JP7145362B2 - Radically photopolymerizable composition containing anthracene-based radical photopolymerization sensitizer and naphthalene-based radical photopolymerization sensitizer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a radically polymerizable composition, and more particularly to a radically photopolymerizable composition containing a radical photopolymerization initiator, an anthracene-based radical photopolymerization sensitizer, and a naphthalene-based radical photopolymerization sensitizer.

Various types of radical polymerization using photoradical polymerization initiators have been conventionally known. Those photo-radical polymerization initiators are usually designed to be most sensitive to the frequently used high-pressure mercury lamps, that is, to have UV absorption around 365 nm. However, in recent years, with the shift to LED light sources, UV-LED light sources having a peak wavelength in a long wavelength range such as 405 nm have been used. A radical photopolymerization initiator composition in combination with a polymerization sensitizer is desired.

Acylphosphine oxides, for example, are known as photoradical polymerization initiators for such long wavelengths (irgacure 819 manufactured by Ciba Spaciality Co., Ltd.) (see Patent Document 1). However, although these acylphosphine oxides are highly active as photoradical polymerization initiators, they contain an organic phosphorous compound and are therefore not environmentally preferred. In addition, when used in a photoradical polymerizable composition for resist, the linearity of the pattern contour is not sufficient, there is a problem with resolution, and the photoradical polymerization initiation is highly sensitive to light in a long wavelength region such as 405 nm. There is a need for agents and compositions thereof.

On the other hand, onium salts are used as photocationic polymerization initiators, and are used to cure cationic polymerizable compounds such as epoxy compounds. is already known (see Patent Document 2).

Furthermore, Patent Documents 3 and 4 disclose a composition useful as a photocationic polymerization sensitizer for a photocationically polymerizable composition, a photosensitive acid generator containing the photocationic polymerization sensitizer, and a photocurable composition. Compositions are disclosed in which cationic photopolymerization sensitizers containing a dialkoxyanthracene compound and a dialkoxynaphthalene compound are disclosed. However, the patent is only for a cationic photopolymerizable composition, and discloses a cationic photopolymerization initiator and a cationic photopolymerization sensitizer for a cationic polymerizable monomer.

Further, in Patent Document 5, (A) a cationically polymerizable compound, (B) a photocationic polymerization initiator, (C) a photosensitizer exhibiting maximum absorption at a wavelength longer than 380 nm, and (D) the following formula A photocurable adhesive comprising the naphthalene-based photosensitizing aid (I) is disclosed. However, this photocurable adhesive is a patent for a cationic photopolymerizable composition, and discloses a cationic photopolymerization initiator and a cationic photopolymerization sensitizer for a cationic polymerizable compound.

Furthermore, Patent Document 6 discloses an ultraviolet curable liquid developer containing a cationic polymerizable liquid monomer, a photopolymerization initiator, and toner particles, wherein the photopolymerization sensitizer is a thioxanthone-based compound or an anthracene-based compound. and the photopolymerization sensitizing aid contains a naphthalene compound. However, this ultraviolet curable liquid developer is also a patent for a cationic photopolymerizable composition, and discloses a cationic photopolymerization initiator and a cationic photopolymerization sensitizer for a cationic polymerizable compound.

Further, Patent Document 7 discloses a photocurable ink composition for inkjet printing, in which a cationic polymerization initiator that exhibits an initiator function by an active energy ray and a sensitizing function that exhibits a sensitizing function by light with a wavelength of 400 nm or more. A photocurable ink composition for inkjet printing is disclosed, which is characterized by containing a sensitizer and a sensitizing aid that exhibits a sensitizing function by light with a wavelength of less than 400 nm. However, this photocurable ink composition for inkjet printing is also a patent for a photocationically polymerizable composition, and discloses a photocationic polymerization initiator and a photocationic polymerization sensitizer for a cationic polymerizable compound.

As described above, sensitizer compositions using both an anthracene-based compound and a naphthalene-based compound have been conventionally known. It is used as a photocationic polymerization sensitizer for a photocationic polymerization initiator. That is, it is used as a sensitizer for decomposing a photocationic polymerization initiator to generate an acid. It is not described that the combination exhibits new effects, nor is there any suggestion that the combination can be applied to radically polymerizable compositions.

Generally, cationic polymerization and radical polymerization have completely different reaction mechanisms, so it cannot be said that a photopolymerization sensitizer that is effective in cationic polymerization is also effective in radical polymerization. In addition, Patent Document 8 discloses dialkoxynaphthalene compounds and dialkoxyanthracene compounds, which are compounds of the present invention, as polymerization inhibitors having a condensed polycyclic aromatic skeleton. That is, the compounds of the present invention have been shown to be excellent polymerization inhibitors against radical polymerization. The examples show that it inhibits polymerization significantly.

Furthermore, when a dialkoxyanthracene is used as a photopolymerization sensitizer, the cured product is colored, but none of the patent documents mentions this problem, nor describes or suggests a method for reducing the coloration. .

Furthermore, it is known that radical polymerization always leaves some unreacted residual components (residual monomers) due to the nature of the polymerization method. It is desired to be reduced as much as possible. Therefore, in order to increase the reaction activity, countermeasures such as increasing the amount of the radical polymerization initiator have been devised (Patent Document 9). There is a need for a method of increasing the activity of initiating polymerization.

JP-A-10-02997 Japanese Patent No. 03437069 International publication 2007/126066 pamphlet JP 2011-246606 A JP 2011-28234 A JP 2016-224406 A International publication 2007/074768 pamphlet JP 2012-111741 A JP 2008-266556 A

Therefore, the present invention contains acylphosphine oxides, which are photoradical polymerization initiators conventionally used in photoradical polymerizable compositions capable of being polymerized by light having a peak wavelength in a long wavelength region such as 405 nm. To provide a new photoradical polymerizable composition which is highly active and environmentally friendly in place of a photoradical polymerizable composition, and which can reduce coloring of cured products.

The inventors have made intensive studies on the action and effect of an anthracene compound and a naphthalene compound in a photopolymerization reaction. In the radically polymerizable composition, the anthracene compound and the naphthalene compound not only do not inhibit radical polymerization, but rather cooperate to promote radical photopolymerization by irradiation with a specific wavelength. acting on a photoradical polymerization initiator as a radical polymerization initiator to significantly increase the radical polymerization rate, and that the cured product obtained by the photoradical polymerization can reduce coloring derived from an anthracene compound, thereby completing the present invention. reached.

That is, the first aspect of the present invention is a photoradical polymerizable composition that undergoes photoradical polymerization by light having a peak wavelength in the wavelength range of 380 nm to 420 nm, wherein at least a radical polymerizable compound, a photoradical polymerization initiator, and light A photoradical characterized by containing an anthracene compound represented by the general formula (1) as a radical polymerization sensitizer and a naphthalene compound represented by the general formula (2) as a photoradical polymerization sensitizer. It resides in the polymerizable composition.

In the above general formula (1), R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 20 carbon atoms, and 6 carbon atoms. represents an arylcarbonyl group having an aryl group of from 20 to 20, an alkyloxycarbonyl group having an alkyl group having 1 to 20 carbon atoms or an aryloxycarbonyl group having an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² are the same may be different. Moreover, X ¹ and Y ¹ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X ¹ and Y ¹ may be the same or different.

In the above general formula (2), R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 20 carbon atoms, represents an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 20 carbon atoms ^, or an aryloxycarbonyl group having an aryl group having 6 to 20 carbon atoms; ⁴ may be the same or different. Moreover, X ² and Y ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X ² and Y ² may be the same or different.

A second invention is the photoradically polymerizable composition according to the first invention, wherein the radically polymerizable compound is (meth)acrylic acid, (meth)acrylate, fumarate, styrene, or an oligomer thereof. resides in

A third invention resides in the radical photopolymerizable composition according to the first invention or the second invention, wherein the radical photopolymerization initiator is an onium salt-based radical photopolymerization initiator.

A fourth invention is characterized in that the light having a peak wavelength within the wavelength range of 380 nm to 420 nm is light having a peak wavelength at any one of 385 nm, 395 nm, 405 nm, and 415 nm. It resides in the photoradical polymerizable composition according to any one of the third inventions.

A fifth invention according to any one of the first to third inventions, wherein the light having a peak wavelength within a wavelength range of 380 nm to 420 nm is light having a peak wavelength at 405 nm. It resides in the photoradical polymerizable composition described.

A sixth invention is characterized in that the addition amount of the anthracene compound represented by the general formula (1) as a radical photopolymerization sensitizer for the radically polymerizable compound is 2.0% by weight or less, It resides in the photoradical polymerizable composition according to any one of inventions 1 to 5.

The photoradical polymerizable composition of the present invention can be highly actively polymerized by light having a peak wavelength in a long wavelength region such as 405 nm, and can reduce coloration of the cured product. Furthermore, since a highly active photoradical polymerizable composition can be obtained without increasing the amount of the photoradical polymerization initiator, it is possible to reduce residual monomers.

(Anthracene radical polymerization sensitizer)
The anthracene-based radical polymerization sensitizer in the present invention is a compound represented by the following general formula (1).

In the above general formula (1), R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 20 carbon atoms, and 6 carbon atoms. represents an arylcarbonyl group having an aryl group of from 20 to 20, an alkyloxycarbonyl group having an alkyl group having 1 to 20 carbon atoms or an aryloxycarbonyl group having an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² are the same may be different. Moreover, X ¹ and Y ¹ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X ¹ and Y ¹ may be the same or different.

In general formula (1), the alkyl groups having 1 to 20 carbon atoms represented by R ¹ and R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group, n-amyl group, i-amyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl linear groups such as groups, n-tridecyl groups, n-tetradecyl groups, n-pentadecyl groups, n-hexadecyl groups, n-heptadecyl groups, n-octadecyl groups, n-nonadecyl groups, n-icosyl groups and cyclohexyl groups, Branched or cyclic alkyl groups may be mentioned. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, naphthyl group, anthranyl group, etc. which may have a substituent.

In general formula (1), the alkylcarbonyl group having an alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² includes an acetyl group, a propionyl group, an n-butanoyl group, an iso-butanoyl group, an n- pentanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, 2-ethylhexanoyl group, n-nonanoyl group, n-decanoyl group, n-dodecanoyl group and the like. Moreover, benzoyl group, naphthoyl group, etc. are mentioned as an arylcarbonyl group which has a C6-C20 aryl group.

In general formula (1), the alkyloxycarbonyl group having an alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² includes a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group and isopropoxycarbonyl. group, n-butoxycarbonyl group, i-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, 2,2-dimethylpropoxycarbonyl group, cyclopentyloxycarbonyl group, n-hexyl oxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, 2-methylpentyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group group, n-undecyloxycarbonyl group, n-dodecyloxycarbonyl group, n-tridecyloxycarbonyl group, n-tetradecyloxycarbonyl group, n-pentadecyloxycarbonyl group, n-hexadecyloxycarbonyl group, n - linear, branched or cyclic alkyloxycarbonyl such as heptadecyloxycarbonyl group, n-octadecyloxycarbonyl group, n-nonadecyloxycarbonyl group, n-icosyloxycarbonyl group and cyclohexyloxycarbonyl group groups can be mentioned. Examples of the aryloxycarbonyl group having an aryl group having 6 to 20 carbon atoms include a phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 3-phenanthryloxycarbonyl group and 2-anthryl An oxycarbonyl group and the like can be mentioned.

