JP2017109980A - 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound, production method, and use therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerization sensitizer of a new skeleton structure that is not an anthracene skeleton, a naphthalene skeleton, or a thioxanthone skeleton.SOLUTION: The present invention provides a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound having an optical dimer structure of 1,4-naphtho quinone represented by general formula (1) (A is an alkyl group having 1-10 carbon atoms, acyl group having 2-11 carbon atoms or carbonate ester group having 2-11 carbon atoms, X is a hydrogen atom, C1-C8 alkyl group or C1-C8 alkoxy group).SELECTED DRAWING: None

Description

The present invention relates to a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound, a production method thereof, and a use as a photopolymerization sensitizer.

Photo-curing resins that are polymerized by active energy rays such as ultraviolet rays and visible rays cure quickly and can significantly reduce the amount of organic solvent used compared to thermosetting resins. It is excellent in that it can be reduced. Conventional photocurable resins themselves have a poor polymerization initiating function, and it is usually necessary to use a photopolymerization initiator for curing. As the photopolymerization initiator, alkylphenone-based polymerization initiators such as hydroxyacetophenone and benzophenone, acylphosphine oxide-based photopolymerization initiators, or onium salts are used (Patent Documents 1, 2, and 3). Among these photopolymerization initiators, when hydroxyacetophenone or an onium salt initiator is used as the photopolymerization initiator, the light absorption of the photopolymerization initiator is in the vicinity of 225 nm to 350 nm and does not absorb at 350 nm or more. When a lamp having a long wavelength of 350 nm or more is used as a light source, there is a problem that the photocuring reaction does not proceed easily, and a photopolymerization sensitizer is generally added. As photopolymerization sensitizers, polycyclic aromatic compounds such as naphthalene compounds, anthracene compounds, and thioxanthone compounds are known. In particular, anthracene compounds are often used (Patent Document 4).

As the anthracene photopolymerization sensitizer, a 9,10-dialkoxyanthracene compound is used. For example, a 9,10-dialkoxyanthracene compound such as 9,10-dibutoxyanthracene or 9,10-diethoxyanthracene is used as a photopolymerization sensitizer for an iodonium salt that is a photopolymerization initiator in photopolymerization. (Patent Documents 5, 6, 7, and 8). In recent years, 9,10-bisoctanoyloxyanthracene has also been developed as a photopolymerization sensitizer (Patent Document 9).

However, the fact is that no photopolymerization sensitizer having a new skeleton has been proposed. This is thought to be because the photopolymerization sensitizer need not have only the physical property of being excited by light of a desired wavelength. That is, in order for the photopolymerization sensitizer to exert its effect, as a main property, it is necessary to have the ability to transfer the excitation energy to the target photopolymerization initiator after being excited by the desired light. For this purpose, it is necessary to have an electronic structure capable of exchanging light energy between the photopolymerization sensitizer and the photopolymerization initiator. Therefore, it is difficult to propose a photopolymerization sensitizer having a new skeleton.

On the other hand, with the aim of improving compatibility with photopolymerization initiators, compatibility with polymerizable compounds, and further physical properties of cured products of polymerizable compounds, new skeleton photopolymerization sensitizers are also required without change. ing. In particular, it is known that the photopolymerization sensitizer oozes to the surface due to blooming during photocuring or during storage of the cured product, causing problems with powdering and coloring of the cured product. For example, when these photopolymerization sensitizers are used as a component of a photoadhesive that bonds the film to the film, the photopolymerization sensitizer may migrate to the film overlaid (migration). On top of this, it may cause problems with powdering and coloring of the photopolymerization sensitizer. In order to solve this problem, a photopolymerization sensitizer having high migration resistance is required.

Japanese Patent Laid-Open No. 06-345614 Japanese Patent Application Laid-Open No. 07-062010 JP 05-249606 A JP-A-10-195117 JP 2002-302507 A JP 11-279212 A JP 2000-344704 A WO2007 / 126066 Japanese Patent Application Laid-Open No. 2015-127281

An object of the present invention is to provide a photopolymerization sensitizer having a new skeleton structure that is not an anthracene skeleton, a naphthalene skeleton, or a thioxanthone skeleton, which are main skeletons of conventional photopolymerization sensitizers.

As a result of intensive studies on the structure and light absorption characteristics of the aromatic compound, the present inventor has a photodimer structure of 1,4-naphthoquinone that has not been known at all as a photopolymerization sensitizer. 11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound acts as a photopolymerization sensitizer in photocationic polymerization and photoradical polymerization, and photopolymerization containing the compound as a photopolymerization sensitizer The present invention has been completed by finding that the photopolymerization sensitizer has high migration resistance in the photosensitive composition and its cured product.

That is, the gist of the present invention is the gist of the following.

In order to achieve the above object, the first invention provides a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1).

In the general formula (1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, and X represents a hydrogen atom or 1 to 8 carbon atoms. An alkyl group or an alkoxy group having 1 to 8 carbon atoms.

The second invention provides a 5,6,11,12-tetraalkoxydibenzo [b, h] biphenylene compound represented by the general formula (2).

In General Formula (2), R ¹ represents an alkyl group having 1 to 10 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

The third invention provides a 5,6,11,12-tetraacyloxydibenzo [b, h] biphenylene compound represented by the general formula (3).

In General Formula (3), R ² represents an alkyl group having 1 to 10 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

The fourth invention provides a 5,6,11,12-tetra (alkoxycarbonyloxy) dibenzo [b, h] biphenylene compound represented by the general formula (4).

In General Formula (4), R ³ represents an alkyl group having 1 to 10 carbon atoms or an allyl group, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

In the fifth invention, the 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound represented by the general formula (5) is converted into an etherifying agent, acylating agent or carbonic acid. Provided is a method for producing a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1) by reacting with an esterifying agent.

In General formula (5), X represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkoxy group.

In the general formula (1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, and X represents a hydrogen atom or 1 to 8 carbon atoms. An alkyl group or an alkoxy group having 1 to 8 carbon atoms.

In the sixth invention, the 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound represented by the general formula (6) is reacted with an etherifying agent, an acylating agent or a carbonic acid esterifying agent. Provided is a method for producing a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1).

In General formula (6), X represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkoxy group.

In the general formula (1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, and X represents a hydrogen atom or 1 to 8 carbon atoms. An alkyl group or an alkoxy group having 1 to 8 carbon atoms.

The seventh invention provides a photopolymerization sensitizer comprising a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1).

In the general formula (1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, and X represents a hydrogen atom or 1 to 8 carbon atoms. An alkyl group or an alkoxy group having 1 to 8 carbon atoms.

The eighth invention provides a photopolymerizable composition comprising the photopolymerization sensitizer according to the seventh invention, a photopolymerization initiator, and a polymerizable compound.

In the ninth invention, there is provided a curing method in which the photopolymerizable composition according to the eighth invention is cured by irradiating with an energy ray containing light having a wavelength in the range of 300 nm to 400 nm.

In the description of the present specification, the numbers of the carbon atom positions in the dibenzobiphenylene skeleton which is the basic skeleton are as follows.

Further, the symbols on the sides of the biphenylene skeleton are as follows.

In addition, the carbon number in the terms of an acyl group having 2 to 11 carbon atoms and a carbonic acid ester group having 2 to 11 carbon atoms includes carbonyl carbon.

The 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound of the present invention is a novel compound and exhibits excellent photopolymerization sensitization effects. And the said compound is a photopolymerization sensitizer called the photodimer of 1, 4- naphthoquinone which has a completely different structure from the conventional photopolymerization sensitizer.

Hereinafter, the present invention will be described in detail.

(Compound)
First, the 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1) will be described.

In the general formula (1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, and X represents a hydrogen atom or 1 to 8 carbon atoms. An alkyl group or an alkoxy group having 1 to 8 carbon atoms.

In the general formula (1), when A is an alkyl group, a 5,6,11,12-tetraalkoxydibenzo [b, h] biphenylene compound represented by the general formula (2) is obtained.

In General Formula (2), R ¹ represents an alkyl group having 1 to 10 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

In the general formula (1), when A is an acyl group, a 5,6,11,12-tetraacyloxydibenzo [b, h] biphenylene compound represented by the general formula (3) is provided.

In General Formula (3), R ² represents an alkyl group having 1 to 10 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

In the general formula (1), when A is a carbonate group, a 5,6,11,12-tetra (alkoxycarbonyloxy) dibenzo [b, h] biphenylene compound represented by the general formula (4) It becomes.

In General Formula (4), R ³ represents an alkyl group having 1 to 10 carbon atoms or an allyl group, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

Next, the details of the compounds of the general formulas (2) to (4) will be described. First, the 5,6,11,12-tetraalkoxydibenzo [b, h] biphenylene compound represented by the general formula (2) will be described.

In the general formula (2), the alkyl group having 1 to 10 carbon atoms represented by R ¹ includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group, an n-pentyl group, Examples include an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, a nonyl group, or a decyl group. Examples of the alkyl group having 1 to 8 carbon atoms represented by X include an ethyl group, n -Propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group Ethoxy group, n-propoxy group, n-butoxy group and the like.

Specific examples of the 5,6,11,12-tetraalkoxydibenzo [b, h] biphenylene compound represented by the general formula (2) include the following compounds.

5,6,11,12-tetramethoxydibenzo [b, h] biphenylene, 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene, 5,6,11,12-tetra (n-propoxy) Dibenzo [b, h] biphenylene, 5,6,11,12-tetra (n-butoxy) dibenzo [b, h] biphenylene, 5,6,11,12-tetra (n-pentyloxy) dibenzo [b, h ] Biphenylene, 5,6,11,12-tetra (n-hexyloxy) dibenzo [b, h] biphenylene, 5,6,11,12-tetra (n-heptyloxy) dibenzo [b, h] biphenylene, 5 , 6,11,12-tetra (n-octyloxy) dibenzo [b, h] biphenylene, 5,6,11,12-tetra (2-ethylhexyloxy) dibenzo [ , H] biphenylene, 2,8-dimethyl-5,6,11,12-tetramethoxydibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetraethoxydibenzo [b, h ] Biphenylene, 2,8-dimethyl-5,6,11,12-tetra (n-propoxy) dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra (n-butoxy) ) Dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra (n-pentyloxy) dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11, 12-tetra (n-hexyloxy) dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra (n-heptyloxy) dibenzo [b, h] biphenyle 2,8-dimethyl-5,6,11,12-tetra (n-octyloxy) dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra (2-ethylhexyloxy) ) Dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetramethoxydibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetraethoxydibenzo [B, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra (n-propoxy) dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra (N-butoxy) dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra (n-pentyloxy) dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra (n-hexyloxy) dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra (n-heptyloxy) Dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra (n-octyloxy) dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12 -Tetra (2-ethylhexyloxy) dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetramethoxydibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6, 11,12-tetraethoxydibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra (n-propoxy) dibenzo [b h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra (n-butoxy) dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra (n- Pentyloxy) dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra (n-hexyloxy) dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6 11,12-tetra (n-heptyloxy) dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra (n-octyloxy) dibenzo [b, h] biphenylene, 1, 10-dihydroxy-5,6,11,12-tetra (2-ethylhexyloxy) dibenzo [b, h] biphenylene, 1,10-diethoxy- , 6,11,12-tetramethoxydibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetraethoxydibenzo [b, h] biphenylene, 1,10-diethoxy-5,6 , 11,12-tetra (n-propoxy) dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetra (n-butoxy) dibenzo [b, h] biphenylene, 1,10 -Diethoxy-5,6,11,12-tetra (n-pentyloxy) dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetra (n-hexyloxy) dibenzo [b , H] biphenylene, 1,10-diethoxy-5,6,11,12-tetra (n-heptyloxy) dibenzo [b, h] biphenylene, 1,10-die Toxi-5,6,11,12-tetra (n-octyloxy) dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetra (2-ethylhexyloxy) dibenzo [b, h] Biphenylene and the like.

