Reference Example 1 Synthesis of 4-methoxycarbonylmethoxyphenyl-2 ', 4', 6'-trimethylphenyliodonium hexafluorophosphate 6.3 g of methyl phenoxyacetate, 13.8 g of iodomesitylene diacetate, 190 g of acetic acid , Acetic anhydride 17.6
g was stirred at room temperature. After dissolution of iodomesitylene diacetate, 3.7 g of sulfuric acid was added dropwise at 15 ° C., and the mixture was stirred at room temperature for 3 hours. After standing overnight, an aqueous solution in which 7.0 g of potassium hexafluorophosphate was dissolved in 50 g of pure water was added dropwise with stirring under ice cooling. The crude reaction solution was poured into 1 liter of water, and the precipitate was separated by filtration, washed with water, and dried at 40 ° C. under reduced pressure to obtain a white powder 1
9.0 g were obtained. This was identified by NMR.

[0033]

Embedded image

Reference Example 2 [Synthesis of 4- (1-ethoxycarbonylethoxy) phenyl-2 ', 4', 6'-trimethylphenyliodonium hexafluorophosphate] 2.5 g of ethyl 2-phenoxypropionate, iodomesitylene diacetate 4.0 g, 36.0 g of acetic acid, and 9.0 g of acetic anhydride were stirred at room temperature. After dissolution of iodomesitylene diacetate, 1.2 g of sulfuric acid was added dropwise at 15 ° C.
Stir at room temperature for 3 hours. After standing overnight, an aqueous solution in which 2.2 g of potassium hexafluorophosphate was dissolved in 200 g of pure water was added dropwise while cooling with ice while stirring. The reaction crude solution is mixed with 500 parts of water.
The precipitate was collected by filtration, washed with water, and dried at 40 ° C. under reduced pressure to obtain 5.7 g of a white powder. This was identified by NMR.

[0035]

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Reference Example 3 [Synthesis of 4- (1-ethoxycarbonylethoxy) phenyl-2 ', 4', 6'-trimethylphenyliodonium hexafluoroantimonate] 9.7 g of ethyl 2-phenoxypropionate, iodomesitylenediene 18.2 g of acetate, 87.3 g of acetic acid, and 7.6 g of acetic anhydride were stirred at room temperature. 3. Sulfuric acid at 15 ° C.
9 g was added dropwise, and the mixture was stirred at room temperature for 3 hours. After standing overnight, the reaction crude liquid was added dropwise with stirring to an aqueous solution in which 5.2 g of sodium bromide was dissolved in 300 ml of pure water. The precipitated light brown crystals were separated by filtration and washed with pure water. The crystals were suspended in 200 g of ethyl acetate and 100 g of pure water, and 14.0 g of potassium hexafluoroantimonate was added, followed by sufficient stirring.
After washing the ethyl acetate layer with water, it was dehydrated with anhydrous magnesium sulfate and concentrated to dryness to obtain 28.9 g of a white powder. This was identified by NMR.

[0037]

Embedded image

Example 1 (Solubility in Cationic Polymerizable Compound) A prescribed amount of a sensitizer shown in Table 1 was added to 100 parts by weight of the resin shown in Table 1, and the mixture was heated to 50 ° C. and stirred appropriately. did.
In Table 1, the sensitizer was completely dissolved after the heat treatment for 4 hours, and there was no insoluble matter even after standing at room temperature.

Comparative Example 1 One part by weight of 9,10-dimethoxyanthracene was added to 100 parts by weight of the resin shown in Table 1, and the same evaluation as in Example 1 was carried out. The results are summarized in Table 1. Shown.

[0040]

[Table 1] UVR-6110: alicyclic epoxy, Union Carbide Adeka Optomer KRM-2410: Epibis epoxy, Asahi Denka Kogyo Co., Ltd. DVE-3: vinyl ether, GAF Chemicals EXOA: Oxetane, Toagosei Co., Ltd. Production a: The value in parentheses represents the number of grams dissolved in 100 g of the resin. b: The value in parentheses indicates the amount of sensitizer added.