In general formula (1), the alkyl group having 1 to 8 carbon atoms represented by X ¹ and Y ¹ includes methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- butyl group, n-amyl group, i-amyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like.

Among the anthracene compounds of the present invention represented by the general formula (1), those in which R ¹ and R ² are alkyl groups or aryl groups are referred to as 9,10-dialkoxyanthracene compounds. Examples include:

First, when both X ¹ and Y ¹ are hydrogen atoms, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9 ,10-diamyloxyanthracene, 9,10-dihexyloxyanthracene, 9,10-diheptyloxyanthracene, 9,10-dioctyloxyanthracene, 9,10-bis(2-ethylhexyl)oxyanthracene, 9,10- Didecyloxyanthracene, 9,10-didodecyloxyanthracene, 9,10-diphenyloxyanthracene, 9,10-dinaphthyloxyanthracene and the like.

Next, when X ¹ is an alkyl group and Y ¹ is a hydrogen atom, examples include 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-methyl -9,10-dipropoxyanthracene, 2-methyl-9,10-dibutoxyanthracene, 2-methyl-9,10-diamyloxyanthracene, 2-methyl-9,10-dihexyloxyanthracene, 2-methyl- 9,10-diheptyloxyanthracene, 2-methyl-9,10-dioctyloxyanthracene, 2-methyl-9,10-bis(2-ethylhexyl)oxyanthracene, 2-methyl-9,10-didecyloxyanthracene , 2-methyl-9,10-didodecyloxyanthracene and the like.

Other examples of 9,10-dioxyanthracene compounds include 2-chloro-9,10-dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-dipropoxyanthracene, 2-chloro-9,10-dibutoxyanthracene, 2-chloro-9,10-diamyloxyanthracene, 2-chloro-9,10-dihexyloxyanthracene, 2-chloro-9,10-diheptyloxyanthracene, 2-chloro-9,10-dioctyloxyanthracene, 2-chloro-9,10-bis(2-ethylhexyl)oxyanthracene, 2-chloro-9,10-didecyloxyanthracene, 2-chloro-9,10- and didodecyloxyanthracene.

Still other examples of 9,10-dioxyanthracene compounds include 2-phenoxy-9,10-dimethoxyanthracene, 2-phenoxy-9,10-diethoxyanthracene, and 2-phenoxy-9,10-dipropoxyanthracene. , 2-phenoxy-9,10-dibutoxyanthracene, 2-phenoxy-9,10-diamyloxyanthracene, 2-phenoxy-9,10-dihexyloxyanthracene, 2-phenoxy-9,10-diheptyloxyanthracene , 2-phenoxy-9,10-dioctyloxyanthracene, 2-phenoxy-9,10-bis(2-ethylhexyl)oxyanthracene, 2-phenoxy-9,10-didecyloxyanthracene, 2-phenoxy-9,10 -didodecyloxyanthracene and the like.

Among the anthracene compounds of the present invention represented by the general formula (1), those in which R ¹ and R ² are an alkylcarbonyl group or an arylcarbonyl group are referred to as 9,10-bis(substituted acyloxy)anthracene compounds. Examples include the following compounds.

First, when both X ¹ and Y ¹ are hydrogen atoms, 9,10-diacetyloxyanthracene, 9,10-dipropionyloxyanthracene, 9,10-bis(n-butanoyloxy)anthracene, 9 , 10-bis(iso-butanoyloxy)anthracene, 9,10-bis(n-pentanoyloxy)anthracene, 9,10-bis(n-hexanoyloxy)anthracene, 9,10-bis(n-hepta noyloxy)anthracene, 9,10-bis(n-octanoyloxy)anthracene, 9,10-bis(2-ethylhexanoyloxy)anthracene, 9,10-bis(n-nonanoyloxy)anthracene, 9,10- bis(n-decanoyloxy)anthracene, 9,10-bis(n-dodecanoyloxy)anthracene and the like.

Next, when X ¹ is an alkyl group and Y ¹ is a hydrogen atom, examples include 1-methyl-9,10-diacetyloxyanthracene, 1-methyl-9,10-dipropionyloxyanthracene, 1 -methyl-9,10-bis(n-butanoyloxy)anthracene, 1-methyl-9,10-bis(iso-butanoyloxy)anthracene, 1-methyl-9,10-bis(n-hexanoyloxy) ) anthracene, 1-methyl-9,10-bis(n-heptanoyloxy)anthracene, 1-methyl-9,10-bis(n-octanoyloxy)anthracene, 1-methyl-9,10-bis(2 -ethylhexanoyloxy)anthracene, 1-methyl-9,10-bis(n-nonanoyloxy)anthracene, 1-methyl-9,10-bis(n-decanoyloxy)anthracene, 1-methyl-9,10- Bis(n-dodecanoyloxy)anthracene, 2-methyl-9,10-diacetyloxyanthracene, 2-methyl-9,10-dipropionyloxyanthracene, 2-methyl-9,10-bis(n-butanoyloxy) ) anthracene, 2-methyl-9,10-bis(iso-butanoyloxy)anthracene, 2-methyl-9,10-bis(n-hexanoyloxy)anthracene, 2-methyl-9,10-bis(n -heptanoyloxy)anthracene, 2-methyl-9,10-bis(n-octanoyloxy)anthracene, 2-methyl-9,10-bis(2-ethylhexanoyloxy)anthracene, 2-methyl-9, 10-bis(n-nonanoyloxy)anthracene, 2-methyl-9,10-bis(n-decanoyloxy)anthracene, 2-methyl-9,10-bis(n-dodecanoyloxy)anthracene, 1-ethyl- 9,10-diacetyloxyanthracene, 1-ethyl-9,10-dipropionyloxyanthracene, 1-ethyl-9,10-bis(n-butanoyloxy)anthracene, 1-ethyl-9,10-bis(iso -butanoyloxy)anthracene, 1-ethyl-9,10-bis(n-hexanoyloxy)anthracene, 1-ethyl-9,10-bis(n-heptanoyloxy)anthracene, 1-ethyl-9,10 -bis(n-octanoyloxy)anthracene, 1-ethyl-9,10-bis(2-ethylhexanoyloxy)anthracene, 1-ethyl -9,10-bis(n-nonanoyloxy)anthracene, 1-ethyl-9,10-bis(n-decanoyloxy)anthracene, 1-ethyl-9,10-bis(n-dodecanoyloxy)anthracene, 2 -ethyl-9,10-diacetyloxyanthracene, 2-ethyl-9,10-dipropionyloxyanthracene, 2-ethyl-9,10-bis(n-butanoyloxy)anthracene, 2-ethyl-9,10- bis(iso-butanoyloxy)anthracene, 2-ethyl-9,10-bis(n-hexanoyloxy)anthracene, 2-ethyl-9,10-bis(n-heptanoyloxy)anthracene, 2-ethyl- 9,10-bis(n-octanoyloxy)anthracene, 2-ethyl-9,10-bis(2-ethylhexanoyloxy)anthracene, 2-ethyl-9,10-bis(n-nonanoyloxy)anthracene, 2 -ethyl-9,10-bis(n-decanoyloxy)anthracene, 2-ethyl-9,10-bis(n-dodecanoyloxy)anthracene and the like.

Further, when both X ¹ and Y ¹ are alkyl groups, examples thereof include 2,3-dimethyl-9,10-diacetyloxyanthracene, 2,3-dimethyl-9,10-dipropionyloxyanthracene, 2, 3-dimethyl-9,10-bis(n-butanoyloxy)anthracene, 2,3-dimethyl-9,10-bis(iso-butanoyloxy)anthracene, 2,3-dimethyl-9,10-bis( n-hexanoyloxy)anthracene, 2,3-dimethyl-9,10-bis(n-heptanoyloxy)anthracene, 2,3-dimethyl-9,10-bis(n-octanoyloxy)anthracene, 2, 3-dimethyl-9,10-bis(2-ethylhexanoyloxy)anthracene, 2,3-dimethyl-9,10-bis(n-nonanoyloxy)anthracene, 2,3-dimethyl-9,10-bis(n -decanoyloxy)anthracene, 2,3-dimethyl-9,10-bis(n-dodecanoyloxy)anthracene, 2,6-dimethyl-9,10-diacetyloxyanthracene, 2,6-dimethyl-9,10 -dipropionyloxyanthracene, 2,6-dimethyl-9,10-bis(n-butanoyloxy)anthracene, 2,6-dimethyl-9,10-bis(iso-butanoyloxy)anthracene, 2,6- Dimethyl-9,10-bis(n-hexanoyloxy)anthracene, 2,6-dimethyl-9,10-bis(n-heptanoyloxy)anthracene, 2,6-dimethyl-9,10-bis(n- octanoyloxy)anthracene, 2,6-dimethyl-9,10-bis(2-ethylhexanoyloxy)anthracene, 2,6-dimethyl-9,10-bis(n-nonanoyloxy)anthracene, 2,6-dimethyl -9,10-bis(n-decanoyloxy)anthracene, 2,6-dimethyl-9,10-bis(n-dodecanoyloxy)anthracene, 2,7-dimethyl-9,10-diacetyloxyanthracene, 2 ,7-dimethyl-9,10-dipropionyloxyanthracene, 2,7-dimethyl-9,10-bis(n-butanoyloxy)anthracene, 2,7-dimethyl-9,10-bis(iso-butanoyl oxy)anthracene, 2,7-dimethyl-9,10-bis(n-hexanoyloxy)anthracene, 2,7-dimethyl-9,10-bis(n-heptanoyloxy)a anthracene, 2,7-dimethyl-9,10-bis(n-octanoyloxy)anthracene, 2,7-dimethyl-9,10-bis(2-ethylhexanoyloxy)anthracene, 2,7-dimethyl-9 , 10-bis(n-nonanoyloxy)anthracene, 2,7-dimethyl-9,10-bis(n-decanoyloxy)anthracene, 2,7-dimethyl-9,10-bis(n-dodecanoyloxy)anthracene etc.

Next, among the anthracene compounds of the present invention represented by the general formula (1), 9,10-bis(alkoxycarbonyloxy)anthracene when R ¹ and R ² are an alkyloxycarbonyl group or an aryloxycarbonyl group Examples of compounds referred to as compounds include the following compounds.

