JP2000344704A - New anthracene compound, resin composition containing the compound and production of 9,10-dietherified anthracene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new anthracene compound having relatively low melting point and excellent solubility to cation-polymerizable compound, producible without using a catalyst recovering step and useful as a sensitizer for a cationic polymerization initiator. SOLUTION: The objective compound is expressed by formula [R1 to R8 are each H, a 1-12C alkyl or the like; X is (CH2)1Y, ((CH2)mO)nZ ((l) is 2-8; (m) and (n) are each 1-4) or the like; Y is F or Cl; Z is a 1-8C alkyl or the like], e.g. 9,10-di(2-bromoethoxy)anthracene. The photopolymerization composition contains a cation-polymerizable compound (e.g. epoxy compound), an energy ray sensitive cationic polymerization initiator (e.g. a sulfonium salt) and the objective compound as essential constituent components preferably at ratios of 100:(0.1-30):(1-30). The composition is useful for printing ink, coating material, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel anthracene compound useful as a photosensitizer, a resin composition containing the same, and a novel method for producing a 9,10-dietherified anthracene compound.

[0002]

2. Description of the Related Art A photopolymerizable composition using a cationically polymerizable compound and a photocationic polymerization initiator has a greater effect of inhibiting curing by oxygen than a photopolymerizable composition using a radically polymerizable compound and a photoradical polymerization initiator. It has the advantage of not undergoing the curing, but has the disadvantage that the curing speed is slow. As a method of increasing the curing rate of a photopolymerizable composition using a cationic polymerizable compound and a photocationic polymerization initiator, for example, Japanese Patent Application Laid-Open No.
There is known a method of using an anthracene compound such as 9,10-dimethoxy-2-ethylanthracene as a sensitizer, such as 502461. Further, JP-A-10-147
608 describes various anthracene derivatives as specific examples of such an anthracene compound having a sensitizing effect.

[0003] As for the method of producing anthracene derivatives, a method of synthesizing an aromatic compound such as anthracene by reducing quinones such as anthraquinone has been known for a long time. For example, JPShaefer is J.Org.Chem., 25,20
27 (1916), a method using Sn-Hg in hydrochloric acid, EL
Martin, in J. Am. Chem. Soc., 58, 1438 (1936), reports on a Zn-Cu process in aqueous sodium hydroxide. Regarding such reduction using metals, K.
Tsuda, E. Ohki, S. Nozoe et al. Described the method using Zn in J. Org. Chem., 28, 786 (1963), and
Has been reported. AJFatiadi and WFSager describe the method using metal salts in the literature "Or
ganic Syntheses, ”Coll.
2 is reported. On the other hand, regarding the metal hydrogen complex compound, HC Brown et al., Israel J. Chem., 1, 43
0 (1963), LiAlH (O-tC4H9) 3, J. Am. Chem. Soc., 87, 5614 (1965).
The production method using (OCH3) 3 is described in J. Am. Chem. Soc., 88, 1458.
(1966) describes the production method using LiAlH4 and J. Am.
m. Soc., 88, 1458 (1966) reports on the production method using AlH3. Also GSPanson and CE
Weill, J. Org. Chem., 22, 120 (1957), reports a process using NaBH4. However, a method of synthesizing an aromatic compound such as 9,10-dietherified anthracene by reducing quinones such as anthraquinone using hydrazines is not known.

[0004]

A conventionally known anthracene compound is a compound having a high melting point and strong crystallinity.
There are drawbacks such as poor solubility in various cationically polymerizable compounds, inability to increase the amount added to the photopolymerizable composition, and separation even after dissolution once depending on storage conditions.

[0005] Regarding the method for producing a 9,10-dietherified anthracene compound, when an organic chemical reaction is carried out, heavy metals are rarely used in ordinary synthesis, but the above-mentioned Zn and Cu are used in a reduction reaction. , S
Heavy metals such as n and Cr are often utilized. After completion of the reaction, these heavy metals are rarely contained in the target compound. However, after completion of the reaction, these heavy metals must be recovered and discarded. These heavy metals easily generate ions harmful to living organisms and the environment in the natural environment, and require special treatment when disposed. In the case of metal hydride complex compounds, lithium aluminum hydride and sodium aluminum hydride violently react with water to generate hydrogen, and if they remain excessively after the reaction, hydrogen is generated when they come into contact with water. With danger. Also, sodium borohydride and lithium borohydride are generally expensive. Note that borane reduction using borane or diborane can also be used to synthesize aromatic compounds by reducing quinones, but the reaction of borane reduction in this case is very slow, There is a high possibility that cost performance does not match for producing aromatic compounds.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. A very important new anthracene derivative, further reducing the anthraquinone derivative with hydrazines to form a leuco form, and then reacting with an appropriate alkylating agent, thereby producing an anthracene derivative having a desired structure at a low cost and a simple method. And succeeded in establishing the present invention. That is, the present invention relates to [1] a 9,10-dietherified anthracene compound represented by the formula (1)

[0007]

Embedded image
(1)