Example 2 (Pigment-based photocuring test) To 100 parts by weight of UVR-6110 was added titanium oxide 100
3 parts by weight of the iodonium salt described in Reference Example 1 as a polymerization initiator and 1 part by weight of each sensitizer were mixed and kneaded with a three-roll mill. This composition is applied to a tin plate with a thickness of 5
It was applied to a thickness of μm and irradiated with light from a 160 W gallium-containing metal halide lamp on a belt conveyor, and the maximum speed (m / min) at which the inside was completely cured was measured. Table 2 summarizes the results.

Comparative Examples 2 and 3 UVI-6990 (manufactured by UCC) as a polymerization initiator
(Comparative Example 2) The same operation as in Example 2 was performed except that 4,4′-di-ter-butyl-diphenyliodonium = hexafluorophosphate (Comparative Example 3) was used. Table 2 summarizes the results.

[0043]

[Table 2]

Example 3 Titanium oxide 100 was added to 100 parts by weight of UVR-6110.
3 parts by weight of the iodonium salt described in Reference Examples 1 and 2 as a polymerization initiator and 2 parts by weight of 9,10-dibutoxyanthracene as a sensitizer were mixed and kneaded with a three-roll mill. This composition was applied to a tin plate at a thickness of 5 μm, irradiated with light from a 160 W gallium-containing metal halide lamp using a belt conveyor, and the maximum speed (m / min) at which the inside was completely cured was measured. The results are summarized in Table 3.

Comparative Example 4 Titanium oxide 100 was added to 100 parts by weight of UVR-6110.
3 parts by weight of UVI-6990 (manufactured by UCC) as a polymerization initiator and 2 parts by weight of 9,10-dibutoxyanthracene as a sensitizer were mixed and kneaded with a three-roll mill. A sample was prepared in the same manner and evaluated similarly.

Comparative Example 5 9,10-Dimethoxyanthracene was used as a sensitizer.
The same operation as in Example 3 was performed except that 4 parts by weight was used. The results are summarized in Table 3.

[0047]

[Table 3]

Example 4 (Thick film curability test) 2 parts by weight of the iodonium salt described in Reference Examples 1, 2 and 3 as a polymerization initiator and 100 parts by weight of UVR-6110 and 9,10-dibutoxyanthracene One part by weight was mixed. 1 g of this compound was placed in a polypropylene cup (20 mm in diameter), and a 250 W ultra-high pressure mercury lamp (illuminance 10
mW / cm ² ) for a predetermined time. The cured resin was taken out of the cup, unreacted resin was removed with acetonitrile, air-dried, and the thickness of the cured resin was measured. The results are summarized in Table 4.

Comparative Example 6 The procedure of Example 4 was repeated except that UVI-6990 (manufactured by UCC) was used as a polymerization initiator. Table 4 summarizes the results.

[0050]

[Table 4]

Example 5 (MEK rubbing test) 100 parts by weight of UVR-6110 were mixed with 100 parts of titanium oxide.
Parts by weight, 2 parts by weight of the iodonium salt described in Reference Example 2 as a polymerization initiator, and 9,10-dibutoxyanthracene as a sensitizer were mixed with each other and kneaded with a three-roll mill. 5 μm thick tin plate
And irradiated with light using a belt conveyor type 160 W gallium-containing metal halide lamp to obtain a cured coating film (belt conveyor speed: 20 m / min). After standing at room temperature for 24 hours, the surface of the cured coating was rubbed with a cotton swab impregnated with methyl ethyl ketone, and the number of times until the coating was removed was measured. Table 5 shows the results.

Comparative Example 7 The same procedure as in Example was carried out except that UVI-6990 (manufactured by UCC) was used as a polymerization initiator. Table 5 summarizes the results.