First, when X ¹ and Y ¹ are both hydrogen atoms, examples include 9,10-bis(methoxycarbonyloxy)anthracene, 9,10-bis(ethoxycarbonyloxy)anthracene, 9,10-bis (n-propoxycarbonyloxy)anthracene, 9,10-bis(i-propoxycarbonyloxy)anthracene, 9,10-bis(n-butoxycarbonyloxy)anthracene, 9,10-bis(i-butoxycarbonyloxy)anthracene , 9,10-bis(n-pentyloxycarbonyloxy)anthracene, 9,10-bis(i-pentyloxycarbonyloxy)anthracene, 9,10-bis(n-hexyloxycarbonyloxy)anthracene, 9,10- bis(n-heptyloxycarbonyloxy)anthracene, 9,10-bis(n-octyloxycarbonyloxy)anthracene, 9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene, 9,10-bis(allyloxycarbonyl) oxy)anthracene and the like.

Next, when X ¹ is an alkyl group and Y ¹ is a hydrogen atom, examples include 1-methyl-9,10-bis(methoxycarbonyloxy)anthracene, 1-methyl-9,10-bis( ethoxycarbonyloxy)anthracene, 1-methyl-9,10-bis(n-propoxycarbonyloxy)anthracene, 1-methyl-9,10-bis(i-propoxycarbonyloxy)anthracene, 1-methyl-9,10- Bis(n-butoxycarbonyloxy)anthracene, 1-methyl-9,10-bis(i-butoxycarbonyloxy)anthracene, 1-methyl-9,10-bis(n-pentyloxycarbonyloxy)anthracene, 1-methyl -9,10-bis(i-pentyloxycarbonyloxy)anthracene, 1-methyl-9,10-bis(n-hexyloxycarbonyloxy)anthracene, 1-methyl-9,10-bis(n-heptyloxycarbonyl) oxy)anthracene, 1-methyl-9,10-bis(n-octyloxycarbonyloxy)anthracene, 1-methyl-9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene, 1-methyl-9,10- Bis(allyloxycarbonyloxy)anthracene, 2-methyl-9,10-bis(methoxycarbonyloxy)anthracene, 2-methyl-9,10-bis(ethoxycarbonyloxy)anthracene, 2-methyl-9,10-bis (n-propoxycarbonyloxy)anthracene, 2-methyl-9,10-bis(i-propoxycarbonyloxy)anthracene, 2-methyl-9,10-bis(n-butoxycarbonyloxy)anthracene, 2-methyl-9 , 10-bis(i-butoxycarbonyloxy)anthracene, 2-methyl-9,10-bis(n-pentyloxycarbonyloxy)anthracene, 2-methyl-9,10-bis(i-pentyloxycarbonyloxy)anthracene , 2-methyl-9,10-bis(n-hexyloxycarbonyloxy)anthracene, 2-methyl-9,10-bis(n-heptyloxycarbonyloxy)anthracene, 2-methyl-9,10-bis(n -octyloxycarbonyloxy)anthracene, 2-methyl-9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene, 2-methyl-9,10-bis(allyloxycarbonyloxy) oxy)anthracene, 1-ethyl-9,10-bis(methoxycarbonyloxy)anthracene, 1-ethyl-9,10-bis(ethoxycarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-propoxycarbonyl oxy)anthracene, 1-ethyl-9,10-bis(i-propoxycarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-butoxycarbonyloxy)anthracene, 1-ethyl-9,10-bis( i-butoxycarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-pentyloxycarbonyloxy)anthracene, 1-ethyl-9,10-bis(i-pentyloxycarbonyloxy)anthracene, 1-ethyl- 9,10-bis(n-hexyloxycarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-heptyloxycarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-octyloxycarbonyloxy) ) anthracene, 1-ethyl-9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene, 1-ethyl-9,10-bis(allyloxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(methoxy carbonyloxy)anthracene, 2-ethyl-9,10-bis(ethoxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-propoxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(i -propoxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-butoxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(i-butoxycarbonyloxy)anthracene, 2-ethyl-9,10 -bis(n-pentyloxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(i-pentyloxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-hexyloxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-heptyloxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-octyloxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(2- ethylhexyloxycarbonyloxy)anthracene, 2-ethyl-9,10-bis(allyloxycarbonyloxy)anthracene and the like.

Examples of the case where both X ¹ and Y ¹ are alkyl groups include 2,3-dimethyl-9,10-bis(methoxycarbonyloxy)anthracene, 2,3-dimethyl-9,10-bis(ethoxy carbonyloxy)anthracene, 2,3-dimethyl-9,10-bis(n-propoxycarbonyloxy)anthracene, 2,3-dimethyl-9,10-bis(i-propoxycarbonyloxy)anthracene, 2,3-dimethyl -9,10-bis(n-butoxycarbonyloxy)anthracene, 2,3-dimethyl-9,10-bis(i-butoxycarbonyloxy)anthracene, 2,3-dimethyl-9,10-bis(n-pentyl oxycarbonyloxy)anthracene, 2,3-dimethyl-9,10-bis(i-pentyloxycarbonyloxy)anthracene, 2,3-dimethyl-9,10-bis(n-hexyloxycarbonyloxy)anthracene, 2, 3-dimethyl-9,10-bis(n-heptyloxycarbonyloxy)anthracene, 2,3-dimethyl-9,10-bis(n-octyloxycarbonyloxy)anthracene, 2,3-dimethyl-9,10- bis(2-ethylhexyloxycarbonyloxy)anthracene, 2,3-dimethyl-9,10-bis(allyloxycarbonyloxy)anthracene, 2,6-dimethyl-9,10-bis(methoxycarbonyloxy)anthracene, 2, 6-dimethyl-9,10-bis(ethoxycarbonyloxy)anthracene, 2,6-dimethyl-9,10-bis(n-propoxycarbonyloxy)anthracene, 2,6-dimethyl-9,10-bis(i- propoxycarbonyloxy)anthracene, 2,6-dimethyl-9,10-bis(n-butoxycarbonyloxy)anthracene, 2,6-dimethyl-9,10-bis(i-butoxycarbonyloxy)anthracene, 2,6- dimethyl-9,10-bis(n-pentyloxycarbonyloxy)anthracene, 2,6-dimethyl-9,10-bis(i-pentyloxycarbonyloxy)anthracene, 2,6-dimethyl-9,10-bis( n-hexyloxycarbonyloxy)anthracene, 2,6-dimethyl-9,10-bis(n-heptyloxycarbonyloxy)anthracene, 2,6-dimethyl-9,10-bis(n-octyloxycarbonyloxy)anthracene , 2,6-dimethyl-9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene, 2,6-dimethyl-9,10-bis(allyloxycarbonyloxy)anthracene, 2,7-dimethyl-9,10 -bis(methoxycarbonyloxy)anthracene, 2,7-dimethyl-9,10-bis(ethoxycarbonyloxy)anthracene, 2,7-dimethyl-9,10-bis(n-propoxycarbonyloxy)anthracene, 2,7 -dimethyl-9,10-bis(i-propoxycarbonyloxy)anthracene, 2,7-dimethyl-9,10-bis(n-butoxycarbonyloxy)anthracene, 2,7-dimethyl-9,10-bis(i -butoxycarbonyloxy)anthracene, 2,7-dimethyl-9,10-bis(n-pentyloxycarbonyloxy)anthracene, 2,7-dimethyl-9,10-bis(i-pentyloxycarbonyloxy)anthracene, 2 ,7-dimethyl-9,10-bis(n-hexyloxycarbonyloxy)anthracene, 2,7-dimethyl-9,10-bis(n-heptyloxycarbonyloxy)anthracene, 2,7-dimethyl-9,10 -bis(n-octyloxycarbonyloxy)anthracene, 2,7-dimethyl-9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene, 2,7-dimethyl-9,10-bis(allyloxycarbonyloxy) anthracene, 1,5-dimethyl-9,10-bis(methoxycarbonyloxy)anthracene, 1,5-dimethyl-9,10-bis(ethoxycarbonyloxy)anthracene, 1,5-dimethyl-9,10-bis( n-propoxycarbonyloxy)anthracene, 1,5-dimethyl-9,10-bis(i-propoxycarbonyloxy)anthracene, 1,5-dimethyl-9,10-bis(n-butoxycarbonyloxy)anthracene, 1, 5-dimethyl-9,10-bis(i-butoxycarbonyloxy)anthracene, 1,5-dimethyl-9,10-bis(n-pentyloxycarbonyloxy)anthracene, 1,5-dimethyl-9,10-bis (i-pentyloxycarbonyloxy)anthracene, 1,5-dimethyl-9,10-bis(n-hexyloxycarbonyloxy)anthracene, 1,5-dimethyl-9,10-bis(n-heptyloxycarbonyl) oxy)anthracene, 1,5-dimethyl-9,10-bis(n-octyloxycarbonyloxy)anthracene, 1,5-dimethyl-9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene, 1,5- dimethyl-9,10-bis(allyloxycarbonyloxy)anthracene and the like.