Among the compounds mentioned above, 5,6,11,12-tetramethoxydibenzo [b, h] biphenylene, 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene, 5 , 6,11,12-tetra (n-propoxy) dibenzo [b, h] biphenylene, 5,6,11,12-tetra (n-butoxy) dibenzo [b, h] biphenylene, 5,6,11,12 -Tetra (n-pentyloxy) dibenzo [b, h] biphenylene, 5,6,11,12-tetra (n-hexyloxy) dibenzo [b, h] biphenylene, 5,6,11,12-tetra (n -Heptyloxy) dibenzo [b, h] biphenylene, 5,6,11,12-tetra (n-octyloxy) dibenzo [b, h] biphenylene, 5,6,11,12- Tora (2-ethylhexyloxy) dibenzo [b, h] biphenylene is preferred, and in particular, 5,6,11,12-tetraethoxydibenzo [b, b) because of its high performance as a photopolymerization sensitizer and ease of production. h] Biphenylene and 5,6,11,12-tetra (n-butoxy) dibenzo [b, h] biphenylene are preferred.

Next, the 5,6,11,12-tetraacyloxydibenzo [b, h] biphenylene compound represented by the general formula (3) will be described.

In the general formula (3), examples of the alkyl group having 1 to 10 carbon atoms represented by R ² include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group, an n-pentyl group, Examples include n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group and the like. Examples of the alkyl group having 1 to 8 carbon atoms represented by X include ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2 -Ethylhexyl group etc. are mentioned, As a C1-C8 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group etc. are mentioned.

Specific examples of the 5,6,11,12-tetraacyloxydibenzo [b, h] biphenylene compound represented by the general formula (3) include the following compounds.

5,6,11,12-tetraacetyloxydibenzo [b, h] biphenylene, 5,6,11,12-tetrapropionyloxydibenzo [b, h] biphenylene, 5,6,11,12-tetrabutyl Ryloxydibenzo [b, h] biphenylene, 5,6,11,12-tetrapentanoyloxydibenzo [b, h] biphenylene, 5,6,11,12-tetrahexanoyloxydibenzo [b, h] biphenylene, 5,6,11,12-tetraheptanoyloxydibenzo [b, h] biphenylene, 5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene, 5,6,11,12-tetra ( 2-ethylhexanoyloxy) dibenzo [b, h] biphenylene, 5,6,11,12-tetranonanoyloxydibenzo [ , H] biphenylene, 5,6,11,12-tetradesanoyloxydibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetraacetyloxydibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetrapropionyloxydibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetrabutyryloxydibenzo [b, h ] Biphenylene, 2,8-dimethyl-5,6,11,12-tetrapentanoyloxydibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetrahexanoyloxydibenzo [b , H] biphenylene, 2,8-dimethyl-5,6,11,12-tetraheptanoyloxydibenzo [b, h] biphenylene, 2,8-dimethyl -5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra (2-ethylhexanoyloxy) dibenzo [b, h] Biphenylene, 2,8-dimethyl-5,6,11,12-tetranonanoyloxydibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetradesanoyloxydibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetraacetyloxydibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetrapropionyloxydibenzo [ b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetrabutyryloxydibenzo [b, h] biphenylene, 1,10-dimethyl Ru-5,6,11,12-tetrapentanoyloxydibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetrahexanoyloxydibenzo [b, h] biphenylene, 1, 10-dimethyl-5,6,11,12-tetraheptanoyloxydibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra (2-ethylhexanoyloxy) dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetranonanoyloxydibenzo [B, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetradesanoyloxydibenzo [b, h] biphenylene, , 10-dihydroxy-5,6,11,12-tetraacetyloxydibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetrapropionyloxydibenzo [b, h] biphenylene 1,10-dihydroxy-5,6,11,12-tetrabutyryloxydibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetrapentanoyloxydibenzo [b, h ] Biphenylene, 1,10-dihydroxy-5,6,11,12-tetrahexanoyloxydibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetraheptanoyloxydibenzo [b , H] biphenylene, 1,10-dihydroxy-5,6,11,12-tetraoctanoyloxydiben [B, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra (2-ethylhexanoyloxy) dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11, 12-tetranonanoyloxydibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetradesanoyloxydibenzo [b, h] biphenylene, 1,10-diethoxy-5,6 11,12-tetraacetyloxydibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetrapropionyloxydibenzo [b, h] biphenylene, 1,10-diethoxy-5 6,11,12-tetrabutyryloxydibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-teto Lapentanoyloxydibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetrahexanoyloxydibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11, 12-tetraheptanoyloxydibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene, 1,10-diethoxy-5,6, 11,12-tetra (2-ethylhexanoyloxy) dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetranonanoyloxydibenzo [b, h] biphenylene, 1,10 -Diethoxy-5,6,11,12-tetradesanoyloxydibenzo [b, h] biphenylene and the like.

Among the above-listed compounds, 5,6,11,12-tetraacetyloxydibenzo [b, h] biphenylene, 5,6,11,12-tetrapropionyloxydibenzo [b, h] are easy to manufacture. ] Biphenylene, 5,6,11,12-tetrabutyryloxydibenzo [b, h] biphenylene, 5,6,11,12-tetrapentanoyloxydibenzo [b, h] biphenylene, 5,6,11,12 Tetrahexanoyloxydibenzo [b, h] biphenylene, 5,6,11,12-tetraheptanoyloxydibenzo [b, h] biphenylene, 5,6,11,12-tetraoctanoyloxydibenzo [b, h ] Biphenylene, 5,6,11,12-tetra (2-ethylhexanoyloxy) dibenzo [b, h] biphenylene, 5,6, 1,12-tetranonanoyloxydibenzo [b, h] biphenylene and 5,6,11,12-tetradesanoyloxydibenzo [b, h] biphenylene are preferable, and particularly high performance as a photopolymerization sensitizer. In view of the ease of production, 5,6,11,12-tetrabutyryloxydibenzo [b, h] biphenylene is preferred.

Next, the 5,6,11,12-tetra (alkoxycarbonyloxy) dibenzo [b, h] biphenylene compound represented by the general formula (4) will be described.

In the general formula (4), the alkyl group having 1 to 10 carbon atoms represented by R ³ includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group, an n-pentyl group, An n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, and the like can be given. Examples of the allyl group include an allyl group and a methallyl group. Examples of the alkyl group having 1 to 8 carbon atoms represented by X include ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2 -Ethylhexyl group etc. are mentioned, As a C1-C8 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group etc. are mentioned.

Specific examples of the 5,6,11,12-tetra (alkoxycarbonyloxy) dibenzo [b, h] biphenylene compound represented by the general formula (4) include the following compounds.

5,6,11,12- (tetramethoxycarbonyloxy) dibenzo [b, h] biphenylene, 5,6,11,12- (tetraethoxycarbonyloxy) dibenzo [b, h] biphenylene, 5,6,11, 12-tetra [(n-propoxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-butoxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6 11,12-tetra [(i-butoxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-pentyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 5 , 6,11,12-tetra [(n-hexyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,1 , 12-tetra [(n-heptyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-octyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 5, , 6,11,12-tetra [(2-ethylhexyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra (allyloxycarbonyloxy) dibenzo [b, h] biphenylene, 5, , 6,11,12-tetra (methallyloxycarbonyloxy) dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12- (tetramethoxycarbonyloxy) dibenzo [b, h] biphenylene 2,8-dimethyl-5,6,11,12- (tetraethoxycarbonyloxy) dibenzo [b h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra [(n-propoxy) carbonyloxy] dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12- Tetra [(n-butoxy) carbonyloxy] dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra [(i-butoxy) carbonyloxy] dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra [(n-pentyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra [( n-hexyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra [(n-heptyloxy) carbo Nyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-octyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12 -Tetra [(2-ethylhexyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetra (allyloxycarbonyloxy) dibenzo [b, h] biphenylene, 2 , 8-dimethyl-5,6,11,12-tetra (methallyloxycarbonyloxy) dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12- (tetramethoxycarbonyloxy) dibenzo [B, h] biphenylene, 1,10-dimethyl-5,6,11,12- (tetraethoxycarbonyloxy) di Benzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra [(n-propoxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6, 11,12-tetra [(n-butoxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra [(i-butoxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra [(n-pentyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12 -Tetra [(n-hexyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra [(n Heptyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-octyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6 , 11,12-tetra [(2-ethylhexyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dimethyl-5,6,11,12-tetra (allyloxycarbonyloxy) dibenzo [b, h ] Biphenylene, 1,10-dimethyl-5,6,11,12-tetra (methallyloxycarbonyloxy) dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12- (tetramethoxy) Carbonyloxy) dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,1 -(Tetraethoxycarbonyloxy) dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra [(n-propoxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10 -Dihydroxy-5,6,11,12-tetra [(n-butoxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra [(i-butoxy) Carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra [(n-pentyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dihydroxy- 5,6,11,12-tetra [(n-hexyloxy) carbonyloxy] dibenzo [b, h] biphenyl Lene, 1,10-dihydroxy-5,6,11,12-tetra [(n-heptyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-octyloxy) ) Carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra [(2-ethylhexyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-dihydroxy -5,6,11,12-tetra (allyloxycarbonyloxy) dibenzo [b, h] biphenylene, 1,10-dihydroxy-5,6,11,12-tetra (methallyloxycarbonyloxy) dibenzo [b, h] Biphenylene, 1,10-diethoxy-5,6,11,12- (tetramethoxycarbonyloxy) Benzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12- (tetraethoxycarbonyloxy) dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12- Tetra [(n-propoxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetra [(n-butoxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetra [(i-butoxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetra [(n -Pentyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetra [(n Hexyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetra [(n-heptyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6 , 11,12-tetra [(n-octyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetra [(2-ethylhexyloxy) carbonyloxy] dibenzo [B, h] biphenylene, 1,10-diethoxy-5,6,11,12-tetra (allyloxycarbonyloxy) dibenzo [b, h] biphenylene, 1,10-diethoxy-5,6,11,12- Tetra (methallyloxycarbonyloxy) dibenzo [b, h] biphenylene and the like.