(Where R₁, R_Two, R_Three, R_Four, R_Five, R₆,
R₇And R₈Is independently a hydrogen atom, C₁~ C₁₂
Alkyl group, fluorine atom, chlorine atom, bromine atom, shea
Group, phenyl group, cyclohexyl group, hydroxyl group, benzyl
Group, cyclohexylmethyl group, 1-naphthyl group, 2-
Naphthyl group, -OR₉, -CO-R₉Or -SR₉
Is one of Further R₉Is C₁~ C₈An alkyl group of
Phenyl, benzyl, cyclohexyl, cyclohexyl
Xylmethyl group, 1-naphthyl group or 2-naphthyl
Any of the groups. X is-(CH_Two) LY,-
((CH_Two)_mO)_nZ,-(CH (CH_Three) CH_TwoO)
_nZ,-(CH_Two)_mO (CH_Two)_nOZ, allyl group, group
Lysidyl group, cyclohexyl group, cyclohexylmethyl
Group, 1-naphthyl group, 2-naphthyl group, 3-hydroxy
Propyl, 4-hydroxybutyl, 4-tert-butyl
Rucyclohexyl group or 4-methyl-3-pentenyl
And Y is a fluorine atom, a chlorine atom
Atom, bromine atom, phenyl group, cyclohexyl group, 1-na
A phenyl group or a 2-naphthyl group;
Is C ₁~ C₈A linear or branched alkyl group of₁~ C₈
Linear or branched saturated or unsaturated acyl groups,
, Glycidyl, phenyl, benzyl, cyclo
Hexyl group, 2-phenylethyl group, 2-hydroxy
Tyl group, 3-hydroxypropyl group, 4-hydroxybut
Tyl group, benzoyl group, cyclohexylmethyl group, 1-
A naphthyl group or a 2-naphthyl group,
l is an integer of 2 to 8, m and n are integers of 1 to 4
You. [2] In the formula (1), R_Two, R_Three, R₆Or R₇of
Any one is a hydrogen atom, C₁~ C₁₂Alkyl group,
Nitrogen, chlorine, bromine, cyano, phenyl
Group, cyclohexyl group, hydroxyl group, benzyl group, cyclohexyl group
Xylmethyl group, 1-naphthyl group, 2-naphthyl group,-
OR₉, -CO-R₉Or -SR₉(R₉Is C₁~ C₈
Alkyl group, phenyl group, benzyl group,
Xyl group, cyclohexylmethyl group, 1-naphthyl group
Or a 2-naphthyl group, and the remaining substituents
Is a hydrogen atom, and R₁, R_Four, R^FiveAnd R₈Is a hydrogen atom
And X is-(CH_l) Y,-((CH_Two)_mO)
_nZ,-(CH (CH_Three) CH_TwoO)_nZ,-(CH_Two)
_mO (CH_Two)_nOZ, allyl group, glycidyl group, shik
Rohexyl group, cyclohexylmethyl group, 1-naphthyl
Group, 2-naphthyl group, 3-hydroxypropyl group, 4-
Hydroxybutyl group, 4-tert-butylcyclohexyl
Any of a sil group or a 4-methyl-3-pentenyl group
And Y is a fluorine atom, a chlorine atom, a bromine atom
Phenyl group, cyclohexyl group, 1-naphthyl group
Or a 2-naphthyl group, and Z is C₁~ C₈
A linear or branched alkyl group of₁~ C₈Straight chain or
Represents a branched saturated or unsaturated acyl group, allyl group,
Sidyl group, phenyl group, benzyl group, cyclohexyl
Group, 2-phenylethyl group, 2-hydroxyethyl group,
3-hydroxypropyl group, 4-hydroxybutyl group,
Benzoyl group, cyclohexylmethyl group, 1-naphthyl
Group or a 2-naphthyl group, and l is 2 to
An integer of 8, m and n are integers of 1 to 4. No)
And the remaining substituents are hydrogen atoms.
The anthracene compound according to [3], wherein in the formula (1),
R_Two, R_Three, R₆Or R₇One of them is a hydrogen atom
Or an ethyl group, and the remaining substituents are hydrogen atoms.
R₁, R_Four, R^FiveAnd R₈Is a hydrogen atom.
The anthracene compound according to [4], in formula (1)
And R_Two, R_Three, R₆Or R₇One of is ethyl
And the remaining substituents are hydrogen atoms, R₁, R_Four,
R^FiveAnd R₈Is a hydrogen atom, and X is 2-methoxyethyl
9. The 9,10-dietherified ether according to claim 1, which is
Anthracene compound, [5] as an essential component, (1)
Cationic polymerizable compound and (2) energy ray-sensitive click
An on-polymerization initiator and (3) the 9,10 diee according to claim 1.
It is characterized by containing an anthracene telluride compound
The photopolymerizable composition, wherein the anthracene compound [6] is used.
9,10-dietherified anthracene compound described in
The photopolymerizable composition according to claim 5, [7] anthra
The 9,10-dietherification according to claim 3, wherein the cene compound is used.
The photopolymerizable group according to claim 5, which is an anthracene compound.
[8] Reduction of anthraquinones with hydrazines
And then reacting with an appropriate alkylating agent
Of 9,10-dietherified anthracene derivative
[9] Anthraquinones of formula (2)

[0009]

Embedded image
(2)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ and R ₈ each independently represent a hydrogen atom, a C ₁ -C ₁₂ alkyl group, a fluorine atom, a chlorine atom, a bromine atom, a cyano group,
Phenyl group, cyclohexyl group, hydroxyl group, benzyl group,
Cyclohexylmethyl group, 1-naphthyl group, 2-naphthyl group, -OR ₉ , -CO-R ₉ or -SR ₉ (R ₉ is an alkyl group from C _{1 to} C ₈ , a phenyl group, a benzyl group ,
A cyclohexyl group, a cyclohexylmethyl group, a 1-naphthyl group or a 2-naphthyl group. ). The method for producing a 9,10-dietherified anthracene derivative according to claim 3, wherein the compound of the formula (2) is R ₂ , R ₃ , or R _6.
Alternatively, any one of R ₇ is a hydrogen atom, a C _{1 to} C ₁₂ alkyl group, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a phenyl group, a cyclohexyl group, a hydroxyl group, a benzyl group, a cyclohexylmethyl group, 1-naphthyl Group, 2-naphthyl group, -OR ₉ , -CO-R ₉ or -SR
₉ (R ₉ is a C ₁ -C ₈ alkyl, phenyl, benzyl, cyclohexyl, cyclohexylmethyl, 1-
It is either a naphthyl group or a 2-naphthyl group. The remaining substituents are hydrogen atoms, and R ₁ , R ₄ , R ⁵ and R ₈ are hydrogen atoms.
The method for producing a 9,10-dietherified anthracene according to the above item [11], wherein the compound of the formula (2) is a compound wherein one of R ₂ , R ₃ , R ₆ or R ₇ is a hydrogen atom or an ethyl group Is a hydrogen atom, and R ₁ , R ₄ , R ₅
9. The method according to claim 8, wherein R and R ₈ are hydrogen atoms.
-A process for the preparation of dietherified anthracene. [12] The alkylating agent has the formula (3)

[0011]

Embedded image (3)

A p-toluenesulfonic acid ester compound represented by the formula or an alkylsulfonic acid ester compound represented by the formula R ₁ SO ₂ OX ′ (4) or a formula (X′O) ₂ SO ₂ (5) Alkyl sulfonic acid ester compound (wherein
R ₁₀ is a methyl group, an ethyl group or a trifluoromethyl group, and X ′ is a C _{1 to} C ₁₈ linear or branched alkyl group, a benzyl group, an α-methylbenzyl group, — (CH _{2) lY, - ((CH} 2) m O) n Z, -
_{(CH (CH 3) CH 2} O) nZ, - (CH 2) m O (C
H ₂ ) _n OZ, allyl group, glycidyl group, cyclohexyl group, cyclohexylmethyl group, 1-naphthyl group, 2-
Naphthyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 4-tert-
A butylcyclohexyl group or a 4-methyl-3-pentenyl group, and Y represents a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a cyclohexyl group,
A naphthyl group or a 2-naphthyl group, and Z represents a C ₁ -C ₈ linear or branched alkyl group;
Linear or branched, saturated or unsaturated acyl group having ₁ -C _8, an allyl group, a glycidyl group, a phenyl group, a benzyl group, a cyclohexyl group, a 2-phenylethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group , 4-hydroxybutyl group, benzoyl group, cyclohexylmethyl group, 1-naphthyl group or 2-naphthyl group, l is an integer of 2-8, and m and n are integers of 1-4. The method for producing a 9,10-dietherified anthracene derivative according to any one of claims 8, 9, 10, and 11;

[13] the alkylating agent is p-toluenesulfonic acid ester represented by the formula (3):
The present invention relates to a method for producing a 9,10-dietherified anthracene derivative according to any one of claims 9, 10 and 11.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (1), R ₁ to
In R _8, the alkyl group of C ₁ -C _12, for example a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, tert- butyl group, n- pentyl group, an isopentyl group , N-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, 2-ethyl-hexyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n- Dodecyl group, isododecyl group and the like. Examples of -OR9 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert- group.
Butoxy group, n-pentoxy group,