Furthermore, 2,3-diethyl-9,10-bis(methoxycarbonyloxy)anthracene, 2,3-diethyl-9,10-bis(ethoxycarbonyloxy)anthracene, 2,3-diethyl-9,10-bis (n-propoxycarbonyloxy)anthracene, 2,3-diethyl-9,10-bis(i-propoxycarbonyloxy)anthracene, 2,3-diethyl-9,10-bis(n-butoxycarbonyloxy)anthracene, 2 ,3-diethyl-9,10-bis(i-butoxycarbonyloxy)anthracene, 2,3-diethyl-9,10-bis(n-pentyloxycarbonyloxy)anthracene, 2,3-diethyl-9,10- bis(i-pentyloxycarbonyloxy)anthracene, 2,3-diethyl-9,10-bis(n-hexyloxycarbonyloxy)anthracene, 2,3-diethyl-9,10-bis(n-heptyloxycarbonyloxy) ) anthracene, 2,3-diethyl-9,10-bis(n-octyloxycarbonyloxy)anthracene, 2,3-diethyl-9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene, 2,3-diethyl -9,10-bis(allyloxycarbonyloxy)anthracene, 2,6-diethyl-9,10-bis(methoxycarbonyloxy)anthracene, 2,6-diethyl-9,10-bis(ethoxycarbonyloxy)anthracene, 2,6-diethyl-9,10-bis(n-propoxycarbonyloxy)anthracene, 2,6-diethyl-9,10-bis(i-propoxycarbonyloxy)anthracene, 2,6-diethyl-9,10- Bis(n-butoxycarbonyloxy)anthracene, 2,6-diethyl-9,10-bis(i-butoxycarbonyloxy)anthracene, 2,6-diethyl-9,10-bis(n-pentyloxycarbonyloxy)anthracene , 2,6-diethyl-9,10-bis(i-pentyloxycarbonyloxy)anthracene, 2,6-diethyl-9,10-bis(n-hexyloxycarbonyloxy)anthracene, 2,6-diethyl-9 , 10-bis(n-heptyloxycarbonyloxy)anthracene, 2,6-diethyl-9,10-bis(n-octyloxycarbonyloxy)anthracene, 2,6-diethyl-9,10-bis(2-ethylhexyl) Oh xycarbonyloxy)anthracene, 2,6-diethyl-9,10-bis(allyloxycarbonyloxy)anthracene, 2,7-diethyl-9,10-bis(methoxycarbonyloxy)anthracene, 2,7-diethyl-9 , 10-bis(ethoxycarbonyloxy)anthracene, 2,7-diethyl-9,10-bis(n-propoxycarbonyloxy)anthracene, 2,7-diethyl-9,10-bis(i-propoxycarbonyloxy)anthracene , 2,7-diethyl-9,10-bis(n-butoxycarbonyloxy)anthracene, 2,7-diethyl-9,10-bis(i-butoxycarbonyloxy)anthracene, 2,7-diethyl-9,10 -bis(n-pentyloxycarbonyloxy)anthracene, 2,7-diethyl-9,10-bis(i-pentyloxycarbonyloxy)anthracene, 2,7-diethyl-9,10-bis(n-hexyloxycarbonyl) oxy)anthracene, 2,7-diethyl-9,10-bis(n-heptyloxycarbonyloxy)anthracene, 2,7-diethyl-9,10-bis(n-octyloxycarbonyloxy)anthracene, 2,7- Diethyl-9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene, 2,7-diethyl-9,10-bis(allyloxycarbonyloxy)anthracene, 1,5-diethyl-9,10-bis(methoxycarbonyl) oxy)anthracene, 1,5-diethyl-9,10-bis(ethoxycarbonyloxy)anthracene, 1,5-diethyl-9,10-bis(n-propoxycarbonyloxy)anthracene, 1,5-diethyl-9, 10-bis(i-propoxycarbonyloxy)anthracene, 1,5-diethyl-9,10-bis(n-butoxycarbonyloxy)anthracene, 1,5-diethyl-9,10-bis(i-butoxycarbonyloxy) Anthracene, 1,5-diethyl-9,10-bis(n-pentyloxycarbonyloxy)anthracene, 1,5-diethyl-9,10-bis(i-pentyloxycarbonyloxy)anthracene, 1,5-diethyl- 9,10-bis(n-hexyloxycarbonyloxy)anthracene, 1,5-diethyl-9,10-bis(n-heptyloxycarbonyloxy)anthracene, 1,5-diethyl-9,10-bis( n-octyloxycarbonyloxy)anthracene, 1,5-diethyl-9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene, 1,5-diethyl-9,10-bis(allyloxycarbonyloxy)anthracene, etc. mentioned.

Among the specific examples of the 9,10-dialkoxyanthracene compounds, 9,10-bis(substituted acyloxy)anthracene compounds, and 9,10-bis(alkoxycarbonyloxy)anthracene compounds described above, particularly, From height, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dihexyloxyanthracene, 9,10-diheptyloxy Anthracene, 9,10-dioctyloxyanthracene, 9,10-diacetyloxyanthracene, 9,10-dipropionyloxyanthracene, 9,10-bis(n-butanoyloxy)anthracene, 9,10-bis(n-hexa noyloxy)anthracene, 9,10-bis(n-heptanoyloxy)anthracene, 9,10-bis(n-octanoyloxy)anthracene, 9,10-bis(2-ethylhexanoyloxy)anthracene, 9, 10-bis(n-nonanoyloxy)anthracene, 9,10-bis(methoxycarbonyloxy)anthracene, 9,10-bis(ethoxycarbonyloxy)anthracene, 9,10-bis(n-propoxycarbonyloxy)anthracene, 9, 10-bis(i-propoxycarbonyloxy)anthracene, 9,10-bis(n-butoxycarbonyloxy)anthracene, 9,10-bis(i-butoxycarbonyloxy)anthracene, 9,10-bis(2-ethylhexyloxy) Carbonyloxy)anthracene is preferred, and from the viewpoint of solubility in solvents and monomers, etc., 9,10-dibutoxyanthracene, 9,10-dihexyloxyanthracene, 9,10-diheptyloxyanthracene, 9,10-dioctyloxy anthracene, 9,10-bis(n-hexanoyloxy)anthracene, 9,10-bis(n-heptanoyloxy)anthracene, 9,10-bis(n-octanoyloxy)anthracene, 9,10-bis( 2-ethylhexanoyloxy)anthracene, 9,10-bis(n-nonanoyloxy)anthracene, 9,10-bis(methoxycarbonyloxy)anthracene, 9,10-bis(ethoxycarbonyloxy)anthracene, 9,10-bis (n-propoxycarbonyloxy)anthracene, 9,10-bis(i-propoxyca) ribonyloxy)anthracene, 9,10-bis(n-butoxycarbonyloxy)anthracene, 9,10-bis(i-butoxycarbonyloxy)anthracene, and 9,10-bis(2-ethylhexyloxycarbonyloxy)anthracene are more preferred. .

Among the 9,10-dioxyanthracene compounds mentioned above, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9, 10-dibutoxyanthracene, 9,10-dihexyloxyanthracene, 9,10-diheptyloxyanthracene, and 9,10-dioctyloxyanthracene are preferred, and 9,10-dibutoxyanthracene is particularly easy to synthesize. preferable.

(Naphthalene-based radical photopolymerization sensitizer)
The radical photopolymerization sensitizing aid is an additive that has a function of improving the efficiency of transferring the electron energy received from ultraviolet light by the photoradical polymerization sensitizer to the initiator. The naphthalene-based radical photopolymerization sensitizer in the present invention is a compound represented by the general formula (2).

In general formula (2), R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 20 carbon atoms, a carbon represents an arylcarbonyl group having 6 to 20 aryl groups, an alkyloxycarbonyl group having an alkyl group having 1 to 20 carbon atoms ^, or an aryloxycarbonyl group having an aryl group having ⁶ to 20 carbon atoms; may be the same or different. Moreover, X ² and Y ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X ² and Y ² may be the same or different.

In general formula (2), the alkyl groups having 1 to 20 carbon atoms represented by R ³ and R ⁴ are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group, n-amyl group, i-amyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl linear groups such as groups, n-tridecyl groups, n-tetradecyl groups, n-pentadecyl groups, n-hexadecyl groups, n-heptadecyl groups, n-octadecyl groups, n-nonadecyl groups, n-icosyl groups and cyclohexyl groups, Branched or cyclic alkyl groups may be mentioned. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, naphthyl group, anthranyl group, etc. which may have a substituent.

In general formula (2), the alkylcarbonyl group having an alkyl group having 1 to 20 carbon atoms represented by R ³ and R ⁴ includes an acetyl group, a propionyl group, an n-butanoyl group, an iso-butanoyl group, an n- pentanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, 2-ethylhexanoyl group, n-nonanoyl group, n-decanoyl group, n-dodecanoyl group and the like. Moreover, benzoyl group, naphthoyl group, etc. are mentioned as an arylcarbonyl group which has a C6-C20 aryl group.

In general formula (1), the alkyloxycarbonyl group having an alkyl group having 1 to 20 carbon atoms represented by R ³ and R ⁴ includes a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group and isopropoxycarbonyl. group, n-butoxycarbonyl group, i-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, 2,2-dimethylpropoxycarbonyl group, cyclopentyloxycarbonyl group, n-hexyl oxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, 2-methylpentyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group group, n-undecyloxycarbonyl group, n-dodecyloxycarbonyl group, n-tridecyloxycarbonyl group, n-tetradecyloxycarbonyl group, n-pentadecyloxycarbonyl group, n-hexadecyloxycarbonyl group, n - linear, branched or cyclic alkyloxycarbonyl such as heptadecyloxycarbonyl group, n-octadecyloxycarbonyl group, n-nonadecyloxycarbonyl group, n-icosyloxycarbonyl group and cyclohexyloxycarbonyl group groups can be mentioned. Examples of the aryloxycarbonyl group having an aryl group having 6 to 20 carbon atoms include a phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 3-phenanthryloxycarbonyl group and 2-anthryl An oxycarbonyl group and the like can be mentioned.

In general formula (1), the alkyl group having 1 to 8 carbon atoms represented by X ² and Y ² includes methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- butyl group, n-amyl group, i-amyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like.

Specific examples of the compound represented by formula (2) are given below. First, in the general formula (2), examples of compounds in which X ² or Y ² is a hydrogen atom include the following compounds. Examples include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-(n-propoxy)-1-naphthol, 4-(i-propoxy)-1-naphthol, 4-(n- butoxy)-1-naphthol, 4-(i-butoxy)-1-naphthol, 4-(n-pentyloxy)-1-naphthol, 4-(n-hexyloxy)-1-naphthol, 4-(n- octyloxy)-1-naphthol, 4-(2-ethylhexyloxy)-1-naphthol, 4-(2-hydroxyethoxy)-1-naphthol, 4-(3-hydroxypropoxy)-1-naphthol, 4-phenethyl Oxy-1-naphthol, 4-(2-phenoxyethoxy)-1-naphthol, 4-(2-methoxyethoxy)-1-naphthol, 4-(2-ethoxyethoxy)-1-naphthol, 4-(2- chloroethoxy)-1-naphthol, 4-(3-chloropropoxy)-1-naphthol, 4-(2-bromoethoxy)-1-naphthol, 2-methyl-4-methoxy-1-naphthol, 2-methoxy- 4-methoxy-1-naphthol, 2-chloro-4-methoxy-1-naphthol, 2-amino-4-methoxy-1-naphthol and the like.

Next, when both X ² and Y ² are hydrogen atoms, 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene, 1,4-dibutoxynaphthalene, 4-diamyloxynaphthalene, 1,4-dihexyloxynaphthalene, 1,4-diheptyloxynaphthalene, 1,4-dioctyloxynaphthalene, 1,4-bis(2-ethylhexyl)oxynaphthalene, 1,4-di decyloxynaphthalene, 1,4-didodecyloxynaphthalene, 1,4-diphenyloxynaphthalene, 1,4-dinaphthyloxynaphthalene, 1,4-dibenzyloxynaphthalene, 1,4-diphenethyloxynaphthalene, 1, 4-diallyloxynaphthalene, 1,4-bis(2-methylallyloxy)naphthalene, 1,4-bis(2-hydroxyethoxy)naphthalene, 1,4-bis(3-hydroxypropoxy)naphthalene, 1,4- bis(2-hydroxypropoxy)naphthalene, 1,4-bis(2-hydroxybutoxy)naphthalene, 1,4-bis(2-methoxyethoxy)naphthalene, 1,4-bis(2-ethoxyethoxy)naphthalene, 1, 4-bis(2-phenoxyethoxy)naphthalene, 1,4-bis(2-chloroethoxy)naphthalene, 1,4-bis(2-bromoethoxy)naphthalene, 1-methoxy-4-ethoxynaphthalene, 1-methoxy- 4-glycidyloxynaphthalene, 1-methoxy-4-(2-hydroxyethoxy)naphthalene, 1-methoxy-4-(chloroethoxy)naphthalene, 1-methoxy-4-(2-phenoxyethoxy)naphthalene, 1-ethoxy- 4-butoxynaphthalene, 1-ethoxy-4-glycidyloxynaphthalene, 1-ethoxy-4-(2-hydroxyethoxy)naphthalene, 1-ethoxy-4-(chloroethoxy)naphthalene and the like.