Among the compounds listed above, 5,6,11,12- (tetramethoxycarbonyloxy) dibenzo [b, h] biphenylene and 5,6,11,12- (tetraethoxycarbonyloxy) dibenzo are easy to manufacture. [B, h] biphenylene, 5,6,11,12-tetra [(n-propoxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-butoxy) carbonyloxy ] Dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(i-butoxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-pentyloxy) ) Carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-hexyloxy) carbonyloxy] Dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-heptyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(n-octyloxy) ) Carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra [(2-ethylhexyloxy) carbonyloxy] dibenzo [b, h] biphenylene, 5,6,11,12-tetra (allyl) Oxycarbonyloxy) dibenzo [b, h] biphenylene and 5,6,11,12-tetra (methallyloxycarbonyloxy) dibenzo [b, h] biphenylene are preferred, and particularly high performance as a photopolymerization sensitizer. And 5,6,11,12-tetraethoxycarbonyloxydibenzo [b, h] biphenylene preferable.

(Production method)
Next, a method for producing the 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1) will be described. As a method for producing the 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound of the present invention, 5,6,11,12-tetraoxo- represented by the general formula (5) is used. 5a, 5b, 11a, 11b-From a method starting from a tetrahydrodibenzo [b, h] biphenylene compound and from a 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound represented by the general formula (6) There are two ways to start.

(Production route 1)
In the first method, according to the following reaction formula (1-1), 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h represented by the general formula (5) ] By reacting a biphenylene compound with a reaction agent comprising any of an etherifying agent, an acylating agent or a carbonic acid esterifying agent in the presence of a basic compound, 5, 6, 11 represented by the general formula (1) , 12-tetra (substituted oxy) dibenzo [b, h] biphenylene compounds can be obtained.

In Reaction Formula (1-1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, and X represents a hydrogen atom or 1 carbon atom. Represents an -8 alkyl group or an alkoxy group having 1 to 8 carbon atoms;

The 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound represented by the general formula (5) used in the reaction formula (1-1) is as follows. As shown in the reaction formula (3), the 1,4-naphthoquinone compound can be produced by light irradiation in a solvent and dimerization.

In Reaction Formula (3), X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

The reaction can be carried out by dissolving a 1,4-naphthoquinone compound in a solvent such as acetonitrile and irradiating with ultraviolet light, for example, light of 300 to 500 nm in a nitrogen atmosphere. By selecting the solvent, the product 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound precipitates with the reaction.

This reaction is a so-called [2 + 2] photocyclization reaction, in which the double bond at the 2- and 3-positions of the naphthoquinone compound is excited by light, and undergoes an addition dimerization reaction to generate a cyclobutane ring. This reaction is forbidden as a thermal reaction, and when heated, triphthaloylbenzene is produced. Therefore, the reaction is performed while removing the generated reaction heat.

As raw material 1,4-naphthoquinone compounds used in the reaction formula (3), 1,4-naphthoquinone, 5-methyl-1,4-naphthoquinone, 6-methyl-1,4-naphthoquinone, 5-methyl-1 , 4-naphthoquinone, 5-methoxy-1,4-naphthoquinone, 5-ethoxy-1,4-naphthoquinone and the like.

As the 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound of the general formula (5) obtained by the reaction formula (3), 5,6,11, 12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene, 2,8-dimethyl-5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene, 1,11-dimethyl-5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene, 1,11-dimethoxy-5,6,11,12 -Tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene, 1,11-diethoxy-5, , 11,12-tetraoxo -5a, 5b, 11a, 11b- tetrahydropyran dibenzo [b, h] biphenylene, and the like.

Next, from the 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound of the general formula (5) obtained by the above reaction, the above general formula (2) A method for producing a 5,6,11,12-tetraalkoxydibenzo [b, h] biphenylene compound represented by the formula:

According to the reaction formula (1-2), the 5,6,11,12-tetraalkoxydibenzo [b, h] biphenylene compound represented by the general formula (2) is 5,6,11,12-tetraoxo-5a, It can be obtained by reacting 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound with an etherifying agent in the presence of a basic compound.

In Reaction Formula (1-2), R ¹ represents an alkyl group having 1 to 10 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

As the etherifying agent used in the reaction formula (1-2), an alkyl halide compound or a dialkyl sulfuric acid is preferably used. Examples of the halogenated alkyl compound include methyl chloride, ethyl chloride, n-propyl chloride, n-butyl chloride, i-butyl chloride, n-amyl chloride, methyl bromide, ethyl bromide, n-propyl bromide, and odor. And n-butyl bromide, i-butyl bromide, n-pentyl bromide, n-hexyl bromide, n-octyl bromide, and 2-ethylhexyl bromide. Examples of the dialkyl sulfuric acid include dimethyl sulfuric acid, diethyl sulfuric acid, dipropyl sulfuric acid and the like.

The amount of the etherifying agent used is usually 4.0 mol times or more, 6.0 times the amount of 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound. It is not more than mol times, preferably not less than 4.2 mol times and not more than 5.5 mol times. When the amount of the etherifying agent used is less than 4.0 mol times, unreacted 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound increases. Even if added over 6.0 mole times, the effect is not increased, and the solubility of the 5,6,11,12-tetraalkoxydibenzo [b, h] biphenylene compound produced on the contrary increases. , The isolation yield decreases.

Examples of basic compounds to be used include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, primary amines, secondary amines, tertiary amines and pyridines.

Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Examples of the alkaline earth metal hydroxide include calcium hydroxide and magnesium hydroxide. Examples of the alkali metal carbonate include sodium carbonate and potassium carbonate.

Examples of the primary amine include methylamine, ethylamine, and propylamine. Examples of the secondary amine include dimethylamine, diethylamine, dibutylamine, and piperidine. Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, Examples thereof include tributylamine, and examples of pyridines include pyridine, α-picoline, β-picoline, γ-picoline, and lutidine.

The addition amount of the basic compound is preferably about equimolar with the etherifying agent to be added.

Solvents used include aromatic solvents such as benzene, toluene, xylene and chlorobenzene, halogenated carbon solvents such as methylene chloride, dichloroethane and dichloroethylene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, Amide solvents such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide, and ether solvents such as tetrahydrofuran and 1,4-dioxane are preferably used.

The reaction temperature is generally 0 to 150 ° C., preferably room temperature to 80 ° C. When the reaction temperature is less than 0 ° C., the reaction rate is too slow and the reaction takes time. When the reaction temperature is higher than 150 ° C., side reaction occurs and the purity of the product decreases. The reaction time is usually 0.5 to 20 hours, although it depends on the reaction temperature. Usually, the reaction is carried out under atmospheric pressure, and the inside of the reaction vessel is preferably in an inert gas atmosphere such as argon or nitrogen.

After completion of the reaction, the reaction mixture is added to a poor solvent such as methanol or hexane, concentrated, and the precipitated crystals are filtered and dried, and then recrystallized as necessary to obtain the desired product with high purity. Can do.

Next, a method for producing a 5,6,11,12-tetraacyloxydibenzo [b, h] biphenylene compound represented by the general formula (3) will be described.

According to the reaction formula (1-3), the 5,6,11,12-tetraacyloxydibenzo [b, h] biphenylene compound represented by the general formula (3) is 5,6,11,12-tetraoxo-5a, It can be obtained by reacting 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound with an acylating agent in the presence of a basic compound.

In Reaction Formula (1-3), R ² represents an alkyl group having 1 to 10 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

The 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound used as a raw material in the reaction formula (1-3) is used in the reaction formula (1-2). Is the same as

As the acylating agent used in the reaction formula (1-3), an acyl halide compound or an organic acid anhydride is used.

Examples of the acyl halide compound include acetyl chloride, propionyl chloride, butyryl chloride, pentanoyl chloride, hexanoyl chloride, heptanoyl chloride, octanoyl chloride, 2-ethylhexanoyl chloride, nonanoyl chloride, desanoyl chloride and the like. Examples of the organic acid anhydride include acetic anhydride, propionic anhydride, butyric anhydride, and the like.

The amount of the acylating agent used is usually 4 mol times or more and 20 mol times or less with respect to 5,6,11,12-tetraoxo-5a, 5b, 11b, tetrahydrodibenzo [b, h] biphenylene compound, Preferably they are 5 mol times or more and 15 mol times or less. When the amount of the acylating agent used is less than 4 mole times, unreacted 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound increases, Even when added in excess of the molar ratio, the effect is not increased, and the solubility of the 5,6,11,12-tetraacyloxydibenzo [b, h] biphenylene compound formed on the contrary increases, and the isolated yield increases. The rate drops.

Examples of basic compounds to be used include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, primary amines, secondary amines, tertiary amines and pyridines.

Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Examples of the alkaline earth metal hydroxide include calcium hydroxide and magnesium hydroxide. Examples of the alkali metal carbonate include sodium carbonate and potassium carbonate.

Examples of the primary amine include methylamine, ethylamine, and propylamine. Examples of the secondary amine include dimethylamine, diethylamine, dibutylamine, and piperidine. Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, Examples thereof include tributylamine, and examples of pyridines include pyridine, α-picoline, β-picoline, γ-picoline, and lutidine.

The addition amount of the basic compound is preferably 0.8 mol times or more and 1.3 mol times or less with respect to the acylating agent to be added.

Solvents used include aromatic solvents such as benzene, toluene, xylene and chlorobenzene, halogenated carbon solvents such as methylene chloride, dichloroethane and dichloroethylene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, Amide solvents such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide, and ether solvents such as tetrahydrofuran and 1,4-dioxane are preferably used.

The reaction temperature is generally 0 to 150 ° C., preferably room temperature to 80 ° C. When the reaction temperature is less than 0 ° C., the reaction rate is too slow and the reaction takes time. When the reaction temperature is higher than 150 ° C., side reaction occurs and the purity of the product decreases. The reaction time is usually 0.5 to 20 hours, although it depends on the reaction temperature. Usually, the reaction is carried out under atmospheric pressure, and the inside of the reaction vessel is preferably in an inert gas atmosphere such as argon or nitrogen.