Isopentoxy, n-hexoxy, isohexoxy, n-heptoxy, isoheptoxy, n-octoxy, isooctoxy, 2-ethylhexoxy, phenoxy, phenylmethyloxy, cyclohexoxy, cyclohexylmethyloxy Group, 1-naphthoxy group, 2-naphthoxy group and the like. As —CO—R ₉ , for example, a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group,
Isopropylcarbonyl group, n-butylcarbonyl group,
Isobutylcarbonyl group, tert-butylcarbonyl group, n-pentylcarbonyl group, isopentylcarbonyl group, n-hexylcarbonyl group, isohexylcarbonyl group, n-heptylcarbonyl group, isoheptylcarbonyl group, n-octylcarbonyl group, Examples include an octylcarbonyl group, a 2-ethylhexylcarbonyl group, a phenylcarbonyl group, a phenylmethylcarbonyl group, a cyclohexylcarbonyl group, a cyclohexylmethylcarbonyl group, a 1-naphthylcarbonyl group, and a 2-naphthylcarbonyl group. As -SR ₉ , for example,
Methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, n-pentylthio, isopentylthio, n-hexylthio, isohexylthio, n -Heptylthio group, isoheptylthio group, n
-Octylthio, isooctylthio, 2-ethylhexylthio, phenylthio, phenylmethylthio, cyclohexylthio, cyclohexylmethylthio, 1-naphthylthio, 2-naphthylthio, and the like.