Next, examples in which X ² is an alkyl group and Y ² is a hydrogen atom include 2-methyl-1,4-dimethoxynaphthalene, 2-methyl-1,4-diethoxynaphthalene, 2-methyl -1,4-dipropoxynaphthalene, 2-methyl-1,4-dibutoxynaphthalene, 2-methyl-1,4-diamyloxynaphthalene, 2-methyl-1,4-dihexyloxynaphthalene, 2-methyl- 1,4-diheptyloxynaphthalene, 2-methyl-1,4-dioctyloxynaphthalene, 2-methyl-1,4-bis(2-ethylhexyl)oxynaphthalene, 2-methyl-1,4-didecyloxynaphthalene , 2-methyl-1,4-didodecyloxynaphthalene and the like.

Other examples of 1,4-dioxinaphthalene compounds include 2-chloro-1,4-diethoxynaphthalene, 2,3-dichloro-1,4-diethoxynaphthalene, 2-hydroxy-1,4-di ethoxynaphthalene, 2-chloro-1,4-dibutoxynaphthalene, 2,3-dichloro-1,4-dibutoxynaphthalene, 2-hydroxy-1,4-dibutylethoxynaphthalene and the like.

Still other examples of 1,4-dioxynaphthalene compounds include 2-methoxy-1,4-dimethoxynaphthalene, 2-methoxy-1,4-diethoxynaphthalene, and 2-methoxy-1,4-dipropoxynaphthalene. , 2-methoxy-1,4-dibutoxynaphthalene, 2-methoxy-1,4-diamyloxynaphthalene, 2-methoxy-1,4-dihexyloxynaphthalene, 2-methoxy-1,4-diheptyloxynaphthalene , 2-methoxy-1,4-dioctyloxynaphthalene, 2-methoxy-1,4-bis(2-ethylhexyl)oxynaphthalene, 2-methoxy-1,4-didecyloxynaphthalene, 2-methoxy-1,4 -didodecyloxynaphthalene and the like.

Among the naphthalene compounds of the present invention represented by general formula (2), those in which R ³ and R ⁴ are an alkylcarbonyl group or an arylcarbonyl group are referred to as 1,4-bis(substituted acyloxy)naphthalene compounds. Examples include the following compounds.

First, when both X ² and Y ² are hydrogen atoms, 1,4-diacetyloxynaphthalene, 1,4-dipropionyloxynaphthalene, 1,4-bis(n-butanoyloxy)naphthalene, 1 ,4-bis(iso-butanoyloxy)naphthalene, 1,4-bis(n-pentanoyloxy)naphthalene, 1,4-bis(n-hexanoyloxy)naphthalene, 1,4-bis(n-hepta noyloxy)naphthalene, 1,4-bis(n-octanoyloxy)naphthalene, 1,4-bis(2-ethylhexanoyloxy)naphthalene, 1,4-bis(n-nonanoyloxy)naphthalene, 1,4- bis(n-decanoyloxy)naphthalene, 1,4-bis(n-dodecanoyloxy)naphthalene and the like.

Next, when X ² is an alkyl group and Y ² is a hydrogen atom, examples include 2-methyl-1,4-diacetyloxynaphthalene, 2-methyl-1,4-dipropionyloxynaphthalene, 2 -methyl-1,4-bis(n-butanoyloxy)naphthalene, 2-methyl-1,4-bis(iso-butanoyloxy)naphthalene, 2-methyl-1,4-bis(n-hexanoyloxy) ) naphthalene, 2-methyl-1,4-bis(n-heptanoyloxy)naphthalene, 2-methyl-1,4-bis(n-octanoyloxy)naphthalene, 2-methyl-1,4-bis(2 -ethylhexanoyloxy)naphthalene, 2-methyl-1,4-bis(n-nonanoyloxy)naphthalene, 2-methyl-1,4-bis(n-decanoyloxy)naphthalene, 2-methyl-1,4- Bis(n-dodecanoyloxy)naphthalene, 2-ethyl-1,4-diacetyloxynaphthalene, 2-ethyl-1,4-dipropionyloxynaphthalene, 2-ethyl-1,4-bis(n-butanoyloxy ) naphthalene, 2-ethyl-1,4-bis(iso-butanoyloxy)naphthalene, 2-ethyl-1,4-bis(n-hexanoyloxy)naphthalene, 2-ethyl-1,4-bis(n -heptanoyloxy)naphthalene, 2-ethyl-1,4-bis(n-octanoyloxy)naphthalene, 2-ethyl-1,4-bis(2-ethylhexanoyloxy)naphthalene, 2-ethyl-1, 4-bis(n-nonanoyloxy)naphthalene, 2-ethyl-1,4-bis(n-decanoyloxy)naphthalene, 2-ethyl-1,4-bis(n-dodecanoyloxy)naphthalene and the like.

Further, when both X ² and Y ² are alkyl groups, examples thereof include 2,3-dimethyl-1,4-diacetyloxynaphthalene, 2,3-dimethyl-1,4-dipropionyloxynaphthalene, 2, 3-dimethyl-1,4-bis(n-butanoyloxy)naphthalene, 2,3-dimethyl-1,4-bis(iso-butanoyloxy)naphthalene, 2,3-dimethyl-1,4-bis( n-hexanoyloxy)naphthalene, 2,3-dimethyl-1,4-bis(n-heptanoyloxy)naphthalene, 2,3-dimethyl-1,4-bis(n-octanoyloxy)naphthalene, 2, 3-dimethyl-1,4-bis(2-ethylhexanoyloxy)naphthalene, 2,3-dimethyl-1,4-bis(n-nonanoyloxy)naphthalene, 2,3-dimethyl-1,4-bis(n -decanoyloxy)naphthalene, 2,3-dimethyl-1,4-bis(n-dodecanoyloxy)naphthalene, 2,6-dimethyl-1,4-diacetyloxynaphthalene, 2,6-dimethyl-1,4 -dipropionyloxynaphthalene, 2,6-dimethyl-1,4-bis(n-butanoyloxy)naphthalene, 2,6-dimethyl-1,4-bis(iso-butanoyloxy)naphthalene, 2,6- Dimethyl-1,4-bis(n-hexanoyloxy)naphthalene, 2,6-dimethyl-1,4-bis(n-heptanoyloxy)naphthalene, 2,6-dimethyl-1,4-bis(n- octanoyloxy)naphthalene, 2,6-dimethyl-1,4-bis(2-ethylhexanoyloxy)naphthalene, 2,6-dimethyl-1,4-bis(n-nonanoyloxy)naphthalene, 2,6-dimethyl -1,4-bis(n-decanoyloxy)naphthalene, 2,6-dimethyl-1,4-bis(n-dodecanoyloxy)naphthalene, 2,7-dimethyl-1,4-diacetyloxynaphthalene, 2 ,7-dimethyl-1,4-dipropionyloxynaphthalene, 2,7-dimethyl-1,4-bis(n-butanoyloxy)naphthalene, 2,7-dimethyl-1,4-bis(iso-butanoyl oxy)naphthalene, 2,7-dimethyl-1,4-bis(n-hexanoyloxy)naphthalene, 2,7-dimethyl-1,4-bis(n-heptanoyloxy)naphthalene, 2,7-dimethyl- 1,4-bis(n-octanoyloxy)naphthalene, 2,7-dimethyl-1,4-bis( 2-ethylhexanoyloxy)naphthalene, 2,7-dimethyl-1,4-bis(n-nonanoyloxy)naphthalene, 2,7-dimethyl-1,4-bis(n-decanoyloxy)naphthalene, 2,7 -dimethyl-1,4-bis(n-dodecanoyloxy)naphthalene and the like.

Next, among the naphthalene compounds of the present invention represented by the general formula (2), 1,4-bis(alkoxycarbonyloxy)naphthalene when R ³ and R ⁴ are an alkyloxycarbonyl group or an aryloxycarbonyl group Examples of compounds referred to as compounds include the following compounds.

First, examples in which both X ² and Y ² are hydrogen atoms include 1,4-bis(methoxycarbonyloxy)naphthalene, 1,4-bis(ethoxycarbonyloxy)naphthalene, 1,4-bis (n-propoxycarbonyloxy)naphthalene, 1,4-bis(i-propoxycarbonyloxy)naphthalene, 1,4-bis(n-butoxycarbonyloxy)naphthalene, 1,4-bis(i-butoxycarbonyloxy)naphthalene , 1,4-bis(n-pentyloxycarbonyloxy)naphthalene, 1,4-bis(i-pentyloxycarbonyloxy)naphthalene, 1,4-bis(n-hexyloxycarbonyloxy)naphthalene, 1,4- Bis(n-heptyloxycarbonyloxy)naphthalene, 1,4-bis(n-octyloxycarbonyloxy)naphthalene, 1,4-bis(2-ethylhexyloxycarbonyloxy)naphthalene, 1,4-bis(allyloxycarbonyl) oxy)naphthalene and the like.

Next, when X ² is an alkyl group and Y ² is a hydrogen atom, examples include 2-methyl-1,4-bis(methoxycarbonyloxy)naphthalene, 2-methyl-1,4-bis( ethoxycarbonyloxy)naphthalene, 2-methyl-1,4-bis(n-propoxycarbonyloxy)naphthalene, 2-methyl-1,4-bis(i-propoxycarbonyloxy)naphthalene, 2-methyl-1,4- Bis(n-butoxycarbonyloxy)naphthalene, 2-methyl-1,4-bis(i-butoxycarbonyloxy)naphthalene, 2-methyl-1,4-bis(n-pentyloxycarbonyloxy)naphthalene, 2-methyl -1,4-bis(i-pentyloxycarbonyloxy)naphthalene, 2-methyl-1,4-bis(n-hexyloxycarbonyloxy)naphthalene, 2-methyl-1,4-bis(n-heptyloxycarbonyl) oxy)naphthalene, 2-methyl-1,4-bis(n-octyloxycarbonyloxy)naphthalene, 2-methyl-1,4-bis(2-ethylhexyloxycarbonyloxy)naphthalene, 2-methyl-1,4- Bis(allyloxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis(methoxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis(ethoxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis (n-propoxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis(i-propoxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis(n-butoxycarbonyloxy)naphthalene, 2-ethyl-1 , 4-bis(i-butoxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis(n-pentyloxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis(i-pentyloxycarbonyloxy)naphthalene , 2-ethyl-1,4-bis(n-hexyloxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis(n-heptyloxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis(n -octyloxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis(2-ethylhexyloxycarbonyloxy)naphthalene, 2-ethyl-1,4-bis(allyloxycarbonyloxy)naphthalene and the like.