[0053]

[Table 5]

[0054]

As described above, a wide range of cationically polymerizable compounds can be used by combining the sensitizer of the present invention with an iodonium salt. Also,
It shows excellent photoactivity regardless of whether it is a clear or pigment-based compound, and can cure a cationically polymerizable compound in a short time by irradiation with active energy rays such as light, electron beam, and X-ray, greatly improving workability. Can be improved.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Akihiro Shirai 12-54 Goi-minamikaigan, Ichihara-shi, Chiba F-term in Functional Products Research Laboratory, Nippon Soda Co., Ltd. 4J011 SA75 SA87 4J031 CA83

Claims (5)

[Claims] (1) Formula (I) (Wherein, R ₁ and R ₂ each independently represent a C1 to C20 alkyl group which may have a substituent, and R ₃ and R ₄ each independently represent a halogen atom or a substituent. Represents a C1 to C20 alkyl group which may have, a C1 to C20 alkoxy group which may have a substituent, and n and m each independently represent an integer of 0 or 1 to 4 , N and m are 2 or more, R ₃ or R ₄ may be the same or different, provided that when n and m are 0, R ₁ and R ₂ are each independently a substituent Represents a C4-C20 alkyl group which may have
An anthracene derivative represented by the formula (2), a cationically polymerizable compound, (3) a formula (II) (R ₅ represents a C1 to C6 linear or branched alkyl group, R ₆ represents a C1 to C6 linear or branched alkyl group, p represents an integer of 1 to 4, and p is 2 or more. Time R
₆ may be the same or different, and R ₇ has 1 carbon atom.
Represents a straight-chain or branched alkyl group of from 6 to 6;
And when q is 2 or more, R ₇ may be the same or different, and Y is a group represented by the formula (III). (Wherein R ₉ and R ₁₀ are each independently a hydrogen atom,
Represents a straight-chain or branched alkyl group of C6, a phenyl group or an aralkyl group, s represents an integer of 1 or 2,
When s is 2, R ₉ and R ₁₀ may be the same or different, and R ₈ and R ₁₁ are each independently a hydrogen atom,
It represents a C1-C12 linear or branched alkyl group which may have a substituent, a phenyl group which may have a substituent, and an aralkyl group which may have a substituent. And r is an integer of 1 to 5, and when r is 2 or more, Y may be the same or different, and X is non-nucleophilic. Represents an anion residue. A photocurable composition containing a diaryliodonium salt represented by the formula: 2. The diaryliodonium salt represented by the formula (II) is a compound represented by the formula (IV): (R ₁₂ , R ₁₃ , and R ₁₄ each independently represent a C1 to C6 linear or branched alkyl group; R ₇ represents a linear or branched alkyl group having 1 to 6 carbon atoms; When q is 2 or more, R ₇ may be the same or different, and Y is a group represented by the formula (III): (Wherein, R ₉ and R ₁₀ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group or an aralkyl group, s represents an integer of 1 or 2, When s is 2, R ₉ and R ₁₀ may be the same or different from each other, and R ₈ and R ₁₁ are each independently a hydrogen atom or a C1 to C12 linear group which may have a substituent. Or a branched alkyl group, a phenyl group which may have a substituent or an aralkyl group which may have a substituent.) Wherein r is 1 to 5 And when r is 2 or more, Y may be the same or different, and X represents a non-nucleophilic anionic residue. The photocurable resin composition according to claim 1, which is a compound represented by the formula: 3. The method according to claim 1, wherein the non-nucleophilic anionic residue is SbF ₆ or As.
F _6, PF _6, BF ₄ or (F ₅ C _{6) 4} photocurable composition according to any one of claims 1-2, characterized in that either B. 4. The photocurable composition according to claim 1, wherein the photocurable composition further contains a pigment. 5. The photocurable composition according to claim 1, wherein the photocurable composition further contains a radical polymerizable compound.