Specific examples of — (CH ₂ ) _l Y in the substituent X in the general formula (1) include, for example, 2-
Fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2- (1-naphthyl) ethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3- Bromopropyl group, 3-phenylpropyl group, 3-cyclohexylpropyl group, 3- (1-naphthyl) propyl group, 4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 4-phenylbutyl group, 4- Cyclohexylbutyl, 4- (1-naphthyl) butyl, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-phenylpentyl, 5-cyclohexylpentyl, 5- (1-naphthyl) ) Pentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-phenyl Hexyl group, 6-cyclohexylhexyl group, 6- (1-naphthyl) hexyl group, 7-fluoroheptyl group, 7-chloroheptyl group, 7-bromoheptyl group, 7-phenylheptyl group, 7-cyclohexylheptyl group, 7 -(1-naphthyl) heptyl group, 8
-Fluorooctyl group, 8-chlorooctyl group, 8-bromooctyl group, 8-phenyloctyl group, 8-cyclohexyloctyl group, 8- (1-naphthyl) octyl group and the like. Specific examples of-((CH2) mO) nZ include, for example, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-n-propoxyethyl group, a 2-isopropoxyethyl group, and a 2-n-butoxyethyl group. , 2-isobutoxyethyl group, 2-n-hexoxyethyl group, 2-
Isohexoxyethyl group, 2-n-octoxyethyl group, 2-isooctoxyethyl group, 2-acetoxyethyl group, 2-allyloxyethyl group, 2-cyclohexoxyethyl group, 2- (1-naphthoxy) Ethyl group, 2-
(2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-n-propoxyethoxy) ethyl group, 2- (2-isopropoxyethoxy)
Ethyl group, 2- (2-n-butoxyethoxy) ethyl group, 2- (2-isobutoxyethoxy) ethyl group, 2-
(2-n-hexoxyethoxy) ethyl group, 2- (2-
Isohexoxyethoxy) ethyl group, 2- (2-n-octoxyethoxy) ethyl group, 2- (2-isooctoxyethoxy) ethyl group, 2- (2-acetoxyethoxy) ethyl group, 2- (2 -Allyloxyethoxy) ethyl group, 2- (2-hydroxyethoxy) ethyl group, 2-
(2-cyclohexoxyethoxy) ethyl group, 2- (2
-(1-naphthoxy) ethoxy) ethyl group, 2- (2-
(2-methoxyethoxy) ethoxy) ethyl group, 2-
(2- (2-ethoxyethoxy) ethoxy) ethyl group,
2- (2- (2-n-propoxyethoxy) ethoxy)
Ethyl group, 2- (2- (2-isopropoxyethoxy)
Ethoxy) ethyl group, 2- (2- (2-n-butoxyethoxy) ethoxy) ethyl group, 2- (2- (2-isobutoxyethoxy) ethoxy) ethyl group, 2- (2- (2
-N-hexoxyethoxy) ethoxy) ethyl group, 2-
(2- (2-isohexoxyethoxy) ethoxy) ethyl group, 2- (2- (2-n-octoxyethoxy) ethoxy) ethyl group, 2- (2- (2-isooctoxyethoxy) ethoxy) Ethyl group, 2- (2- (2-acetoxyethoxy) ethoxy) ethyl group, 2- (2- (2-allyloxyethoxy) ethoxy) ethyl group, 2- (2-
(2-hydroxyethoxy) ethoxy) ethyl group, 2-
(2- (2-cyclohexoxyethoxy) ethoxy) ethyl group, 2- (2- (2- (1-naphthoxy) ethoxy) ethoxy) ethyl group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ) Ethoxy) ethyl group, 2-
(2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2- (2- (2-n-propoxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2
-(2- (2-isopropoxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2- (2- (2-n-butoxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2
-(2- (2-isobutoxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2- (2- (2-n-hexoxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2
-(2- (2-isohexoxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2- (2- (2-n-octoxyethoxy) ethoxy) ethoxy) ethyl group, 2-
(2- (2- (2-isooctoxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2- (2- (2-acetoxyethoxy) ethoxy) ethoxy) ethyl group, 2-
(2- (2- (2-allyloxyethoxy) ethoxy)
An ethoxy) ethyl group, a 2- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) ethyl group, a 2- (2
-(2- (2-phenoxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2- (2- (2-cyclohexoxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2
-(2- (2- (1-naphthoxy) ethoxy) ethoxy) ethoxy) ethyl group, 3-methoxypropyl group, 3
-Ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3-n-butoxypropyl group, 3-isobutoxypropyl group, 3-n-hexoxypropyl group, 3-isohexoxypropyl Group,
3-n-octoxypropyl group, 3-isooctoxypropyl group, 3-acetoxypropyl group, 3-allyloxypropyl group, 3-phenoxypropyl group, 3-cyclohexoxypropyl group, 3- (1-naphthoxy) Propyl group, 3- (3-methoxypropoxy) propyl group, 3
-(3-ethoxypropoxy) propyl group, 3- (3-
n-propoxypropoxy) propyl group, 3- (3-isopropoxypropoxy) propyl group, 3- (3-n-
Butoxypropoxy) propyl group, 3- (3-isobutoxypropoxy) propyl group, 3- (3-n-hexoxypropoxy) propyl group, 3- (3-isohexoxypropoxy) propyl group, 3- (3- n-octoxypropoxy) propyl group, 3- (3-isooctoxypropoxy) propyl group, 3- (3-acetoxypropoxy) propyl group, 3- (3-allyloxypropoxy)
Propyl group, 3- (3-hydroxypropoxy) propyl group, 3- (3-phenoxypropoxy) propyl group,
3- (3-cyclohexoxypropoxy) propyl group,
3- (3- (1-naphthoxy) propoxy) propyl group, 3- (3- (3-methoxypropoxy) propoxy) propyl group, 3- (3- (3-ethoxypropoxy) propoxy) propyl group, 3- ( 3- (3-n-propoxypropoxy) propoxy) propyl group, 3-
(3- (3-isopropoxypropoxy) propoxy)
Propyl group, 3- (3- (3-n-butoxypropoxy) propoxy) propyl group, 3- (3- (3-isobutoxypropoxy) propoxy) propyl group, 3- (3
-(3-n-hexoxypropoxy) propoxy) propyl group, 3- (3- (3-isohexoxypropoxy)
Propoxy) propyl group, 3- (3- (3-n-octoxypropoxy) propoxy) propyl group, 3- (3-
(3-isooctoxypropoxy) propoxy) propyl group, 3- (3- (3-acetoxypropoxy) propoxy) propyl group, 3- (3- (3-allyloxypropoxy) propoxy) propyl group, 3- (3 -(3-hydroxypropoxy) propoxy) propyl group, 3-
(3- (3-phenoxypropoxy) propoxy) propyl group, 3- (3- (3-cyclohexoxypropoxy) propoxy) propyl group, 3- (3- (3- (1-
Naphthoxy) propoxy) propoxy) propyl group, 3
-(3- (3- (3-methoxypropoxy) propoxy) propoxy) propyl group, 3- (3- (3- (3- (3-
Ethoxypropoxy) propoxy) propoxy) propyl group, 3- (3- (3- (3-n-propoxypropoxy) propoxy) propoxy) propyl group, 3- (3-
(3- (3-isopropoxypropoxy) propoxy)
Propoxy) propyl group, 3- (3- (3- (3-n-
Butoxypropoxy) propoxy) propoxy) propyl group, 3- (3- (3- (3-isobutoxypropoxy) propoxy) propoxy) propyl group, 3- (3-
(3- (3-n-hexoxypropoxy) propoxy)
Propoxy) propyl group, 3- (3- (3- (3-isohexoxypropoxy) propoxy) propoxy) propyl group, 3- (3- (3- (3-n-octoxypropoxy) propoxy) propoxy) propyl Group, 3- (3
-(3- (3-isooctoxypropoxy) propoxy) propoxy) propyl group, 3- (3- (3- (3-
Acetoxypropoxy) propoxy) propoxy) propyl group, 3- (3- (3- (3-allyloxypropoxy) propoxy) propoxy) propyl group, 3- (3-
(3- (3-hydroxypropoxy) propoxy) propoxy) propyl group, 3- (3- (3- (3-phenoxypropoxy) propoxy) propoxy) propyl group,
3- (3- (3- (3-cyclohexoxypropoxy)
Propoxy) propoxy) propyl group, 3- (3- (3
-(3- (1-naphthoxy) propoxy) propoxy)
Propoxy) propyl group, 4-methoxybutyl group, 4-
Ethoxybutyl group, 4-n-propoxybutyl group, 4-
Isopropoxybutyl group, 4-n-butoxybutyl group,
4-isobutoxybutyl group, 4-n-hexoxybutyl group, 4-isohexoxybutyl group, 4-n-octoxybutyl group, 4-isooctoxybutyl group, 4-acetoxybutyl group, 4-allyloxybutyl Group, 4-phenoxybutyl group, 4-cyclohexoxybutyl group, 4- (1
-Naphthoxy) butyl group, 4- (4-methoxybutoxy) butyl group, 4- (4-ethoxybutoxy) butyl group, 4- (4-n-propoxybutoxy) butyl group,
-(4-isopropoxybutoxy) butyl group, 4- (4
-N-butoxybutoxy) butyl group, 4- (4-isobutoxybutoxy) butyl group, 4- (4-n-hexoxybutoxy) butyl group, 4- (4-isohexoxybutoxy) butyl group, 4- (4-n-octoxybutoxy) butyl group, 4- (4-isooctoxybutoxy) butyl group, 4- (4-acetoxybutoxy) butyl group, 4-
(4-allyloxybutoxy) butyl group, 4- (4-hydroxybutoxy) butyl group, 4- (4-phenoxybutoxy) butyl group, 4- (4-cyclohexoxybutoxy) butyl group, 4- (4- ( 1-naphthoxy) butoxy) butyl group, 4- (4- (4-methoxybutoxy) butoxy) butyl group, 4- (4- (4-ethoxybutoxy) butoxy) butyl group, 4- (4- (4-n -Propoxybutoxy) butoxy) butyl group, 4- (4- (4-
Isopropoxybutoxy) butoxy) butyl group, 4-
(4- (4-n-butoxybutoxy) butoxy) butyl group, 4- (4- (4-isobutoxybutoxy) butoxy) butyl group, 4- (4- (4-n-hexoxybutoxy) butoxy) butyl Group, 4- (4- (4-isohexoxybutoxy) butoxy) butyl group, 4- (4- (4-
n-octoxybutoxy) butoxy) butyl group, 4-
(4- (4-isooctoxybutoxy) butoxy) butyl group, 4- (4- (4-acetoxybutoxy) butoxy) butyl group, 4- (4- (4-allyloxybutoxy) butoxy) butyl group, -(4- (4-hydroxybutoxy) butoxy) butyl group, 4- (4- (4-phenoxybutoxy) butoxy) butyl group, 4- (4- (4
-Cyclohexoxybutoxy) butoxy) butyl group, 4
-(4- (4- (1-naphthoxy) butoxy) butoxy) butyl group, 4- (4- (4- (4-methoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4-
(4-ethoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4- (4-n-propoxybutoxy)
Butoxy) butoxy) butyl group, 4- (4- (4- (4
-Isopropoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4- (4-n-butoxybutoxy)
Butoxy) butoxy) butyl group, 4- (4- (4- (4
-Isobutoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4- (4-n-hexoxybutoxy))
Butoxy) butoxy) butyl group, 4- (4- (4- (4
-Isohexoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4- (4-n-octoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4-
(4-isooctoxybutoxy) butoxy) butoxy)
Butyl group, 4- (4- (4- (4-acetoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4-
(4-allyloxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4- (4-hydroxybutoxy)
Butoxy) butoxy) butyl group, 4- (4- (4- (4
-Phenoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4- (4-cyclohexoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4-
(4- (1-naphthoxy) butoxy) butoxy) butoxy) butyl and the like. -(CH (CH3) CH
Specific examples of 2O) nZ include, for example, 2-methoxy-1
-Methylethyl group, 2-ethoxy-1-methylethyl group, 2-acetoxy-1-methylethyl group, 1-methyl-2-phenoxyethyl group, 2-cyclohexyloxy-1-methylethyl group, 2- (2 -Methoxy-1-methylethoxy) -1-methylethyl group, 2- (2-ethoxy-1-methylethoxy) -1-methylethyl group, 2-
(2-acetoxy-1-methylethoxy) -1-methylethyl group, 2- (1-methyl-2-phenoxyethoxy) -1-methylethyl group, 2- (2-cyclohexyloxy-1-methylethoxy)- 1-methylethyl group,
2- (2- (2-methoxy-1-methylethoxy) -1
-Methylethoxy) -1-methylethyl group, 2- (2-
(2-ethoxy-1-methylethoxy) -1-methylethoxy) -1-methylethyl group, 2- (2- (2-acetoxy-1-methylethoxy) -1-methylethoxy)
-1-methylethyl group, 2- (2- (1-methyl-2-
Phenoxyethoxy) -1-methylethoxy) -1-methylethyl group, 2- (2- (2-cyclohexyloxy-1-methylethoxy) -1-methylethoxy) -1-
Methyl ethyl group, 2- (2- (2- (2-methoxy-1)
-Methylethoxy) -1-methylethoxy) -1-methylethoxy) -1-methylethyl group, 2- (2- (2-
(2-ethoxy-1-methylethoxy) -1-methylethoxy) -1-methylethoxy) -1-methylethyl group, 2- (2- (2- (2-acetoxy-1-methylethoxy) -1-) Methylethoxy) -1-methylethoxy) -1-methylethyl group, 2- (2- (2- (1-methyl-2-phenoxyethoxy) -1-methylethoxy) -1-methylethoxy) -1-methyl Ethyl group, 2
-(2- (2- (2-cyclohexyloxy-1-methylethoxy) -1-methylethoxy) -1-methylethoxy) -1-methylethyl group and the like. − (CH
2) Specific examples of mO (CH2) nOZ include, for example, a 2- (3-methoxypropoxy) ethyl group,
(3-ethoxypropoxy) ethyl group, 2- (3-n-
Propoxypropoxy) ethyl group, 2- (3-isopropoxypropoxy) ethyl group, 2- (3-n-butoxypropoxy) ethyl group, 2- (3-isobutoxypropoxy) ethyl group, 2- (3-n- Hexoxypropoxy) ethyl group, 2- (3-isohexoxypropoxy)
Ethyl group, 2- (3-n-octoxypropoxy) ethyl group, 2- (3-isooctoxypropoxy) ethyl group, 2- (3-acetoxypropoxy) ethyl group, 2-
(3-allyloxypropoxy) ethyl group, 2- (3-
Hydroxypropoxy) ethyl group, 2- (3-phenoxypropoxy) ethyl group, 2- (3-cyclohexyloxypropoxy) ethyl group, 2- (3- (1-naphthoxy) propoxy) ethyl group, 2- (4-methoxy Butoxy) ethyl group, 2- (4-ethoxybutoxy) ethyl group, 2- (4-n-propoxybutoxy) ethyl group, 2
-(4-isopropoxybutoxy) ethyl group, 2- (4
-N-butoxybutoxy) ethyl group, 2- (4-isobutoxybutoxy) ethyl group, 2- (4-n-hexoxybutoxy) ethyl group, 2- (4-isohexoxybutoxy) ethyl group, 2- (4-n-octoxybutoxy) ethyl group, 2- (4-isooctoxybutoxy) ethyl group, 2- (4-acetoxybutoxy) ethyl group, 2-
(4-allyloxybutoxy) ethyl group, 2- (4-hydroxybutoxy) ethyl group, 2- (4-phenoxybutoxy) ethyl group, 2- (4-cyclohexyloxybutoxy) ethyl group, 2- (4- ( 1-naphthoxy) butoxy) ethyl group, 3- (2-methoxyethoxy) propyl group, 3- (2-ethoxyethoxy) propyl group, 3-
(2-n-propoxyethoxy) propyl group, 3- (2
-Isopropoxyethoxy) propyl group, 3- (2-n
-Butoxyethoxy) propyl group, 3- (2-isobutoxyethoxy) propyl group, 3- (2-n-hexoxyethoxy) propyl group, 3- (2-isohexoxyethoxy) propyl group, 3- (2 -N-octoxyethoxy) propyl group, 3- (2-isooctoxyethoxy)
Propyl group, 3- (2-acetoxyethoxy) propyl group, 3- (2-allyloxyethoxy) propyl group, 3
-(2-hydroxyethoxy) propyl group, 3- (2-
Phenoxyethoxy) propyl group, 3- (2-cyclohexyloxyethoxy) propyl group, 3- (2- (1-
Naphthoxy) ethoxy) propyl group, 3- (4-methoxybutoxy) propyl group, 3- (4-ethoxybutoxy) propyl group, 3- (4-n-propoxybutoxy)
Propyl group, 3- (4-isopropoxybutoxy) propyl group, 3- (4-n-butoxybutoxy) propyl group, 3- (4-isobutoxybutoxy) propyl group, 3
-(4-n-hexoxybutoxy) propyl group, 3-
(4-isohexoxybutoxy) propyl group, 3- (4
-N-octoxybutoxy) propyl group, 3- (4-isooctoxybutoxy) propyl group, 3- (4-acetoxybutoxy) propyl group, 3- (4-allyloxybutoxy) propyl group, 3- (4 -Hydroxybutoxy)
Propyl group, 3- (4-phenoxybutoxy) propyl group, 3- (4-cyclohexyloxybutoxy) propyl group, 3- (4- (1-naphthoxy) butoxy) propyl group, 4- (2-methoxyethoxy) butyl Group, 4-
(2-ethoxyethoxy) butyl group, 4- (2-n-propoxyethoxy) butyl group, 4- (2-isopropoxyethoxy) butyl group, 4- (2-n-butoxyethoxy) butyl group, 4- ( 2-isobutoxyethoxy) butyl group, 4- (2-n-hexoxyethoxy) butyl group,
4- (2-isohexoxyethoxy) butyl group, 4-
(2-n-octoxyethoxy) butyl group, 4- (2-
Isooctoxyethoxy) butyl group, 4- (2-acetoxyethoxy) butyl group, 4- (2-allyloxyethoxy) butyl group, 4- (2-hydroxyethoxy) butyl group, 4- (2-phenoxyethoxy) Butyl group, 4-
(2-cyclohexyloxyethoxy) butyl group, 4-
(2- (1-naphthoxy) ethoxy) butyl group, 4-
(3-methoxypropoxy) butyl group, 4- (3-ethoxypropoxy) butyl group, 4- (3-n-propoxypropoxy) butyl group, 4- (3-isopropoxypropoxy) butyl group, 4- (3- n-butoxypropoxy) butyl group, 4- (3-isobutoxypropoxy) butyl group, 4- (3-n-hexoxypropoxy) butyl group, 4- (3-isohexoxypropoxy) butyl group,
4- (3-n-octoxypropoxy) butyl group, 4-
(3-isooctoxypropoxy) butyl group, 4- (3
-Acetoxypropoxy) butyl group, 4- (3-allyloxypropoxy) butyl group, 4- (3-hydroxypropoxy) butyl group, 4- (3-phenoxypropoxy) butyl group, 4- (3-cyclohexyloxypropoxy) Butyl group and 4- (3- (1-naphthoxy) propoxy) butyl group.