After completion of the reaction, the reaction mixture is added to a poor solvent such as methanol or hexane, concentrated, and the precipitated crystals are filtered and dried, and then recrystallized as necessary to obtain the desired product with high purity. Can do.

Next, a method for producing a 5,6,11,12-tetra (alkoxycarbonyloxy) dibenzo [b, h] biphenylene compound represented by the general formula (4) will be described.

The 5,6,11,12-tetra (alkoxycarbonyloxy) dibenzo [b, h] biphenylene compound represented by the general formula (4) is obtained according to the reaction formula (1-4). It can be obtained by reacting tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound with a carbonic acid esterifying agent in the presence of a basic compound.

In Reaction Formula (1-4), R ³ represents an alkyl group having 1 to 10 carbon atoms or an allyl group, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. Represent.

The 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound used as a raw material in the reaction formula (1-4) is used in the reaction formula (1-2). Is the same as

Examples of the carbonate esterifying agent used in the reaction formula (1-4) include halogenated carbonates. Methyl chloride carbonate, ethyl chloride carbonate, n-propyl chloride, i-propyl chloride, n-propyl chloride, i-butyl chloride, hexyl chloride, hexyl chloride, octyl chloride, 2-ethylhexyl chloride, carbonate Such as allyl.

The amount of the carbonic acid esterifying agent used is usually 4.0 mol times or more and 6,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound. It is 0 mol times or less, preferably 4.2 mol times or more and 5.5 mol times or less. When the amount of carbonic acid esterifying agent used is less than 4.0 mol times, the amount of unreacted 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound increases. However, even if added over 6.0 mole times, the effect is not increased, and the solubility of the 5,6,11,12-tetraacyloxydibenzo [b, h] biphenylene compound produced on the contrary is high. And the isolation yield decreases.

Examples of basic compounds to be used include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, primary amines, secondary amines, tertiary amines and pyridines.

Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Examples of the alkaline earth metal hydroxide include calcium hydroxide and magnesium hydroxide. Examples of the alkali metal carbonate include sodium carbonate and potassium carbonate.

Examples of the primary amine include methylamine, ethylamine, and propylamine. Examples of the secondary amine include dimethylamine, diethylamine, dibutylamine, and piperidine. Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, Examples thereof include tributylamine, and examples of pyridines include pyridine, α-picoline, β-picoline, γ-picoline, and lutidine.

The addition amount of the basic compound is preferably 0.8 mol times or more and 1.3 mol times or less with respect to the acylating agent to be added.

Solvents used include aromatic solvents such as benzene, toluene, xylene and chlorobenzene, halogenated carbon solvents such as methylene chloride, dichloroethane and dichloroethylene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, Amide solvents such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide, and ether solvents such as tetrahydrofuran and 1,4-dioxane are preferably used.

The reaction temperature is generally 0 to 150 ° C., preferably room temperature to 80 ° C. When the reaction temperature is less than 0 ° C., the reaction rate is too slow and the reaction takes time. When the reaction temperature is higher than 150 ° C., side reaction occurs and the purity of the product decreases. The reaction time is usually 0.5 to 20 hours, although it depends on the reaction temperature. Usually, the reaction is carried out under atmospheric pressure, and the inside of the reaction vessel is preferably in an inert gas atmosphere such as argon or nitrogen.

After completion of the reaction, the reaction mixture is added to a poor solvent such as methanol or hexane, concentrated, and the precipitated crystals are filtered and dried, and then recrystallized as necessary to obtain the desired product with high purity. Can do.

(Production route 2)
Next, a method for producing a 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound represented by the general formula (6) as a starting material will be described.

5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound is represented by general formula (6) according to the following reaction formula (2-1). It can be obtained by reacting a tetrahydroxydibenzo [b, h] biphenylene compound with a reaction reagent comprising any of an etherifying agent, an acylating agent or a carbonic acid esterifying agent in the presence of a basic compound.

In the reaction formula (2-1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, and X represents a hydrogen atom or 1 carbon atom. Represents an -8 alkyl group or an alkoxy group having 1 to 8 carbon atoms;

The 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound represented by the general formula (6) used in the reaction formula (2-1) is a compound represented by the general formula (5). The 6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound can be obtained by a reaction (7) in which it is enolized by heating in the presence of a base.

In Reaction Formula (4), X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

The enolization reaction proceeds under normal enolization reaction conditions. For example, 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound is dissolved in a solvent such as N, N-dimethylacetamide and a base catalyst such as triethylamine is added. The enol body can be enolized with good yield by heating and stirring, and the produced enol body is precipitated in a slurry state and can be isolated only by filtration.

As the 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound obtained by the reaction formula (4), 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene, 2, 8-dimethyl-5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene, 1,11-dimethyl-5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene, 1,11- Examples include dihydroxy-5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene, 1,11-diethoxy-5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene, and the like.

The 5,6,11,12-tetraalkoxydibenzo [b, h] biphenylene compound represented by the general formula (2) using the 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound As a method for producing a compound, a 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound and an etherifying agent are reacted in the presence of a basic compound according to the following reaction formula (2-2). Can be obtained.

In Reaction Formula (2-2), R ¹ represents an alkyl group having 1 to 10 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

The etherifying agent used in the reaction formula (2-2) and the amount of use thereof are the same as the etherifying agent used in the reaction formula (1-2) and the amount of use thereof.

Moreover, the basic compound to be used and its usage-amount are the same as the basic compound and its usage-amount used in Reaction formula (1-2). Furthermore, the solvent used, the reaction temperature, the reaction time, the reaction atmosphere, and the treatment method after the reaction are the same as in the reaction formula (1-2).

Next, 5,6,11,12-tetraacyloxydibenzo [b, h] represented by the general formula (3) using a 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound. A method for producing a biphenylene compound. According to the following reaction formula (2-3), a 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound and an acylating agent are added in the presence of a basic compound. It can be obtained by reacting.

In Reaction Formula (2-3), R ² represents an alkyl group having 1 to 10 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

The acylating agent used in Reaction Formula (2-3) and the amount used thereof are the same as the acylating agent used in Reaction Formula (1-3) and the amount used.

Moreover, the basic compound to be used and its usage-amount are the same as the basic compound and its usage-amount used in Reaction formula (1-3). Furthermore, the solvent used, the reaction temperature, the reaction time, the reaction atmosphere, and the treatment method after the reaction are the same as in the reaction formula (1-3).

Next, using a 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound, a 5,6,11,12-tetra (alkoxycarbonyloxy) dibenzo [ b, h] is a method for producing a biphenylene compound. According to the following reaction formula (2-4), 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound and a carbonic acid esterifying agent are made basic. It can be obtained by reacting in the presence of a compound.

In Reaction Formula (2-4), R ³ represents an alkyl group having 1 to 10 carbon atoms or an allyl group, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. Represent.

The carbonic acid esterifying agent used in the reaction formula (2-4) and the amount of use thereof are the same as the carbonic acid esterifying agent used in the reaction formula (1-4) and the amount of use thereof.

Moreover, the basic compound to be used and its usage-amount are the same as the basic compound and its usage-amount used in Reaction formula (1-4). Furthermore, the solvent used, the reaction temperature, the reaction time, the reaction atmosphere, and the treatment method after the reaction are the same as in the reaction formula (1-4).

(Photopolymerization sensitizer)
The 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1) of the present invention thus obtained is a photocationically polymerizable compound or a photoradical. When the polymerizable compound is polymerized in the presence of a photopolymerization initiator, it can be used as a photocationic polymerization sensitizer or a photoradical polymerization sensitizer.

In the general formula (1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, and X represents a hydrogen atom or 1 to 8 carbon atoms. An alkyl group or an alkoxy group having 1 to 8 carbon atoms.

Moreover, the photopolymerization sensitizer containing the 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1) of the present invention is 5,6,11. , 12-Tetra (substituted oxy) dibenzo [b, h] biphenylene compound as an active ingredient, the total amount of which is 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound In addition to the above, a photopolymerization sensitizer other than the 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound may be included as long as the effects of the present invention are not impaired.

Examples of photopolymerization sensitizers other than such 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compounds include thioxanthone compounds (for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone). , Naphthalene compounds (for example, 1,4-diethoxynaphthalene, 1,4-bis (n-octyloxy) -naphthalene, 1,4-bis (substituted oxy) naphthalene, 4-methoxy-1-naphthol), anthracene compounds ( For example, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene), an amine compound (for example, methyl diethylaminobenzoate), etc. are mentioned.

Photopolymerization sensitizers other than 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compounds with respect to 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compounds Although the addition ratio of is not particularly limited, it is 0.1 to 10 times the weight of the 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound.

(Photopolymerization initiator)
As the photopolymerization initiator, onium salts, benzylmethyl ketal-based, α-hydroxyalkylphenone-based polymerization initiators and the like are preferable. As the onium salt, an iodonium salt or a sulfonium salt is usually used. Examples of the iodonium salt include 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexamethoxyantimonate, 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentamethoxyphenylborate, 4- Examples thereof include isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenylborate and the like. For example, IRGACURE 250 manufactured by BASF (Irgacure is a registered trademark of BASF), manufactured by Rhodia A load sill 2074 (a load sill is a registered trademark of Rhodia Co., Ltd.), IK-1 manufactured by Sun Apro, etc. can be used. On the other hand, examples of the sulfonium salt include S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexamethoxyphosphate, diphenyl-4-phenylthiophenylsulfonium hexanium. Examples thereof include methoxyphosphate, triphenylsulfonium hexamethoxyphosphate, etc., for example, using CPI-100P, CPI101P, CPI-200K manufactured by Daicel, Irgacure 270 manufactured by BAS, UVI6992 manufactured by Dow Chemical Can do. These photopolymerization initiators may be used alone or in combination of two or more.

Moreover, radical polymerization initiators, such as a benzyl methyl ketal type | system | group and an alpha-hydroxyalkyl phenone type polymerization initiator, are mentioned.

Specific examples of the benzylmethyl ketal radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” manufactured by BSF Corporation). As an α-hydroxyalkylphenone radical polymerization initiator, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocur 1173” manufactured by BASF Corporation), 1-hydroxycyclohexyl phenyl ketone (product) Name “Irgacure 184” manufactured by BSF Corporation), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name “Irgacure 2959” BSF Corporation) , 2-hydroxy-1- {4- [4- (2-hydroxy 2-methyl-propionyl) - benzyl] phenyl} -2-methyl-1-one (trade name "Irgacure 127" BASF Corporation).