Examples of the case where both X ² and Y ² are alkyl groups include 2,3-dimethyl-1,4-bis(methoxycarbonyloxy)naphthalene, 2,3-dimethyl-1,4-bis(ethoxy carbonyloxy)naphthalene, 2,3-dimethyl-1,4-bis(n-propoxycarbonyloxy)naphthalene, 2,3-dimethyl-1,4-bis(i-propoxycarbonyloxy)naphthalene, 2,3-dimethyl -1,4-bis(n-butoxycarbonyloxy)naphthalene, 2,3-dimethyl-1,4-bis(i-butoxycarbonyloxy)naphthalene, 2,3-dimethyl-1,4-bis(n-pentyl oxycarbonyloxy)naphthalene, 2,3-dimethyl-1,4-bis(i-pentyloxycarbonyloxy)naphthalene, 2,3-dimethyl-1,4-bis(n-hexyloxycarbonyloxy)naphthalene, 2, 3-dimethyl-1,4-bis(n-heptyloxycarbonyloxy)naphthalene, 2,3-dimethyl-1,4-bis(n-octyloxycarbonyloxy)naphthalene, 2,3-dimethyl-1,4- bis(2-ethylhexyloxycarbonyloxy)naphthalene, 2,3-dimethyl-1,4-bis(allyloxycarbonyloxy)naphthalene, 2,6-dimethyl-1,4-bis(methoxycarbonyloxy)naphthalene, 2, 6-dimethyl-1,4-bis(ethoxycarbonyloxy)naphthalene, 2,6-dimethyl-1,4-bis(n-propoxycarbonyloxy)naphthalene, 2,6-dimethyl-1,4-bis(i- propoxycarbonyloxy)naphthalene, 2,6-dimethyl-1,4-bis(n-butoxycarbonyloxy)naphthalene, 2,6-dimethyl-1,4-bis(i-butoxycarbonyloxy)naphthalene, 2,6- Dimethyl-1,4-bis(n-pentyloxycarbonyloxy)naphthalene, 2,6-dimethyl-1,4-bis(i-pentyloxycarbonyloxy)naphthalene, 2,6-dimethyl-1,4-bis( n-hexyloxycarbonyloxy)naphthalene, 2,6-dimethyl-1,4-bis(n-heptyloxycarbonyloxy)naphthalene, 2,6-dimethyl-1,4-bis(n-octyloxycarbonyloxy)naphthalene , 2,6-dimethyl-1,4-bis(2-ethylhexyloxycarbonyloxy)naphthalene, 2,6- Dimethyl-1,4-bis(allyloxycarbonyloxy)naphthalene, 2,7-dimethyl-1,4-bis(methoxycarbonyloxy)naphthalene, 2,7-dimethyl-1,4-bis(ethoxycarbonyloxy)naphthalene , 2,7-dimethyl-1,4-bis(n-propoxycarbonyloxy)naphthalene, 2,7-dimethyl-1,4-bis(i-propoxycarbonyloxy)naphthalene, 2,7-dimethyl-1,4 -bis(n-butoxycarbonyloxy)naphthalene, 2,7-dimethyl-1,4-bis(i-butoxycarbonyloxy)naphthalene, 2,7-dimethyl-1,4-bis(n-pentyloxycarbonyloxy) Naphthalene, 2,7-dimethyl-1,4-bis(i-pentyloxycarbonyloxy)naphthalene, 2,7-dimethyl-1,4-bis(n-hexyloxycarbonyloxy)naphthalene, 2,7-dimethyl- 1,4-bis(n-heptyloxycarbonyloxy)naphthalene, 2,7-dimethyl-1,4-bis(n-octyloxycarbonyloxy)naphthalene, 2,7-dimethyl-1,4-bis(2- ethylhexyloxycarbonyloxy)naphthalene, 2,7-dimethyl-1,4-bis(allyloxycarbonyloxy)naphthalene, and the like.

Furthermore, 2,3-diethyl-1,4-bis(methoxycarbonyloxy)naphthalene, 2,3-diethyl-1,4-bis(ethoxycarbonyloxy)naphthalene, 2,3-diethyl-1,4-bis (n-propoxycarbonyloxy)naphthalene, 2,3-diethyl-1,4-bis(i-propoxycarbonyloxy)naphthalene, 2,3-diethyl-1,4-bis(n-butoxycarbonyloxy)naphthalene, 2 ,3-diethyl-1,4-bis(i-butoxycarbonyloxy)naphthalene, 2,3-diethyl-1,4-bis(n-pentyloxycarbonyloxy)naphthalene, 2,3-diethyl-1,4- Bis(i-pentyloxycarbonyloxy)naphthalene, 2,3-diethyl-1,4-bis(n-hexyloxycarbonyloxy)naphthalene, 2,3-diethyl-1,4-bis(n-heptyloxycarbonyloxy) ) naphthalene, 2,3-diethyl-1,4-bis(n-octyloxycarbonyloxy)naphthalene, 2,3-diethyl-1,4-bis(2-ethylhexyloxycarbonyloxy)naphthalene, 2,3-diethyl -1,4-bis(allyloxycarbonyloxy)naphthalene, 2,6-diethyl-1,4-bis(methoxycarbonyloxy)naphthalene, 2,6-diethyl-1,4-bis(ethoxycarbonyloxy)naphthalene, 2,6-diethyl-1,4-bis(n-propoxycarbonyloxy)naphthalene, 2,6-diethyl-1,4-bis(i-propoxycarbonyloxy)naphthalene, 2,6-diethyl-1,4- Bis(n-butoxycarbonyloxy)naphthalene, 2,6-diethyl-1,4-bis(i-butoxycarbonyloxy)naphthalene, 2,6-diethyl-1,4-bis(n-pentyloxycarbonyloxy)naphthalene , 2,6-diethyl-1,4-bis(i-pentyloxycarbonyloxy)naphthalene, 2,6-diethyl-1,4-bis(n-hexyloxycarbonyloxy)naphthalene, 2,6-diethyl-1 ,4-bis(n-heptyloxycarbonyloxy)naphthalene, 2,6-diethyl-1,4-bis(n-octyloxycarbonyloxy)naphthalene, 2,6-diethyl-1,4-bis(2-ethylhexyl oxycarbonyloxy)naphthalene, 2,6-diethyl-1,4-bis(allyloxycarbonyloxy)naphthalene phthalene, 2,7-diethyl-1,4-bis(methoxycarbonyloxy)naphthalene, 2,7-diethyl-1,4-bis(ethoxycarbonyloxy)naphthalene, 2,7-diethyl-1,4-bis( n-propoxycarbonyloxy)naphthalene, 2,7-diethyl-1,4-bis(i-propoxycarbonyloxy)naphthalene, 2,7-diethyl-1,4-bis(n-butoxycarbonyloxy)naphthalene, 2, 7-diethyl-1,4-bis(i-butoxycarbonyloxy)naphthalene, 2,7-diethyl-1,4-bis(n-pentyloxycarbonyloxy)naphthalene, 2,7-diethyl-1,4-bis (i-pentyloxycarbonyloxy)naphthalene, 2,7-diethyl-1,4-bis(n-hexyloxycarbonyloxy)naphthalene, 2,7-diethyl-1,4-bis(n-heptyloxycarbonyloxy) Naphthalene, 2,7-diethyl-1,4-bis(n-octyloxycarbonyloxy)naphthalene, 2,7-diethyl-1,4-bis(2-ethylhexyloxycarbonyloxy)naphthalene, 2,7-diethyl- 1,4-bis(allyloxycarbonyloxy)naphthalene and the like.

Furthermore, 1-ethoxy-4-(2-phenoxyethoxy)naphthalene, 2-methyl-1,4-dimethoxynaphthalene, 2-methyl-1,4-diethoxynaphthalene, 2-methyl-1,4-di(n -propoxy)naphthalene, 2-methyl-1,4-di(i-propoxy)naphthalene, 2-methyl-1,4-di(n-butoxy)naphthalene, 2-methyl-1,4-di(i-butoxy) ) naphthalene, 2-methyl-1,4-di(n-pentyloxy)naphthalene, 2-methyl-1,4-di(n-hexyloxy)naphthalene, 2-methyl-1,4-bis(2-ethylhexyl oxy)naphthalene, 2-methyl-1,4-di(n-dodecyloxy)naphthalene, 2-methyl-1,4-dibenzyloxynaphthalene, 2-methyl-1,4-diphenethyloxynaphthalene, 2-methyl -1,4-diallyloxynaphthalene, 2-methyl-1,4-bis(2-methylallyloxy)naphthalene, 2-methyl-1,4-bis(2-hydroxyethoxy)naphthalene, 2-methyl-1, 4-bis(3-hydroxypropoxy)naphthalene, 2-methyl-1,4-bis(2-hydroxypropoxy)naphthalene, 2-methyl-1,4-bis(2-hydroxybutoxy)naphthalene, 2-methyl-1 , 4-bis(2-methoxyethoxy)naphthalene, 2-methyl-1,4-bis(2-ethoxyethoxy)naphthalene, 2-methyl-1,4-bis(2-phenoxyethoxy)naphthalene, 2-methyl- 1,4-diglycidyloxynaphthalene, 2-methyl-1,4-bis(2-chloroethoxy)naphthalene, 2-methyl-1,4-bis(2-bromoethoxy)naphthalene, 2-methyl-1-methoxy -4-ethoxynaphthalene, 2-methyl-1-methoxy-4-glycidyloxynaphthalene, 2-methyl-1-methoxy-4-(2-hydroxyethoxy)naphthalene, 2-methyl-1-methoxy-4-(chloro ethoxy)naphthalene, 2-methyl-1-methoxy-4-(2-phenoxyethoxy)naphthalene, 2-methyl-1-ethoxy-4-butoxynaphthalene, 2-methyl-1-ethoxy-4-glycidyloxynaphthalene, 2 -methyl-1-ethoxy-4-(2-hydroxyethoxy)naphthalene, 2-methyl-1-ethoxy-4-(chloroethoxy)naphthalene, 2-methyl-1-ethoxy-4-(2-phenoxyethoxy)naphthalene , 2- Chloro-1,4-dimethoxynaphthalene, 2-chloro-1,4-diethoxynaphthalene, 2-methyl-1,4-di(n-propoxy)naphthalene, 2-chloro-1,4-di(i-propoxy ) naphthalene, 2-chlorochloro-1,4-di(n-butoxy)naphthalene, 2-chloro-1,4-di(i-butoxy)naphthalene, 2-chloro-1,4-di(n-pentyloxy ) naphthalene, 2-chloro-1,4-di(n-hexyloxy)naphthalene, 2-chloro-1,4-bis(2-ethylhexyloxy)naphthalene, 2-chloro-1,4-di(n-dodecyl oxy)naphthalene, 2-chloro-1,4-dibenzyloxynaphthalene, 2-chloro-1,4-diphenethyloxynaphthalene, 2-chloro-1,4-diallyloxynaphthalene, 2-chloro-1,4- bis(2-methylallyloxy)naphthalene, 2-chloro-1,4-bis(2-hydroxyethoxy)naphthalene, 2-chloro-1,4-bis(3-hydroxypropoxy)naphthalene, 2-chloro-1, 4-bis(2-hydroxypropoxy)naphthalene, 2-chloro-1,4-bis(2-hydroxybutoxy)naphthalene, 2-chloro-1,4-bis(2-methoxyethoxy)naphthalene, 2-chloro-1 ,4-bis(2-ethoxyethoxy)naphthalene, 2-chloro-1,4-bis(2-phenoxyethoxy)naphthalene, 2-chloro-1,4-diglycidyloxynaphthalene, 2-chloro-1,4-bis (2-chloroethoxy)naphthalene, 2-chloro-1,4-bis(2-bromoethoxy)naphthalene, 2-chloro-1-methoxy-4-ethoxynaphthalene, 2-chloro-1-methoxy-4-glycidyloxy Naphthalene, 2-chloro-1-methoxy-(2-hydroxyethoxy)naphthalene, 2-chloro-1-methoxy-4-(chloroethoxy)naphthalene, 2-chloro-1-methoxy-4-(2-phenoxyethoxy) Naphthalene, 2-chloro-1-ethoxy-4-butoxynaphthalene, 2-chloro-1-ethoxy-4-glycidyloxynaphthalene, 2-chloro-1-ethoxy-4-(2-hydroxyethoxy)naphthalene, 2-chloro -1-ethoxy-4-(chloroethoxy)naphthalene, 2-chloro-1-ethoxy-4-(2-phenoxyethoxy)naphthalene, 1,2,4-trimethoxynaphthalene, 1,2,4-triethoxynaphthalene , 2,3-dichloro-1,4-diethoxynaphthalene, 2,3-dimethoxy-1,4-diethoxynaphthalene, 2-amino-3-chloro-1,4-diethoxynaphthalene, 2,3-dichloro -1,4-dimethoxynaphthalene, 2,3-dimethoxy-1,4-dimethoxynaphthalene, 2-amino-3-chloro-1,4-dimethoxynaphthalene, 1,4,5-triethoxynaphthalene, 1,4, 5-trimethoxynaphthalene, 6-methyl-1,4-diethoxynaphthalene, 6-methyl-1,4-dimethoxynaphthalene and the like.