Among the anthracene compounds represented by the above general formula (1), preferred compounds are those described in the above item [2], and more preferred are those described in the above item [3]. As representative examples, 9,10-di (2-bromoethoxy) anthracene, 9,10-di (allyloxy) anthracene, 9,10-di (2-phenylethoxy) anthracene, 9,10-di (2- Methoxyethoxy) anthracene, 9,10-di (2- (2-methoxyethoxy) ethoxy) anthracene, 9,10-di (2-ethoxyethoxy) anthracene, 9,10-di (2-acetoxyethoxy) anthracene, 9 , 10-di (2-allyloxyethoxy) anthracene, 9,10-di (2
-Benzyloxyethoxy) anthracene, 2-ethyl-9,10-di (allyloxy) anthracene, 9.1
0-di (2-cyclohexyloxyethoxy) anthracene, 9,10-di (2- (2-phenylethoxy) ethoxy) anthracene, 9,10-di (2- (2-hydroxyethoxy) ethoxy) anthracene, 9, 10-
Di (2-benzoyloxyethoxy) anthracene,
9,10-di (2-cyclohexylmethyloxyethoxy) anthracene, 9,10-di (4-methoxybutoxy) anthracene, 9,10-di (4- (2-methoxyethoxy) butoxy) anthracene, 9,10- Dicyclohexylmethyloxyanthracene, 9,10-di (4-tert-butylcyclohexyloxy) anthracene, 9,10-di (4-methyl-3-pentenyloxy) anthracene, 2-ethyl-9,10-di (2-
Phenylethoxy) anthracene, 2-ethyl-9,1
0-di (2-methoxyethoxy) anthracene, 2-ethyl-9,10-di (2-allyloxyethoxy) anthracene, 2-ethyl-9,10-di (2- (1-methyl-2-methoxy) Ethoxy) anthracene, 2-ethyl-9,10-di (3-hydroxypropoxy) anthracene, 2-ethyl-9,10-di (4-hydroxybutoxy) anthracene, 2-ethyl-9,10-di (2
-(1-naphthoxy) ethoxy) anthracene, 2-ethyl-9,10-di (2- (2-naphthoxy) ethoxy) anthracene, 1-phenylthio-9,10-di (2-methoxyethoxy) anthracene, 2- Dodecyl-9,10-di (2-methoxyethoxy) anthracene, 2-stearyl-9,10-di (2-methoxyethoxy) anthracene, 2,4-dimethyl-9,10-di (2-methoxyethoxy) anthracene , 1-chloro-
9,10-di (2-methoxyethoxy) anthracene,
2-Chloro-9,10-di (2-methoxyethoxy) anthracene and the like.
-Ethyl-9,10-di (2-methoxyethoxy) anthracene.