In particular, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” manufactured by BASF), which is a benzylmethyl ketal radical polymerization initiator, and α-hydroxyalkylphenone radical polymerization initiation 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocur 1173” manufactured by BASF), 1-hydroxycyclohexyl phenylketone (trade name “Irgacure 184” manufactured by BASF) Is preferred.

Further, acetophenone radical polymerization initiators such as acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, 2 -Isobutoxy-2-phenylacetophenone, benzyl radical polymerization initiator benzyl, 4,4'-dimethoxybenzyl, anthraquinone radical polymerization initiator 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-phenoxyanthraquinone 2- (phenylthio) anthraquinone, 2- (hydroxyethylthio) anthraquinone, and the like can also be used.

The amount of the photopolymerization sensitizer containing the 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1) of the present invention to the photopolymerization initiator is: Although not particularly limited, it is usually in the range of 5 to 100% by weight, preferably in the range of 10 to 60% by weight, based on the photopolymerization initiator. If the amount of the photopolymerization sensitizer used is less than 5% by weight, it takes too much time to photopolymerize the photopolymerizable compound. On the other hand, even if it exceeds 100% by weight, an effect commensurate with the addition is obtained. Absent.

A photopolymerization sensitizer containing a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1) of the present invention and a photopolymerization initiator are mixed in advance. May be used as a photopolymerization initiator composition, separately added to the photoradical polymerizable compound or the photocationic polymerizable compound, and in the photoradical polymerizable compound or the photocationic polymerizable compound, as a result, the photopolymerization start An agent composition may be formed.

(Photopolymerizable composition)
Furthermore, a photopolymerizable composition can be prepared by blending the photopolymerization initiator composition and a photopolymerizable compound. The photopolymerizable composition of the present invention is a photopolymerization sensitization containing a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1) of the present invention. It is a composition containing the photoinitiator composition containing an agent and a photoinitiator, and a radical photopolymerizable compound or a photocationic polymerizable compound.

Photopolymerizable compounds include photoradical polymerizable compounds and photocationic polymerizable compounds.

As the photoradical polymerizable compound, for example, an organic compound having a double bond such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, and methacrylic acid ester can be used. . Of these radical polymerizable compounds, acrylic acid esters and methacrylic acid esters (hereinafter, both are referred to as (meth) acrylic acid esters) are preferable from the viewpoint of film forming ability and the like. (Meth) acrylic acid esters include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid. Examples include acid cyclohexyl, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, and imide acrylate. These radical photopolymerizable compounds may be one kind or a mixture of two or more kinds.

Examples of the cationic photopolymerizable compound include epoxy compounds and vinyl ethers. Examples of general epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl ethers. Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, and examples thereof include UVR6105, UVR6110, manufactured by Dow Chemical Co., Ltd. Daicel's Celoxide 2021P (Celoxide is a registered trademark of Daicel Corporation) and the like can be used. Examples of the epoxy-modified silicone include UV-9300 manufactured by Toshiba GE Silicone. Examples of the aromatic glycidyl compound include 2,2'-bis (4-glycidyloxyphenyl) propane. Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like. These photocationically polymerizable compounds may be one kind or a mixture of two or more kinds.

In the photopolymerizable composition of the present invention, the photopolymerization initiator composition is used in an amount of 0.005% by weight or more and less than 10% by weight, preferably 0.025% by weight, based on the photopolymerizable composition. The content is 5% by weight or less. If it is 0.005% by weight or less, it takes time to photopolymerize the photopolymerizable composition. On the other hand, if it exceeds 10% by weight, the hardness of the photocured product obtained by photopolymerization decreases, This is not preferable because the physical properties of the cured product are deteriorated.

In addition, the photopolymerizable composition of the present invention has a diluent, a colorant, an organic or inorganic filler, a leveling agent, a surfactant, an antifoaming agent, a thickener, within a range not impairing the effects of the present invention. Various resin additives such as flame retardants, antioxidants, stabilizers, lubricants, and plasticizers may be blended.

(Photocured product)
A photocured product can be obtained by polymerizing the photopolymerizable composition of the present invention by irradiating light. When the photopolymerizable composition is irradiated with light to be polymerized and photocured, the photopolymerizable composition can be formed into a film and photocured, or can be formed into a lump and photocured. When forming into a film shape and photocuring, the liquid photopolymerizable composition is applied to a substrate such as a polyester film so as to have a film thickness of 5 to 300 microns using a bar coater or the like. On the other hand, it can also be applied with a thinner or thicker film by spin coating or screen printing.

A photocured product is obtained by irradiating the coating film made of the photopolymerizable composition thus prepared with ultraviolet light having a wavelength range of 250 to 500 nm at an intensity of about 1 to 1000 mW / cm ^2. Can do. As a light source to be used, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, xenon lamp, gallium doped lamp, black light, 395 nm ultraviolet LED, 385 nm ultraviolet LED, 365 nm ultraviolet LED, blue LED, white LED, D manufactured by Fusion Examples thereof include a valve and a V valve. Natural light such as sunlight can also be used. In particular, ultraviolet rays including a wavelength range of 300 to 400 nm are preferable, and 395 nm ultraviolet LEDs, 385 nm ultraviolet LEDs, and 365 nm ultraviolet LEDs are particularly preferable as the irradiation light source.

(Tack free test)
As a method for determining whether or not the photopolymerizable composition of the present invention has been photocured, there is a tack free test. That is, when the photopolymerizable composition is irradiated with light, it is polymerized and there is no tack (stickiness) on the surface. Therefore, the photocuring time is measured by measuring the time from when the light is irradiated until tack (stickiness) disappears. Can be measured.

(Determination of migration resistance)
As a method for determining whether or not the photopolymerization sensitizer contained in the photopolymerizable composition of the present invention migrates to a film or the like, the photopolymerizable composition containing the photopolymerization sensitizer is a thin film. Create a product applied to the object, cover it with a polyethylene film, store it at a constant temperature (26 ° C) for a certain period of time, then peel off the polyethylene film, and examine whether the photopolymerization sensitizer has transferred to the polyethylene film The migration resistance was determined. The peeled polyethylene film was washed after washing the surface composition with acetone, measured for UV resistance of the polyethylene film, and measured for migration resistance by examining the increase in absorption intensity caused by the photopolymerization sensitizer. did. For the measurement, an ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2200) was used. In order to quantitatively compare with 9,10-dibutoxyanthracene, which is the compound of the comparative example, the obtained absorbance was converted to the absorbance value of 9,10-dibutoxyanthracene. In conversion, the absorbance at 260 nm of the compound of the present invention and 9,10-dibutoxyanthracene was measured with an ultraviolet / visible spectrophotometer, the respective molar extinction coefficients were calculated from the absorbance value and molar concentration, and the ratio And converted.

The present invention is illustrated by the following examples which are not intended to limit the scope of the invention. Unless otherwise specified, all parts are parts by weight. The product was confirmed based on the measurement by the following equipment.

(1) Melting point: Melting point measuring device manufactured by Gelen Camp, model MFB-595 (conforms to JIS K0064)
(2) Infrared (IR) spectrophotometer: Model IR-810 manufactured by JASCO Corporation
(3) Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model GSX FT NMR Spectrometer

Synthesis Example 1 Synthesis of 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene 3.0 g (19.0) of 1,4-naphthoquinone in a 100 ml eggplant flask Mmol) was dissolved in 30 g of acetonitrile. Subsequently, irradiation was performed at an irradiation intensity of 50 mW / cm ² using a 365 nm UV-LED (irradiation area: 10 cm ² ) LHPUV365 manufactured by Iwasaki Electric under a nitrogen atmosphere. After irradiation for 10 hours, the precipitated white precipitate was suction filtered and dried, and 1.8 g (11.4 mmol) of 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h ] Biphenylene was obtained.
(1) Melting point: 254-255 ° C
(2) IR (KBr, cm ⁻¹ ): 1676, 1681, 1287, 1252, 945, 780, 703, 678, 541.
(3) ¹ H-NMR (400 MHz, heavy acetone): δ 3.96 (s, 4H), 7.91 (s, 4H), 8.10 (s, 4H).

Synthesis Example 2 Synthesis of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene 5,6,11 synthesized in the same manner as in Synthesis Example 1 in a 100 ml three-necked eggplant flask equipped with a thermometer and a condenser. , 12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene (3.16 g, 10 mmol) is dispersed in 30 g of N, N-dimethylacetamide, and 1.0 g (10 mmol) of triethylamine is dispersed. In addition, it was heated at 60 ° C. for 2 hours. Since the white slurry becomes a true yellow slurry, suction filtration and drying are performed, and 2.84 g (9.1 mmol) of a true yellow powder of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene is obtained. Obtained. The yield based on the raw material 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene was 91 mol%.
(1) Melting point: 252-254 ° C
(2) IR (KBr, cm ⁻¹ ): 3180, 1583, 1508, 1292, 1257, 1187, 1097, 965, 762, 632, 595.
(3) ¹ H-NMR (400 MHz, heavy acetone): δ 7.30 (s, 4H), 7.98 (s, 4H), 8.56 (bs, 4H)

(Synthesis Example 1) 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene synthesis thermometer according to production route 1 in a 100 ml three-necked flask equipped with a condenser in a nitrogen atmosphere under Synthesis Example 1 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene (2.0 g, 6.3 mmol) synthesized in the same manner; To a yellow slurry of 25 g of N-dimethylacetamide and 4.6 g (30 mmol) of diethyl sulfate, a solution of 12 g of sodium hydroxide (12 g) in 12 g of water was added dropwise. Since it became a blackish green solution immediately, it was heated at 60 ° C. for 30 minutes. Since yellow crystals were precipitated, suction filtration, washing with methanol, and drying were performed to obtain 1.7 g (3.97 mmol) of a yellow powder of 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene. . The isolated yield based on the starting material 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene was 63 mol%.
(1) Melting point: 135-137 ° C
(2) IR (KBr, cm ⁻¹ ): 3080, 2980, 2945, 2900, 1670, 1610, 1580, 1565, 1370, 1330, 1279, 1188, 1095, 1026, 934, 895, 759, 659
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.50 (t, J = 8 Hz, 12H), 4.44 (q, J = 8 Hz, 8H), 7.38 (s, 4H), 7 .96 (s, 4H)