Furthermore, in the general formula (2), examples of compounds in which both X ² and Y ² are hydrogen atoms include the following compounds. For example, 1,4-naphthohydroquinone, 2-methyl-1,4-naphthohydroquinone, 2-hydroxy-1,4-naphthohydroquinone, 2-methoxy-1,4-naphthohydroquinone, 2-ethoxy-1,4- naphthohydroquinone, 2-chloro-1,4-naphthohydroquinone, 2-carboxy-1,4-naphthohydroquinone, 1,4-dihydroxynaphthalen-2-ylsulfonic acid, 5-methoxy-1,4-naphthohydroquinone, 5- ethoxy-1,4-naphthohydroquinone, 5-hydroxy-1,4-naphthohydroquinone, 5-amino-1,4-naphthohydroquinone, 6-methyl-1,4-naphthohydroquinone, 6-chloro-1,4- naphthohydroquinone, 2,3-dichloro-1,4-naphthohydroquinone, 2,3-dihydroxy-1,4-naphthohydroquinone, 2,3-dimethoxy-1,4-naphthohydroquinone, 2-amino-3-chloro- 1,4-naphthohydroquinone and the like

Among these compounds, 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-di(n-propoxy)naphthalene, 1,4-di(i-propoxy)naphthalene, 1,4- Di(n-butoxy)naphthalene, 1,4-di(i-butoxy)naphthalene, 1,4-di(n-pentyloxy)naphthalene, 1,4-di(n-hexyloxy)naphthalene, 1,4- Bis(2-ethylhexyloxy)naphthalene and 1,4-di(n-dodecyloxy)naphthalene are preferred because they are easy to synthesize, and 1,4-diethoxynaphthalene is particularly preferred.

(Photoradical polymerization initiator)
The photoradical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used. For example, acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone ketone-based compounds, oxime ester-based compounds, phosphine oxide-based compounds, titanocene-based compounds, onium salts and the like can be exemplified.

Of these, onium salt-based radical photopolymerization initiators are preferred. Examples of the onium salt-based photopolymerization initiator include sulfonium salts, iodonium salts, pyridinium salts, phosphonium salts and the like, but sulfonium salts and iodonium salts are preferred from the viewpoint of sensitivity to irradiation light. Examples of the sulfonium salt include diphenylalkylsulfonium salts, dinaphthylalkylsulfonium salts, and triphenylsulfonium salts. Triphenylsulfonium salts are preferred from the viewpoint of sensitivity to irradiation light. Triphenylsulfonium salts include S,S,S',S'-tetraphenyl-S,S'-(4,4'-thiodiphenyl)disulfonium bishexafluorophosphate and diphenyl-4-phenylthiophenylsulfonium. Hexafluorophosphate, triphenylsulfonium hexafluorophosphate and the like, for example UVI-6992 manufactured by Dow Chemical {Compound name: S,S,S',S'-tetraphenyl-S,S'-(4, 4'-thiodiphenyl)disulfonium bishexafluorophosphate}.

On the other hand, the iodonium salts include iodonium salts such as diphenyliodonium salts, phenylnaphthyliodonium salts, dinaphthyliodonium salts, etc. Diphenyliodonium salts are preferred in terms of sensitivity to irradiation light. Diphenyliodonium salts include 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenylborate, and the like. For example, BASF Corp. irgaure 250 {Compound name: 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate}, Rhodia Corp. 2074 {Compound name: 4-isopropylphenyl-4'- methyl phenyl iodonium tetrakis pentafluorophenyl borate}.

Among these onium salts, the iodonium salts may have lower storage stability than the sulfonium salts, which may cause problems such as discoloration during long-term storage. Therefore, when long-term storage stability is required, it is more preferable to use a sulfonium salt as the onium salt.

(Radical polymerizable compound)
Examples of radically polymerizable compounds include organic compounds having double bonds such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid esters, methacrylic acid esters, and fumaric acid esters. can do Among these radically polymerizable compounds, acrylic acid esters and methacrylic acid esters (hereinafter, both are collectively referred to as (meth)acrylic acid esters) are preferred from the viewpoint of film-forming ability and the like. (Meth)acrylate esters include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and tetraethylene. Glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, imide acrylate and the like. These radically polymerizable compounds may be one kind, a mixture of two or more kinds, or an oligomer.

In the present invention, the amount of the onium salt photoradical polymerization initiator added is 0.1 to 10 parts by weight, more preferably 0.5 to 5.0 parts by weight, per 100 parts by weight of the radically polymerizable compound. be.

(Photoradical polymerizable composition)
The photoradical polymerizable composition of the present invention comprises at least the above radical polymerizable compound, a photoradical polymerization initiator, an anthracene compound represented by the general formula (1) as a photoradical polymerization sensitizer, and a photoradical polymerization sensitizer. It contains a naphthalene compound represented by the general formula (2) as an agent.

The total addition amount of the anthracene compound represented by the general formula (1) of the present invention and the naphthalene compound represented by the general formula (2) of the present invention is 0.1 per 100 parts by weight of the radically polymerizable monomer. ~5.0 parts by weight, more preferably 0.2 to 2 parts by weight. If the concentration of the photo-onium salt-based photopolymerization initiator is too low, the curing speed becomes slow, and if the concentration is too high, the physical properties of the cured product deteriorate. In particular, when the anthracene compound represented by the general formula (1) is added in an amount exceeding 2 parts by weight, when the photoradical polymerizable composition is cured, the transparency of the cured product is impaired, which is not preferable. .

In the radically photopolymerizable composition of the present invention, the weight ratio of the anthracene compound represented by the general formula (1) to the naphthalene compound represented by the general formula (2) is 0.1 or more and 10 or less. . Especially preferably, it is 0.2 or more and 1.2 or less. If it is less than 0.1, the effect as a sensitizer is not sufficient, and if it exceeds 10, when the photoradical polymerizable composition is cured, the transparency of the cured product is impaired. It is not preferable because

The photocurable composition according to the present invention may further contain diluents, colorants, organic or inorganic fillers, leveling agents, surfactants, antifoaming agents, and thickeners as long as the effects of the present invention are not impaired. Various resin additives such as additives, flame retardants, antioxidants, stabilizers, lubricants, plasticizers, etc. can be blended within the usual range of use.

Examples of diluents include epoxy diluents such as epoxy acrylate, oxetane diluents such as oxacyclobutane, vinyl ether diluents, and (meth)acrylic monomer diluents. Colorants include blue pigments, red pigments, white pigments, black pigments, and the like. Examples of black pigments include carbon black, acetylene black, lamp black, and aniline black. Examples of yellow pigments include yellow lead, zinc yellow, cadmium yellow, iron oxide yellow, mineral fast yellow, nickel titanium yellow, navels yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, and benzidine yellow. GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake and the like.

Examples of red pigments include red iron oxide, cadmium red, red lead, cadmium mercury sulfide, permanent red 4R, resole red, lake red D brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, and brilliant carmine 3B. . Examples of blue pigments include Prussian blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, and indanthrene blue BC. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide. Other pigments include, for example, barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

(Photoradical polymerization)
Curing can be performed in the form of a film, and it is also possible to cure in the form of blocks. In the case of curing in the form of a film, for example, the photocurable composition is applied to a substrate such as a polyester film using a bar coater and then irradiated with light. The lamp to be used preferably emits light having a peak wavelength within a wavelength range of preferably 380 to 420 nm. Examples of light sources include metal halide lamps, xenon lamps, ultraviolet LED lamps, blue LEDs, white LED lamps, D lamps and V lamps manufactured by Fusion. It is also possible to use sunlight. In particular, an ultraviolet LED light source having a peak wavelength of 385 nm, 395 nm, 405 nm, or 415 nm is preferred, and an ultraviolet LED light source having a peak wavelength of 405 nm is particularly preferred.

Light irradiation is desirably performed in the absence of oxygen. In the presence of oxygen, it is difficult to remove the tackiness of the film surface due to oxygen inhibition, and it is necessary to add a large amount of initiator. Curing methods in the absence of oxygen include an atmosphere of nitrogen gas, helium gas, or the like. A method of covering with an oxygen-impermeable film and photocuring is also effective.

Several examples are presented below to more specifically describe the present invention. However, the scope of the present invention is not limited to the scope of these examples.

<Optical DSC measurement>
In this example, the optical DSC measurement was performed as follows. As the DSC measurement device, XDSC-7000 manufactured by Hitachi High-Tech Co., Ltd. was used, and an optical DSC measurement unit was attached to it so that DSC measurement could be performed while irradiating light.