Next, a method for producing the 9,10-dietherified anthracene derivative of the formula (1) of the present invention will be described. Specific examples of the anthraquinone compound represented by the formula (2) as a raw material include, for example, unsubstituted anthraquinone,
1-methylanthraquinone, 2-ethylanthraquinone, 1-n-propylanthraquinone, 2-n-propylanthraquinone, 1-isopropylanthraquinone,
2-isopropylanthraquinone, 1-n-butylanthraquinone, 2-n-butylanthraquinone, 1-isobutylanthraquinone, 2-isobutylanthraquinone, 2-tert-butylanthraquinone, 1-n-pentylanthraquinone, 2-n-pentylanthraquinone, 1-isopentyl anthraquinone, 2-isopentyl anthraquinone, 1-n-hexyl anthraquinone,
2-n-hexylanthraquinone, 1-isohexylanthraquinone, 2-isohexylanthraquinone, 1-
n-heptyl anthraquinone, 2-n-heptyl anthraquinone, 1-n-octyl anthraquinone, 2-n-
Octyl anthraquinone, 1-n-nonyl anthraquinone, 2-n-nonyl anthraquinone, 1-n-decyl anthraquinone, 2-n-decyl anthraquinone, 1-n
-Dodecyl anthraquinone, 2-n-dodecyl anthraquinone, 1-methoxyanthraquinone, 2-methoxyanthraquinone, 1-ethoxyanthraquinone, 2-ethoxyanthraquinone, 1-phenoxyanthraquinone,
2-phenoxyanthraquinone, 1,2-dimethylanthraquinone, 1,3-dimethylanthraquinone, 1,4
-Dimethylanthraquinone, 2,3-dimethylanthraquinone, 2,4-dimethylanthraquinone, 2,5-dimethylanthraquinone, 2,6-dimethylanthraquinone, 3,4-dimethylanthraquinone, 1,2-diethylanthraquinone, 1,3- Diethyl anthraquinone,
1,4-diethylanthraquinone, 2,3-diethylanthraquinone, 2,4-diethylanthraquinone, 2,
5-diethylanthraquinone, 2,6-diethylanthraquinone, 3,4-diethylanthraquinone, 1,2,2
3-trimethylanthraquinone, 1,2,4-trimethylanthraquinone, 2,3,6,7-tetramethylanthraquinone, 1-fluoroanthraquinone, 2-fluoroanthraquinone, 1-cyanoanthraquinone, 2-cyanoanthraquinone, 2-phenylanthraquinone , 1
-Benzylanthraquinone, 2-benzylanthraquinone, 1- (1-naphthyl) anthraquinone, 1-methylcarbonylanthraquinone, 2-methylcarbonylanthraquinone, 1-ethylcarbonylanthraquinone, 2
-Ethylcarbonylanthraquinone, 1-phenylcarbonylanthraquinone, 2-phenylcarbonylanthraquinone, 1-methylthioanthraquinone, 2-methylthioanthraquinone, 1-ethylthioanthraquinone,
2-ethylthioanthraquinone, 1-phenylthioanthraquinone, 2-phenylthioanthraquinone, and the like.

First, when an anthraquinone, for example, an anthraquinone represented by the formula (2) is reduced with a hydrazine to form a leuco compound, the anthraquinone is added to an aqueous alkali solution with stirring. The aqueous alkali solution used is preferably an aqueous alkali metal salt solution, for example, an aqueous alkali metal hydroxide solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, an aqueous alkali metal carbonate solution such as an aqueous sodium hydrogen carbonate solution and an aqueous potassium hydrogen carbonate solution, An aqueous solution of an inorganic alkali metal salt such as an aqueous solution of an alkali metal bicarbonate such as an aqueous solution of sodium or an aqueous solution of potassium carbonate can be given. Further, the concentration of the aqueous alkali solution is such that the alkali metal salt is
w%, most preferably 25-35%.
w%. Furthermore, the charged amount of the anthraquinone derivative is
The amount is preferably 3 to 20 parts, more preferably 10 to 15 parts, per 100 parts of the aqueous alkali solution.

For the purpose of acclimating the anthraquinone to the aqueous alkali solution and further promoting the reduction reaction, it is possible to add an alcohol before adding the anthraquinone derivative to the aqueous alkali solution. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol and the like. The proportion of the alcohol to be added is preferably 5 to 40 parts, more preferably 15 to 25 parts, per 100 parts of the alkaline aqueous solution.