(Synthesis Example 2) Synthesis route 2 and 5,6,11,12-tetramethoxydibenzo [b, h] biphenylene synthesis thermometer, in a 100 ml three-necked flask with a condenser, in a nitrogen atmosphere, in Synthesis Example 2 1.0 g (3.1 mmol) of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene synthesized in the same manner; To a yellow slurry of 16 g of N-dimethylacetamide and 1.89 g (15 mmol) of dimethyl sulfate, a solution of 8 g of water of 0.60 g (15 mmol) of sodium hydroxide was added dropwise. Since it became a blackish green solution immediately, it was heated at 60 ° C. for 30 minutes. After cooling, crystals precipitate. Suction filtration, washing with methanol, and drying to obtain 0.70 g (1.88 mmol) of a yellow powder of 5,6,11,12-tetramethoxydibenzo [b, h] biphenylene. It was. The isolated yield based on the starting material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 63 mol%.
(1) Melting point: 217-218 ° C
(2) IR (KBr, cm ⁻¹ ): 3070, 3010, 2940, 2850, 1613, 1570, 1510, 1450, 1337, 1281, 1200, 1179, 1097, 1078, 1011, 960, 769, 747, 663 560
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 4.18 (s, 12H), 7.40 (s, 4H), 7.97 (s, 4H)

(Synthesis Example 3) Synthesis route 2 and 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene synthesis thermometer, in a 100 ml three-necked flask equipped with a condenser, in a nitrogen atmosphere, in Synthesis Example 2 0.49 g (1.55 mmol) of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene synthesized in the same manner; To a yellow slurry of 10 g of N-dimethylacetamide and 1.23 g (8 mmol) of diethylsulfuric acid, a 5 g solution of 0.32 g (8 mmol) of sodium hydroxide was added dropwise. Since it became a blackish green solution immediately, it was heated at 60 ° C. for 30 minutes. After cooling, the pH of the reaction solution is returned to neutral, and crystals are precipitated. Thus, suction filtration, washing with methanol, and drying are performed, and yellow powder of 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene is obtained. .37 g (0.87 mmol) was obtained. The isolated yield based on 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene as a raw material was 56 mol%.
(1) Melting point: 254-255 ° C
(2) IR (KBr, cm ⁻¹ ): 1676, 1681, 1287, 1252, 945, 780, 703, 678, 541.
(3) ¹ H-NMR (400 MHz, heavy acetone): δ 3.96 (s, 4H), 7.91 (s, 4H), 8.10 (s, 4H).

(Synthesis Example 4) Synthesis route of 5,6,11,12-tetrabutoxydibenzo [b, h] biphenylene according to production route 2 in a 100 ml three-necked flask with a condenser in a nitrogen atmosphere under Synthesis Example 2 1.0 g (3.2 mmol) of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene synthesized in the same manner; A solution of sodium hydroxide (0.60 g, 15 mmol) in water (7 g) was added dropwise to a yellow slurry of N-dimethylacetamide (15 g) and butyl bromide (2.1 g, 15 mmol). Since it became a blackish green solution immediately, it was heated at 60 ° C. for 30 minutes. After cooling, the pH of the reaction solution is returned to neutral, and crystals are precipitated. Thus, suction filtration, washing with methanol, and drying are performed, and a yellow powder of 5,6,11,12-tetrabutoxydibenzo [b, h] biphenylene is obtained. Obtained .54 g (1.02 mmol). The isolated yield based on the starting material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 31 mol%.
(1) Melting point: 81-82 ° C
(2) IR (KBr, cm ⁻¹ ): 3070, 2960, 2930, 2870, 1540, 1600, 1332, 1280, 1185, 1094, 1073, 1059, 1020, 942, 763, 744, 660, 555 cm−1.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ1.00 (t, J = 8 Hz, 12H), 1.49-1.59 (m, 8H), 1.78-1.88 (m, 8H), 4.32 (t, J = 8 Hz, 8H), 7.39 (s, 4H), 7.98 (s, 4H).

(Synthesis Example 5) Synthesis route 2 and 5,6,11,12-tetraacetyloxydibenzo [b, h] biphenylene thermometer, in a 100 ml three-necked flask equipped with a cooler, in Synthesis Example 2 In the same manner, 2.2 g (7.0 mmol) of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene, 25 g of N, N-dimethylacetamide and 5.9 g (50 mmol) of acetic anhydride were synthesized. In addition, a light yellow slurry was obtained. Next, 4.04 g (40 mmol) of triethylamine was added and stirred for 30 minutes. The slurry turned white. Suction filtered, washed with hexane and dried to give 2.4 g (4.56 mmol) of white powder of 5,6,11,12-tetraacetoxydibenzo [b, h] biphenylene. The isolated yield based on the starting material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 65 mol%.
(1) Melting point: 255 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 2920, 1761, 1645, 1520, 1410, 1370, 1340, 1285, 1192, 1173, 1089, 1058, 1007, 942, 896 863, 758, 659, 597, 573.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 4.00 (s, 12H), 7.45 (t, J = 9 Hza, 4H), 7.80 (d, J = 9 Hz, 4H).

(Synthesis Example 6) 5,6,11,12-tetrapropionyloxydibenzo [b, h] biphenylene synthesis thermometer according to production route 2 and a 100 ml three-neck flask with a condenser in a nitrogen atmosphere under Synthesis Example 2 Similarly synthesized 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene 0.9 g (2.85 mmol), N, N-dimethylacetamide 15 g, propionic anhydride 3.9 g (30 mmol) Was added to obtain a light yellow slurry. Next, 3.03 g (30 mmol) of triethylamine was added and stirred for 5 minutes. When the solution was further stirred, a large amount of white crystals precipitated after 10 minutes, and the mixture was further stirred for 20 minutes. The resulting white slurry was filtered with suction, washed with methanol, and dried to obtain 0.7 g (1.3 mmol) of white powder of 5,6,11,12-tetrapropionyloxydibenzo [b, h] biphenylene. It was. The isolated yield based on the starting material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 46 mol%.
(1) Melting point: 255 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3045, 2970, 2930, 1758, 1555, 1410, 1335, 1285, 1139, 1119, 1093, 1072, 880, 810, 754
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ1.31 (t, J = 8 Hz, 12H), 2,85 (q, J = 8 Hz, 8H), 7.50 (t, J = 9 Hz, 4H), 7.79 (d, J = 9 Hz, 4H).

(Synthesis Example 7) Synthesis route 2 for 5,6,11,12-tetrabutyryloxydibenzo [b, h] biphenylene synthesis route 2 in a 100 ml three-necked flask equipped with a condenser under a nitrogen atmosphere, Synthesis Example 2 5,8,11,12-tetrahydroxydibenzo [b, h] biphenylene 1.58 g (5.0 mmol), N, N-dimethylacetamide 20 g, butyryl chloride 3.18 g (30 mmol) Was added to obtain a light yellow slurry. Next, 4.04 g (40 mmol) of triethylamine was added and stirred for 30 minutes. Subsequently, 30 g of methanol was added, and the resulting white slurry was suction filtered, dried, and 2.1 g (3.5 mmol) of white powder of 5,6,11,12-tetrabutyryloxydibenzo [b, h] biphenylene. ) The isolated yield based on the starting material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 70 mol%.
(1) Melting point: 260 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3040, 2960, 2940, 2865, 1758, 1339, 1282, 1179, 1130, 1099, 1073, 943, 754.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.10 (t, J = 8 Hz, 12 H), 1.83-1.94 (m, 8 H), 2.68 (t, J = 8 Hz, 8H), 7.39 (t, J = 9 Hz, 4H), 7.65 (d, J = 9 Hz, 4H).

(Synthesis Example 8) 5,6,11,12-tetraheptanoyloxydibenzo [b, h] biphenylene synthesis thermometer according to production route 2 Synthesis Example 2 in a 100 ml three-necked flask equipped with a condenser in a nitrogen atmosphere 5,11,12-tetrahydroxydibenzo [b, h] biphenylene 1.11 g (3.48 mmol), N, N-dimethylacetamide 15 g, octanoyl chloride 8.13 g (50 mmol) Was added to obtain a light yellow slurry. Next, 5.05 g (50 mmol) of triethylamine was added and stirred for 30 minutes. Next, 20 g of methanol was added, and the resulting white slurry was suction filtered, dried, and 1.50 g (1.9 mmol) of white powder of 5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene. ) The isolated yield based on the starting material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 55 mol%.
(1) Melting point: 184-186 ° C
(2) IR (KBr, cm ⁻¹ ): 2960, 2926, 2840, 1755, 1660, 1520, 1460, 1410, 1380, 1337, 1280, 1131, 1104, 758, 723
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.91 (t, J = 8 Hz, 12H), 1.31-1.40 (m, 16H), 1.40-1.60 (m, 8H), 1.80-1.90 (m, 8H), 2.69 (t, J = 8 Hz, 8H), 7.39 (t, J = 9 Hz, 4H), 7.64 (d, J = 9Hz, 4H).

(Synthesis Example 9) 5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene synthesis thermometer according to production route 2 Synthesis Example 2 in a 100 ml three-necked flask equipped with a condenser in a nitrogen atmosphere 5,11,12-tetrahydroxydibenzo [b, h] biphenylene 1.11 g (3.48 mmol), N, N-dimethylacetamide 15 g, octanoyl chloride 8.13 g (50 mmol) Was added to obtain a light yellow slurry. Next, 5.05 g (50 mmol) of triethylamine was added and stirred for 30 minutes. Next, 20 g of methanol was added, and the resulting white slurry was suction filtered, dried, and 1.50 g (1.9 mmol) of white powder of 5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene. ) The isolated yield based on the starting material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 55 mol%.
(1) Melting point: 184-186 ° C
(2) IR (KBr, cm ⁻¹ ): 2950, 2915, 2850, 1759, 1700, 1580, 1510, 1460, 1450, 1340, 1285, 1271, 1222, 1113, 942, 919, 754, 719, 703 541.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.87 (t, J = 8 Hz, 12H), 1.11-1.66 (m, 32H), 1.75-1.92 (m, 8H), 2.70 (t, J = 8 Hz, 8H), 7.39 (t, J = 9 Hz, 4H), 7.63 (d, J = 9 Hz, 4H).