LA-410UV manufactured by Hayashi Tokei Kogyo Co., Ltd. was used as a light source for light irradiation, and 405 nm light was extracted by a band-pass filter so that the sample could be irradiated with the light. A glass fiber was used to guide the light from the light source to the top of the sample, and the shutter of the light source was trigger-controlled so that DSC measurement could be performed simultaneously with the start of light irradiation.

For the optical DSC measurement, about 1 mg of a sample was precisely weighed in an aluminum pan for measurement, placed in the DSC measuring section, and then attached to the optical DSC unit. Nitrogen was passed through the measurement part of the DSC at a rate of 100 mL/min, and the measurement was continued for 5 minutes while irradiating light in a nitrogen atmosphere. After the first measurement, the sample was left as it was and another measurement was performed under the same conditions. A value obtained by subtracting the second measurement result from the first measurement result was used as the measurement result of the sample. The results were compared in terms of the total calorific value per 1 mg of sample 5 minutes after light irradiation, unless otherwise specified.

In addition, the conversion rate was thermally analyzed by sealing trimethylolpropane triacrylate (TMPTA) (manufactured by Tokyo Chemical Industry Co., Ltd.) in an aluminum sealed pan and increasing the temperature from 30 ° C. to 300 ° C. at a rate of 5 ° C./min by DSC. Measurement was performed, and the total calorific value of the obtained exothermic peak was calculated as 100%.

<Creation of cured product and measurement of YI>
The radical polymerization cured product was prepared as follows. First, a polyethylene terephthalate (PET) film (width 18 mm×height 1 cm×thickness 0.1 mm) is placed on both ends of a cover glass (width 18 mm×height 18 mm×thickness 0.16 mm). An appropriate amount of the radically polymerizable composition is dropped between the PET films, and the film is covered with another cover glass. This was irradiated with ultraviolet rays for 5 minutes using an ultraviolet LED irradiation machine (RX-Firefly manufactured by Phoseon Technology, center wavelength 395 nm, illuminance 135 mW/cm ² ) to obtain a radically polymerized cured product.

The transmittance of the obtained cured product was measured with an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation) from 200 to 800 nm, and YI was calculated using color measurement software.

<Evaluation>
In general, if the conversion ratio of the radically polymerizable composition is 60% or more, the cured product is not sticky, that is, it can be said to be sufficiently cured in a tack-free state. In addition, when the YI value is 0.1 mm, if it is 10 or less, yellowing of the cured product is unlikely to be a problem, but if it exceeds 10, yellowing of the cured product will be a problem becomes.
Therefore, if the conversion rate is 65% or more and the YI of the cured product is 10 or less, the evaluation is "○", if only one of them is satisfied, "△", and if neither is satisfied or the YI is not cured, the YI is measured. When it was not possible, it was judged as "x", and the examples and comparative examples were evaluated and described in Table 1.

(Example 1)
100 parts by weight of trimethylolpropane triacrylate (TMPTA) (manufactured by Tokyo Kasei Co., Ltd.) as a radical polymerizable compound, and 4.0 parts of Irgacure 250 (manufactured by BASF, Irgacure is a registered trademark of BASF) as a photoradical polymerization initiator. 0.25 parts by weight of 9,10-dibutoxyanthracene (DBA) as a radical photopolymerization sensitizer and 0.25 part by weight of 1,4-diethoxynaphthalene as a radical photopolymerization sensitizer. parts were added to prepare a radically photopolymerizable composition. 1 mg of the photo-radical polymerizable composition was precisely weighed in an aluminum pan for measurement, placed in a DSC measurement section, and then attached to a photo-DSC unit. The sample was irradiated with light of 405 nm at an illuminance of 50 mW/cm 2 for 5 minutes, and the calorific value at that time was 486 mJ/mg, and the sample was in a cured state after measurement. Moreover, the YI of the cured product of the photoradical polymerizable composition was 9.42. The results are listed in Table 1.

(Comparative example 1)
Measurements were carried out in the same manner as in Example 1, except that neither the radical photopolymerization sensitizer nor the auxiliary photoradical polymerization sensitizer was added. As a result, the calorific value was 7.63 mJ/mg, and the sample was in an uncured state after the measurement. Moreover, the YI of the cured product of the photoradical polymerizable composition could not be measured because it was uncured. The results are listed in Table 1.

(Comparative example 2)
Measurement was carried out in the same manner as in Example 1, except that the amount of 9,10-dibutoxyanthracene (DBA), a photoradical polymerization sensitizer, was 0.5 parts by weight, and no photoradical polymerization sensitizer was added. Carried out. As a result, the calorific value was 397 mJ/mg, and the sample was in a cured state after the measurement. Moreover, the YI of the cured product of the photoradical polymerizable composition was 20.13. The results are listed in Table 1.

(Comparative Example 3)
Measured in the same manner as in Example 1, except that no radical photopolymerization sensitizer was added and the amount of 1,4-diethoxynaphthalene (DEN), a photoradical polymerization sensitizer, was changed to 0.5 parts by weight. carried out. As a result, the calorific value was 195 mJ/mg, and the sample was in an uncured state after the measurement. Moreover, the YI of the cured product of the photoradical polymerizable composition could not be measured because it was uncured. The results are listed in Table 1.

(Example 2)
To 100 parts by weight of trimethylolpropane triacrylate (TMPTA) (manufactured by Tokyo Chemical Industry Co., Ltd.) as a radically polymerizable compound, 3.0 parts by weight of UVI-6992 (manufactured by Dow Chemical Co., Ltd.) as a photoradical polymerization initiator was added. Furthermore, 0.25 parts by weight of 9,10-dibutoxyanthracene (DBA) as a photoradical polymerization sensitizer and 0.25 parts by weight of 1,4-diethoxynaphthalene (DEN) as a photoradical polymerization sensitizer. was added to prepare a photoradical polymerizable composition. 1 mg of the photo-radical polymerizable composition was precisely weighed in an aluminum pan for measurement, placed in a DSC measurement section, and then attached to a photo-DSC unit. The sample was irradiated with light of 405 nm at an illuminance of 50 mW/cm 2 for 5 minutes, and the calorific value at that time was 394 mJ/mg, and the sample was in a cured state after measurement. Moreover, the YI of the cured product of the photoradical polymerizable composition was 5.18. The results are listed in Table 1.

(Comparative Example 4)
Measurement was carried out in the same manner as in Example 2, except that neither the radical photopolymerization sensitizer nor the photoradical polymerization sensitizing aid was added. As a result, the calorific value was 12.1 mJ/mg, and the sample was in an uncured state after the measurement. Moreover, the YI of the cured product of the photoradical polymerizable composition could not be measured because it was uncured. The results are listed in Table 1.

(Comparative Example 5)
Measurement was carried out in the same manner as in Example 2, except that the amount of 9,10-dibutoxyanthracene (DBA), a photoradical polymerization sensitizer, was 0.5 parts by weight, and no photoradical polymerization sensitizer was added. Carried out. As a result, the calorific value was 402 mJ/mg, and the sample was in a cured state after the measurement. The YI of the cured product of the photoradical polymerizable composition was 11.61. The results are listed in Table 1.

(Comparative Example 6)
Measured in the same manner as in Example 2, except that no radical photopolymerization sensitizer was added and the amount of 1,4-diethoxynaphthalene (DEN), a photoradical polymerization sensitizer, was changed to 0.5 parts by weight. carried out. As a result, the calorific value was 87.7 mJ/mg, and the sample was in a cured state after the measurement. Moreover, the YI of the cured product of the photoradical polymerizable composition could not be measured because it was uncured. The results are listed in Table 1.

As can be seen from Comparative Examples 1 and 4, Irgacure 250 and UVI-6992 do not undergo radical polymerization when irradiated with light of 405 nm. On the other hand, as can be seen from Comparative Examples 2 and 5, by adding 9,10-dibutoxyanthracene (DBA) as a radical photopolymerization sensitizer, radical polymerization proceeded with light of 405 nm. The YI value of the cured product of the radically polymerizable composition is high, and the evaluation is poor due to the coloring of the cured product. Furthermore, as can be seen from Comparative Examples 3 and 6, radical polymerization of 1,4-diethoxynaphthalene (DEN), which is a photoradical polymerization sensitizing aid, hardly progresses.

However, as can be seen from Example 1 and Comparative Examples 2 and 3, and Example 2 and Comparative Examples 5 and 6, the amounts of the radical photopolymerization sensitizer and the photoradical polymerization sensitizing aid are halved and mixed. It can be seen that by using each of them alone, the amount of heat generated by polymerization is clearly improved, that is, the polymerization progresses more and the conversion rate to the polymer is improved. Moreover, since the YI value of the cured product is low, there is almost no coloring of the cured product, and favorable results are obtained as an evaluation.

Therefore, by using a photoradical polymerization sensitizer and a photoradical polymerization sensitizing aid in combination, excellent sensitization performance can be achieved in radical polymerization performed using light of a relatively long wavelength such as 405 nm. It can be said that it works.

Claims (4)

In the photoradically polymerizable composition that undergoes photoradical polymerization with light having a peak wavelength in the wavelength range of 380 nm to 420 nm, the radically polymerizable compound is (meth)acrylic acid, (meth)acrylate, fumarate or styrene. or an anthracene compound represented by the general formula (1) as a photoradical polymerization sensitizer and a photoradical polymerization sensitizer containing an onium salt-based photoradical polymerization initiator as a photoradical polymerization initiator; A radically photopolymerizable composition comprising a naphthalene compound represented by the general formula (2) as a sensitizer.

(In the above general formula (1), R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 20 carbon atoms, represents an arylcarbonyl group having 6 to 20 aryl groups, an alkyloxycarbonyl group having an alkyl group having ¹ to 20 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to ²⁰ carbon atoms; X 1 and Y 1 may be the same or different, and X ¹ and Y ¹ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X ¹ and Y ¹ may be the same or different. )

(In general formula (2) above, R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylcarbonyl group having an alkyl group having 1 to 20 carbon atoms. , represents an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 20 carbon atoms, or an aryloxycarbonyl group having an aryl group having ⁶ to 20 carbon atoms; R ⁴ may be the same or different, X ² and Y ² each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X ² and Y ² may be the same or different; is also good.) 2. The photoradically polymerizable composition according to claim 1, wherein the light having a peak wavelength within the wavelength range of 380 nm to 420 nm is light having a peak wavelength at any one of 385 nm, 395 nm, 405 nm and 415 nm. thing. 3. The photoradically polymerizable composition according to claim 1, wherein the light having a peak wavelength within the wavelength range of 380 nm to 420 nm is light having a peak wavelength at 405 nm. 4. The method according to any one of claims 1 to 3 , wherein the amount of the anthracene compound represented by the general formula (1) as a radical photopolymerization sensitizer added to the radically polymerizable compound is 2.0% by weight or less. 1. Photoradical polymerizable composition according to item 1.