After the addition of the anthraquinones, the hydrazines are added to reduce the anthraquinones. As the hydrazine used at this time, 100% hydrazine anhydride can be used alone. However, in consideration of safety and ease of handling, usually, hydrazine hydrate, a hydrazine salt compound or an alkyl hydrazine compound is used. It is better to do. In the case of hydrated hydrazine, the concentration of the hydrazine is 5
The concentration is preferably 0% to 90%, more preferably 60 to 85%. Examples of the hydrazine salt compound include hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine monohydrobromide, hydrazine dihydrobromide, hydrazine sulfate, dihydrazine sulfate, hydrazine phosphate, and hydrazine carbonate. Examples of the alkylhydrazine compound include benzylhydrazine, isopropylhydrazine sulfate, tert-butylhydrazine hydrochloride, and methyl hydrazinoacetate. In the case of hydrated hydrazine, the hydrazine is preferably used in an amount of 0.5 to 10.0 times, more preferably 0.8 to 1.8 times, the hydrazine anhydride component per mole of anthraquinone. It is better to add twice as much. In the case of a hydrazine salt compound, it is preferably added in an amount of 0.8 to 10.0 times, and more preferably 1.0 to 2.0 times, a mole of anthraquinones. In addition, in the case of an alkyl hydrazine compound, it is preferably added in an amount of 1.8 to 15.0 moles, more preferably 2.0 to 5.0 moles per mole of anthraquinones.

When a leuco compound is obtained by adding hydrazines to reduce anthraquinones, nitrogen gas or the like may be blown into the reaction solution to expel dissolved oxygen in advance in order to promote the reaction. The reaction is preferably carried out at 20 to 150 ° C, more preferably at 40 to 90 ° C. The reaction time is usually preferably 30 minutes to 10 hours.

The anthraquinones are reduced with hydrazines to form the leuco form, and then the reaction is carried out by gradually adding an alkylating agent. Examples of the alkylating agent used in the reaction include, for example, the p-toluenesulfonic acid ester represented by the formula (3), the alkylsulfonic acid ester represented by the formula (4), Sulfuric esters or alkyl halides represented by (5) can be mentioned. From the viewpoint of the reaction yield and the like, p-toluenesulfonic acid esters, alkylsulfonic acid esters, and sulfuric acid esters are used. It is preferred to use. As the alkylating agent used in the reaction, commercially available compounds such as methyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl methanesulfonate, ethyl methanesulfonate, dimethyl sulfate and diethyl sulfate are used as they are. Alternatively, a desired alkylating agent may be synthesized and used. When the desired alkylating agent is a solid such as a wax, it can be diluted with a solvent not involved in the reaction system before use. Examples of the solvent that does not participate in the reaction system include aromatic hydrocarbon compounds such as toluene and xylene, ethers such as diethyl ether and isopropyl ether, aliphatic hydrocarbon compounds such as n-hexane and cyclohexane, methanol, ethanol, isopropanol, and the like. Alcohols and the like. Further, when the desired ester compound is diluted with a solvent and used, the dilution ratio is usually 1 to 99 w%, preferably 20 to 80 w%.

The amount of the alkylating agent to be charged is preferably 1.0 to 10.0 mol, more preferably 4.0 to 7.0 mol, per 1.0 mol of anthraquinones. . The temperature during the preparation of the ester compound was 30 ° C.
To 100 ° C, preferably 50 ° C to 70 ° C.
C is good. Further, the reaction temperature after charging the alkylating agent is preferably 50 ° C. to 100 ° C., and the reaction time is preferably 0.5 to 10.0 hours, preferably 1.0 hour.
It is preferable to perform for up to 4.0 hours.

After completion of the reaction, the obtained reaction product is added to water while stirring. The amount of water at this time is 9,10
5 relative to the theoretical amount of the dietherified anthracene derivative
It is 100 parts by weight, preferably 10 to 30 parts by weight. After stirring for 1 hour, the crystals are separated by filtration, and usually 5 to 10 parts by weight of a 10 w% aqueous hydrosulfite aqueous solution based on the theoretical amount of the obtained 9,10-dietherified anthracene derivative, and then usually 20 to 50 times The crystals are washed with parts by weight of water and usually with 2 to 5 parts by weight of methanol, and then dried to obtain the desired 9,10-dietherified anthracene derivative.

The obtained 9,10-dietherified anthracene derivative may be dried as it is, or may be recrystallized using an organic solvent. Examples of the organic solvent that can be used for recrystallization include alcohols such as methanol, ethanol, and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and n-butyl acetate; and aromatics such as toluene and xylene. Compounds can be mentioned. These organic solvents may be used alone or in combination of two or more.

When a p-toluenesulfonic acid ester or alkylsulfonic acid ester compound is obtained by synthesis, alcohols are mixed with either p-toluenesulfonic acid halide or alkylsulfonic acid halide and an alkali compound is added. Thus, a desired ester compound can be obtained. As the halide, chlorides or bromides are preferable. In the case of monohydric alcohol, the charged amount of the halides to alcohols is 0.9 to 1.0 mol of alcohols.
２．０2.0 mol is preferably charged, more preferably 1.
0 to 1.3 mol, and in the case of a dihydric alcohol, a halide is used in an amount of 0.1 mol per 1.0 mol of alcohol.
モ ル 1.0 mol is preferably charged, more preferably 0.1 to 1.0 mol.
It is preferable to charge 2 to 0.5 mol. If the alcohols do not easily react with the halides, the alcohols may be converted into alcoholates with lithium hydride, sodium hydride, potassium hydride, or the like before reacting with the halides.
The reaction is preferably performed at -50 to 30C. The reaction time is 3 to 30 hours, more preferably 7 to 15 hours.
Time.

After charging halides to alcohols,
The esterification reaction is performed by gradually adding an alkali compound.
Examples of the alkali compound used at this time include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, etc., monoethylamine, diethylamine, triethylamine, isopropylamine, diisopropylamine, n -Butylamine, n-dibutylamine, n-tributylamine, isobutylamine, diisobutylamine, n-pentylamine, dipentylamine, tripentylamine, 2-ethylbutylamine, n
-Heptylamine, 2-ethylhexylamine, dioctylamine, cyclohexylamine, dicyclohexylamine, aniline, monomethylaniline, dimethylaniline, diethylaniline, o-toluidine, pyridine,
α-picoline, β-picoline, γ-picoline, 2,4-
Lutidine, 2,6-lutidine, quinoline, morpholine,
Organic amines such as ethyl morpholine can be mentioned.

The amount of the alkali compound to be charged is preferably from 1.0 to 10.0 mol, more preferably from 2.0 to 4.0 mol, per 1.0 mol of the alcohol. These alkali compounds may be used as they are or as an aqueous solution.
The content of the alkali compound is preferably 10 to 50% by weight relative to water, and most preferably 20 to 30% by weight. In addition, when adding an alkali compound, when using as it is, without using it as an aqueous solution, it is good to charge it little by little, and when using as an aqueous solution, it is preferable to dripping gradually. During the charging of the alkali compound, the liquid temperature is preferably maintained at 0 to 50C, more preferably at 10 to 20C.