(Synthesis Example 10) Synthesis route for 5,6,11,12-tetra (2-ethylhexanoyloxy) dibenzo [b, h] biphenylene according to production route 2 and nitrogen atmosphere in a 100 ml three-necked flask equipped with a condenser Below, 1.56 g (5.0 mmol) of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene synthesized in the same manner as in Synthesis Example 2, 20 g of N, N-dimethylacetamide, 2-ethyl chloride 4.86 g (30 mmol) of hexanoyl was added to form a pale yellow slurry. Next, 4.04 g (40 mmol) of triethylamine was added and stirred for 30 minutes. Next, 20 g of methanol was added, and the resulting white slurry was suction filtered, dried, and 1.90 g of white powder of 5,6,11,12-tetra (2-ethylhexanoyloxy) dibenzo [b, h] biphenylene. (2.4 mmol) was obtained. The isolated yield based on the starting material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 48 mol%.
(1) Melting point: 100-101 ° C
(2) IR (KBr, cm ⁻¹ ): 2950, 2932, 2865, 1755, 1630, 1450, 1336, 1280, 1159, 1092, 759.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.92 (t, J = 8 Hz, 12H), 1.08 (t, J = 8 Hz, 12H), 1.34-1.49 (m, 16H), 1.70-2.00 (m, 16H), 2.64-2.76 (m, 4H), 7.37 (t, J = 9 Hz, 4H), 7.61 (d, J = 9Hz, 4H).

(Synthesis Example 11) 5,6,11,12-tetranonanoyloxydibenzo [b, h] biphenylene synthesis thermometer according to production route 2 Synthesis Example 2 in a 100 ml three-necked flask equipped with a condenser in a nitrogen atmosphere 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene 1.10 g (3.48 mmol), N, N-dimethylacetamide 15 g, nonanoyl chloride 8.8 g (50 mmol) Was added to obtain a light yellow slurry. Next, 5.05 g (50 mmol) of triethylamine was added and stirred for 30 minutes. Next, 20 g of methanol was added, and the resulting white slurry was suction filtered, dried, and 2.10 g (2.4 mmol) of white powder of 5,6,11,12-tetranonanoyldibenzo [b, h] biphenylene. Got. The isolated yield based on the starting material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 69 mol%.
(1) Melting point: 173-174 ° C
(2) IR (KBr, cm ⁻¹ ): 2916, 2850, 1758, 1338, 1284, 1261, 1130, 1116, 1061, 755, 719.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.89 (t, J = 8 Hz, 12H), 1.13-1.40 (m, 32H), 1.40-1.50 (m, 8H), 1.79-1.90 (m, 8H), 2.69 (t, J = 8 Hz, 8H), 7.40 (t, J = 9 Hz, 4H), 7.64 (d, J = 9Hz, 4H).

(Synthesis Example 12) Synthesis route of 5,6,11,12-tetramethoxycarbonyloxydibenzo [b, h] biphenylene according to production route 2 and synthesis in a 100 ml three-necked flask equipped with a condenser under a nitrogen atmosphere 2,6,11,12-tetrahydroxydibenzo [b, h] biphenylene 1.0 g (3.2 mmol), N, N-dimethylacetamide 15 g, methyl chloride 1.5 g (16 Millimoles). A solution of 1.3 g (13 mmol) of triethylamine in 4 g of N, N-dimethylacetamide was added to the pale yellow slurry. After stirring for 30 minutes, 15 g of water was added to the obtained yellow-green slurry and reslurried, followed by suction filtration, washing with water, washing with methanol and drying, and then 5,6,11,12- (tetramethoxycarbonyloxy) dibenzo [b, h ] 1.3 g (2.4 mmol) of biphenylene was obtained as a pale yellow powder. The isolated yield based on the raw material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 75 mol%.
(1) Melting point: 255 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3075, 3030, 2970, 2840, 1769, 1440, 1294, 1234, 1183, 1090, 1056, 929, 762, 602, 539.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 4.00 (s, 12H), 7.45 (t, J = 9 Hza, 4H), 7.80 (d, J = 9 Hz, 4H).

(Synthesis Example 13) Synthesis route of 5,6,11,12-tetra (n-propoxycarbonyloxy) dibenzo [b, h] biphenylene according to production route 2 and nitrogen atmosphere in a 100 ml three-necked flask equipped with a condenser Below, 1.0 g (3.2 mmol) of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene synthesized in the same manner as in Synthesis Example 2, 15 g of N, N-dimethylacetamide, n-chlorocarbonate 1.83 g (15 mmol) of propyl was charged. A solution of 1.3 g (13 mmol) of triethylamine in 4 g of N, N-dimethylacetamide was added to the pale yellow slurry. After stirring for 30 minutes, 15 g of water was added to the resulting yellow-green slurry and reslurried, followed by suction filtration, washing with water, washing with methanol, and drying, 5,6,11,12- [tetra (n-propoxy) carbonyloxy) dibenzo [B, h] A pale white powder of 1.3 g (2.0 mmol) of biphenylene was obtained. The isolated yield based on the raw material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 62 mol%.
(1) Melting point: 173-174 ° C
(2) IR (KBr, cm ⁻¹ ): 2960, 2930, 2870, 1760, 1214, 1180, 1154, 1052, 934, 764.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ1.00 (t, J = 8 Hz, 12H), 1.83-1.94 (m, 8H), 4.30 (t, J = 8 Hz, 8H), 7.43 (t, J = 9 Hz, 4H), 7.81 (d, J = 9 Hz, 4H).

(Synthesis Example 14) Synthesis route of 5,6,11,12-tetra (i-propoxycarbonyloxy) dibenzo [b, h] biphenylene according to production route 2 and nitrogen atmosphere in a 100 ml three-necked flask equipped with a condenser Below, 1.1 g (3.5 mmol) of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene synthesized in the same manner as in Synthesis Example 2, 15 g of N, N-dimethylacetamide, i-chlorocarbonate 2.13 g (17.5 mmol) of propyl was charged. A solution of 1.8 g (18 mmol) of triethylamine in 5 g of N, N-dimethylacetamide was added to the light yellow slurry. After stirring for 30 minutes, 15 g of water was added to the obtained yellow-green slurry and reslurried, followed by suction filtration, washing with water, washing with methanol, and drying, 5,6,11,12- [tetra (i-propoxy) carbonyloxy) dibenzo [B, h] 1.5 g (2.3 mmol) of yellowish white powder was obtained. The isolated yield based on the raw material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 65 mol%.
(1) Melting point: 260 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3060, 2970, 2920, 2840, 1757, 1222, 1179, 1077, 983, 928, 906, 842, 771, 740, 711 601,538,425.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ1.41 (d, J = 8 Hz, 24H), 5.01-5.10 (m, 4H), 7.45 (t, J = 9 Hz, 4H), 7.78 (d, J = 9 Hz, 4H).

(Synthesis Example 15) 5,6,11,12-tetra (i-butoxycarbonyloxy) dibenzo [b, h] biphenylene synthesis thermometer according to production route 2 and nitrogen atmosphere in a 100 ml three-necked flask equipped with a condenser Below, 1.56 g (5.0 mmol) of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene synthesized in the same manner as in Synthesis Example 2, 20 g of N, N-dimethylacetamide, i-chlorocarbonate 4.08 g (30 mmol) of butyl was charged. A solution of 4 g (40 mmol) of triethylamine in 10 g of N, N-dimethylacetamide was added to the pale yellow slurry. After stirring for 30 minutes, 25 g of water was added to the obtained yellow-green slurry and reslurried, followed by suction filtration, washing with water, washing with methanol, and drying, 5,6,11,12- [tetra (i-butoxy) carbonyloxy) dibenzo [B, h] biphenylene 2.3 g (32 mmol) of yellowish white powder was obtained. The isolated yield based on the raw material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 64 mol%.
(1) Melting point: 180-181 ° C
(2) IR (KBr, cm ⁻¹ ): 2960, 2870, 1763, 1217, 1177, 1151, 1084, 1042, 949, 768, 752.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ0.99 (d, J = 8 Hz, 24H), 2.01-2.11 (m, 4H), 4.12 (d, J = 9 Hz, 8H), 7.45 (t, J = 9 Hz, 4H), 7.80 (d, J = 9 Hz, 4H).

(Synthesis Example 16) 5,6,11,12-tetra (2-ethylhexyloxycarbonyloxy) dibenzo [b, h] biphenylene synthesis thermometer according to production route 2 and nitrogen in a 100 ml three-necked flask equipped with a condenser Under an atmosphere, 1.75 g (5.5 mmol) of 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene synthesized in the same manner as in Synthesis Example 2, 20 g of N, N-dimethylacetamide, 2 carbonic acid chloride -5.0 g (26 mmol) of ethylhexyl was charged. A solution of 2.5 g (25 mmol) of triethylamine in 5 g of N, N-dimethylacetamide was added to the light yellow slurry. After stirring for 30 minutes, 15 g of water was added to the resulting yellow-green slurry, and the pale orange candy that settled on the bottom was washed thoroughly with water and dried to give 5,6,11,12- [tetra (2-ethylhexyloxy) carbonyl Oxy) dibenzo [b, h] biphenylene 5.1 g (52 mmol) of pale orange candy was obtained. The isolated yield based on the raw material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 96 mol%.
(1) Melting point: room temperature candy-like (2) IR (Nujol, cm ⁻¹ ): 2950, 2915, 2850, 1770, 1460, 1217, 1182, 1153, 940, 766.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.82 (t, J = 8 Hz, 12H), 0.92 (t, J = 9 Hz, 12H), 1.21-1.48 (m, 32H), 1.64-1.74 (m, 4H), 4.28 (t, J = 8 Hz, 8H), 7.44 (t, J = 9 Hz, 4H), 7.79 (d, J = 9Hz, 4H).

(Synthesis Example 17) Synthesis route for 5,6,11,12-tetra (allyloxycarbonyloxy) dibenzo [b, h] biphenylene according to production route 2 in a 100 ml three-necked flask equipped with a condenser under nitrogen atmosphere 1,6,11,12-tetrahydroxydibenzo [b, h] biphenylene 1.0 g (3.2 mmol), N, N-dimethylacetamide 20 g, allyl chloride 1. 92 g (16 mmol) was charged. A solution of 1.5 g (15 mmol) of triethylamine in 5 g of N, N-dimethylacetamide was added to the pale yellow slurry. After stirring for 30 minutes, 20 g of water was added to the obtained yellow-green slurry and reslurried, followed by suction filtration, water washing, methanol washing and drying, and then 5,6,11,12- (tetraallyloxycarbonyloxy) dibenzo [b, h] 2.3 g (35 mmol) of yellowish white powder was obtained. The isolated yield based on the raw material 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene was 70 mol%.
(1) Melting point: 181-182 ° C
(2) IR (KBr, cm ⁻¹ ): 3065, 2940, 1767, 1755, 1216, 1181, 1150, 1090, 1045, 991, 979, 956, 930, 821, 755, 614.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 4.82 (d, J = 8 Hz, 8H), 5.33 (d, J = 9 Hz, 4H), 5.45 (d, J = 17 Hz, 4H), 5.97-6.09 (m, 4H), 7.45 (t, J = 9 Hz, 4H), 7.82 (d, J = 9 Hz, 4H).

Examples of photocationic curing evaluation are shown below.

(Evaluation Example 1)
A photopolymerization initiator 4-isobutylphenyl-4′-methylphenyliodonium was added to 100 parts of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P, manufactured by Daicel) as a photocationically polymerizable compound. Photopolymerization sensitizer 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene 1 synthesized in the same manner as in Synthesis Example 1 with 2.0 parts of hexafluorophosphate (Irgacure 250 manufactured by BASF) 0.0 part was added to obtain a uniform composition. This composition was applied using a bar coater to a film thickness of 18 microns on a polyester film mirror (film thickness 100 microns, Lumirror is a registered trademark of Toray Industries, Inc.). Subsequently, ultraviolet LED was irradiated using LHPUV365 made from Iwasaki Electric. The central wavelength of the irradiation light is 365 nm and the irradiation intensity is 15 mW / cm ² . The light irradiation time “tack free time” until stickiness disappears was 14 seconds.

(Evaluation Comparative Example 1-1)
A photopolymerizable composition was prepared in the same manner as in Evaluation Example 1 except that 5,6,11,12-tetramethoxydibenzo [b, h] biphenylene was not used as a photopolymerization sensitizer, The polymerizable composition was applied, and irradiated with light under the same conditions as in Evaluation Example 1 using a 365-nm UV-LED. It was not photocured even after 1000 seconds of irradiation.

(Evaluation Comparative Example 1-2)
Evaluation was made except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, was used instead of 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene as the photopolymerization sensitizer. A photopolymerizable composition was prepared in the same manner as in Example 1, then the photopolymerizable composition was applied, and irradiated with light under the same conditions as in Evaluation Example 1 using a 365-nm UV-LED. The light irradiation time “tack free time” until stickiness disappears was 18 seconds.
(Evaluation Example 2)
As a photocationically polymerizable compound, 100 parts of 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel) was added to a photopolymerization initiator 4-isobutylphenyl-4′-methylphenyliodonium hexa. Photopolymerization sensitizer 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene synthesized in the same manner as in Synthesis Example 1 with 2.0 parts of fluorophosphate (Irgacure 250 manufactured by BASF). 0 parts was added to obtain a uniform composition. This composition was applied using a bar coater to a film thickness of 18 microns on a polyester film mirror (film thickness 100 microns, Lumirror is a registered trademark of Toray Industries, Inc.). Subsequently, ultraviolet LED was irradiated using FireFly395 of Phoseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 25 mW / cm ² . The light irradiation time “tack free time” until stickiness disappears was 16 seconds.

(Evaluation Comparative Example 2-1)
A photopolymerizable composition was prepared in the same manner as in Evaluation Example 2, except that 5,6,11,12-tetramethoxydibenzo [b, h] biphenylene was not used as the photopolymerization sensitizer, The polymerizable composition was applied, and irradiated with light under the same conditions as in Evaluation Example 2 using a 395 nm UV-LED. It was not photocured even after 1000 seconds of irradiation.

As is clear by comparing Evaluation Example 1 with Evaluation Comparative Example 1-1 and Evaluation Example 2 with Evaluation Comparative Example 2-1, in the case of any polymerization conditions of 365 nm and 395 nm light irradiation in the photocationic polymerization. Also, in the present invention, the remarkable curing rate promoting effect by adding 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene of the present invention, that is, photopolymerization sensitizing effect is recognized. Furthermore, as is clear by comparing Evaluation Example 1 and Evaluation Example 1-2, the sensitizing effect is superior to 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer. I understand.

Next, a photo-radical curing evaluation example is shown.

(Evaluation Example 3)
As a photo-radically polymerizable compound, 100 parts of pentaerythritol tetraacrylate (Osaka Organic Chemical Co., Ltd. Biscoat 400, Biscoat is a registered trademark of Osaka Organic Chemical Co., Ltd.), photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (manufactured by BISF) Irgacure 184) 1.0 part and 1.0 part of photopolymerization sensitizer 5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene synthesized in the same manner as in Synthesis Example 9 were added, and uniform. Composition. This composition was applied on a polyester film mirror (thickness: 100 microns, Lumirror is a registered trademark of Toray Industries, Inc.) to a thickness of 30 microns using a bar coater. The coated photopolymerizable composition was covered with a tack film having a thickness of 50 microns and then irradiated with an ultraviolet LED. The central wavelength of the irradiation light is 365 nm and the irradiation intensity is 10 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 3 seconds.

(Evaluation Comparative Example 3-1)
As a photopolymerization sensitizer, except that 5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene is used as 9,10-bisoctanoyloxyanthracene which is a known photopolymerization sensitizer. Then, a photopolymerizable composition was prepared in the same manner as in Evaluation Example 3, and then the photopolymerizable composition was applied and irradiated with light under the same conditions as in Evaluation Example 3 using a 365-nm UV-LED. The light irradiation time “tack free time” until tackiness disappears was 9 seconds.

Comparison of the results of (Evaluation Example 3) and (Evaluation Comparative Example 3-1) reveals the following. When the photoradical polymerization is performed using the 5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene of the present invention as a photopolymerization sensitizer, it exhibits an excellent photopolymerization sensitization effect and is a tack-free test. From these results, it can be seen that the photopolymerization sensitizing ability is equivalent to or higher than 9,10-bis (octanoyloxy) anthracene which is a known photopolymerization sensitizer.

Next, evaluation examples of migration resistance in photocationic polymerization and photoradical polymerization are shown.

(Evaluation Example of Migration Resistance in Photocationic Polymerization)
(Evaluation Example 4)
In the same manner as in Synthesis Example 1 as a photopolymerization sensitizer, 100 parts of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel) was used as the photocationically polymerizable compound. 1 part of the synthesized 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene was mixed, and the prepared composition was coated on a polyester film using a bar coater so that the film thickness was 12 microns. . Next, a low-density polyethylene film (film thickness of 30 microns) was put on the obtained coating and stored in the dark for one day, stored for two days, or stored for four days. The film was peeled off, the polyethylene film was washed with acetone and dried, then the UV spectrum of the film was measured, and the absorbance at 304 nm was measured. The absorbance of the obtained 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene was converted to 9,10-dibutoxyanthracene. The absorbance was 0.10 after 1 day storage, 0.11 after 2 days storage, and 0.11 after 4 days storage.

(Evaluation Comparative Example 4)
Evaluation was performed except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, was used instead of 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene as a photopolymerization sensitizer. Prepared as in Example 4. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9,10-dibutoxyanthracene was 0.68 after 1 day storage, 0.72 after 2 days storage, and 0.74 after 4 days storage. It was.

(Evaluation Example of Migration Resistance in Photoradical Polymerization)
(Evaluation Example 5)
1 part of 5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene synthesized in the same manner as in Synthesis Example 9 was mixed with 100 parts of trimethylolpropane triacrylate as a photoradical polymerizable compound. The prepared composition was applied on a polyester film using a bar coater so as to have a film thickness of 12 microns. Next, a low-density polyethylene film (film thickness of 30 microns) was put on the obtained coating and stored in the dark for one day, stored for two days, or stored for four days. The film was peeled off, the polyethylene film was washed with acetone and dried, then the UV spectrum of the film was measured, and the absorbance at 295 nm was measured. The absorbance of the obtained 5,6,11,12-tetraoctanoyloxydibenzo [b, h] biphenylene was converted to 9,10-dibutoxyanthracene. The absorbance was 0.001 after 1 day storage, 0.0015 after 2 days storage, and 0.001 after 4 days storage.

(Evaluation Comparative Example 5)
Evaluation was performed except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, was used instead of 5,6,11,12-tetraethoxydibenzo [b, h] biphenylene as a photopolymerization sensitizer. Prepared as in Example 3. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9,10-dibutoxyanthracene was 1.14 after 1 day storage, 1.24 after 2 days storage, and 1.20 after 4 days storage. It was.

From the above results, the 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound of the present invention is a known photopolymerization sensitizer in photocationic polymerization and photoradical polymerization. , 10-Dibutoxyanthracene has not only the same photopolymerization sensitizing ability, but also a transfer rate to a polyethylene film placed on the polymerizable composition is a known photopolymerization sensitizer. Since it is remarkably lower than 10-dibutoxyanthracene, it can be seen that it is an excellent compound with high migration resistance and is a very useful compound as a photopolymerization sensitizer.

Claims (9)

5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1).

(In General Formula (1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, X is a hydrogen atom, 8 represents an alkyl group or an alkoxy group having 1 to 8 carbon atoms.) 5,6,11,12-tetraalkoxydibenzo [b, h] biphenylene compound represented by the general formula (2).

(In General Formula (2), R ¹ represents an alkyl group having 1 to 10 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.) 5,6,11,12-tetraacyloxydibenzo [b, h] biphenylene compound.

(In General Formula (3), R ² represents an alkyl group having 1 to 10 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.) There is provided a 5,6,11,12-tetra (alkoxycarbonyloxy) dibenzo [b, h] biphenylene compound represented by the general formula (4).

(In General Formula (4), R ³ represents an alkyl group having 1 to 10 carbon atoms or an allyl group, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. .) Reaction of 5,6,11,12-tetraoxo-5a, 5b, 11a, 11b-tetrahydrodibenzo [b, h] biphenylene compound represented by general formula (5) with an etherifying agent, acylating agent or carbonic acid esterifying agent To produce a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1).

(In General Formula (5), X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.)

(In General Formula (1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, X is a hydrogen atom, 8 represents an alkyl group or an alkoxy group having 1 to 8 carbon atoms.) By reacting the 5,6,11,12-tetrahydroxydibenzo [b, h] biphenylene compound represented by the general formula (6) with an etherifying agent, an acylating agent or a carbonic acid esterifying agent, the general formula (1) A process for producing a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the formula:

(In General Formula (6), X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.)

(In General Formula (1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, X is a hydrogen atom, 8 represents an alkyl group or an alkoxy group having 1 to 8 carbon atoms.) A photopolymerization sensitizer comprising a 5,6,11,12-tetra (substituted oxy) dibenzo [b, h] biphenylene compound represented by the general formula (1).

(In General Formula (1), A represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 11 carbon atoms, or a carbonic acid ester group having 2 to 11 carbon atoms, X is a hydrogen atom, 8 represents an alkyl group or an alkoxy group having 1 to 8 carbon atoms.) A photopolymerizable composition comprising the photopolymerization sensitizer according to claim 7, a photopolymerization initiator, and a polymerizable compound. The hardening method which hardens | cures by irradiating the photopolymerizable composition of Claim 8 with the energy ray containing the light of the wavelength of the range of 300 nm to 400 nm.