After completion of the reaction, the alkali compound is neutralized with an acid, washed with water, and then a desired p-toluenesulfonic acid ester compound or an alkylsulfonic acid ester compound is obtained by means of liquid separation or solvent extraction. When a p-toluenesulfonic acid ester compound or an alkylsulfonic acid ester compound is taken out by solvent extraction, examples of an organic solvent that can be used include toluene, xylene, ethyl acetate, n-propyl acetate, isopropyl acetate, and acetic acid-n. -Butyl, isobutyl acetate, sec-butyl acetate, methyl isobutyl ketone, and the like.After extraction with these organic solvents, the solvent is removed, and the desired p-toluenesulfonic acid ester compound or An alkyl sulfonic acid ester compound can be obtained.

The alcohols used in the esterification reaction used herein include, for example, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-pentyl alcohol, isopentyl alcohol, n-hexyl Alcohol, isohexyl alcohol, n-heptyl alcohol, isoheptyl alcohol, n-octyl alcohol, isooctyl alcohol, n-nonyl alcohol, isononyl alcohol, n-decyl alcohol,
Isodecyl alcohol, n-dodecyl alcohol, isododecyl alcohol, n-stearyl alcohol, isostearyl alcohol, 2-fluoroethanol, benzyl alcohol, cyclohexyl alcohol, cyclohexyl methanol, 4-tert-butylcyclohexanol, 4-methyl-3- Pentenyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisopentyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono -N-hexyl ether, methoxymethoxyethanol, ethylene Recall monoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono -n
-Butyl ether, diethylene glycol acetate,
Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, 1-butoxy Monohydric alcohols such as ethoxypropanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether, ethylene glycol, diethylene glycol, triethylene glycol,
2 such as tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, etc.
Valent alcohols can be mentioned.

Specific examples of the p-toluenesulfonic acid ester compound represented by the formula (3) include, for example, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, n-propyl p-toluenesulfonate, Isopropyl p-toluenesulfonate, n-butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, p
-Toluenesulfonic acid-n-pentyl, p-toluenesulfonic acid isopentyl, p-toluenesulfonic acid-n-
Hexyl, isohexyl p-toluenesulfonate, p-
Toluenesulfonic acid-n-heptyl, p-toluenesulfonic acid isoheptyl, p-toluenesulfonic acid-n-octyl, p-toluenesulfonic acid isooctyl, p-toluenesulfonic acid-n-nonyl, p-toluenesulfonic acid isononyl, p -N-decyl toluenesulfonic acid,
isodecyl p-toluenesulfonate, n-dodecyl p-toluenesulfonate, isododecyl p-toluenesulfonate, n-stearyl p-toluenesulfonate, p
-Isostearyl toluenesulfonate, p-toluenesulfonic acid- (2-fluoroethyl), benzyl p-toluenesulfonate, cyclohexyl p-toluenesulfonate, cyclohexylmethyl p-toluenesulfonate, p
-Cyclohexylethyl toluenesulfonate, p-toluenesulfonic acid- (4-tert-butylcyclohexyl), p-toluenesulfonic acid- (4-methyl-3-pentenyl), p-toluenesulfonic acid- (2-hydroxyethyl) P-toluenesulfonic acid- (2-methoxyethyl), p-toluenesulfonic acid- (2-ethoxyethyl), p-toluenesulfonic acid- (2-n-propoxyethyl), p-toluenesulfonic acid- (2 -Isopropoxyethyl), p-toluenesulfonic acid- (2-n-
Butoxyethyl), p-toluenesulfonic acid- (2-isobutoxyethyl), p-toluenesulfonic acid- (2-
Isopentoxyethyl), p-toluenesulfonic acid-
(2-phenoxyethyl), p-toluenesulfonic acid-
(2-benzoxyethyl), p-toluenesulfonic acid-
(2-n-hexoxyethyl), p-toluenesulfonic acid- (2-methoxymethoxyethyl), p-toluenesulfonic acid- (2- (2-hydroxyethoxy) ethyl), p-toluenesulfonic acid- (2- ( 2-methoxyethoxy) ethyl), p-toluenesulfonic acid- (2-
(2-ethoxyethoxy) ethyl), p-toluenesulfonic acid- (2- (2-n-butoxyethoxy) ethyl), p-toluenesulfonic acid- (3-fluoropropyl), p-toluenesulfonic acid- (3 -Hydroxypropyl), p-toluenesulfonic acid- (3-methoxypropyl), p-toluenesulfonic acid- (3-ethoxypropyl), p-toluenesulfonic acid- (3-n-propoxypropyl), p-toluenesulfone Acid- (3-isopropoxypropyl), p-toluenesulfonic acid- (3-
n-butoxypropyl), p-toluenesulfonic acid-
(3-isobutoxypropyl), p-toluenesulfonic acid- (3-isopentoxypropyl), p-toluenesulfonic acid- (3-phenoxypropyl), p-toluenesulfonic acid- (3-benzoxypropyl), p-toluenesulfonic acid- (3-n-hexoxypropyl), p-
Toluenesulfonic acid- (3-methoxymethoxypropyl), p-toluenesulfonic acid- (3- (2-hydroxyethoxy) propyl), p-toluenesulfonic acid-
(3- (2-methoxyethoxy) propyl), p-toluenesulfonic acid- (3- (2-ethoxyethoxy) propyl), p-toluenesulfonic acid- (3- (2-n-butoxyethoxy) propyl), p-toluenesulfonic acid- (3- (3-hydroxypropoxy) propyl), p
-Toluenesulfonic acid- (4-fluorobutyl), p-
Toluenesulfonic acid- (4-hydroxybutyl), p-
Toluenesulfonic acid- (4-methoxybutyl), p-toluenesulfonic acid- (4-ethoxybutyl), p-toluenesulfonic acid- (4-n-propoxybutyl), p-
-(4-isopropoxybutyl) toluenesulfonic acid,
p-toluenesulfonic acid- (4-n-butoxybutyl), p-toluenesulfonic acid- (4-isobutoxybutyl), p-toluenesulfonic acid- (4-isopentoxybutyl), p-toluenesulfonic acid- (4-phenoxybutyl), p-toluenesulfonic acid- (4-benzoxybutyl), p-toluenesulfonic acid- (4-n-hexoxybutyl), p-toluenesulfonic acid- (4-methoxymethoxybutyl), p -Toluenesulfonic acid- (4
-(2-hydroxyethoxy) butyl), p-toluenesulfonic acid- (4- (2-methoxyethoxy) butyl), p-toluenesulfonic acid- (4- (2-ethoxyethoxy) butyl), p-toluenesulfone Acid- (4-
(2-n-butoxyethoxy) butyl), p-toluenesulfonic acid- (4- (3-n-butoxypropoxy) butyl), p-toluenesulfonic acid- (4- (4-n-butoxybutoxy) butyl) And the like.

Specific examples of the alkyl sulfonic acid ester compound represented by the formula (4) include, for example, methyl methanesulfonate, ethyl methanesulfonate, n-propyl methanesulfonate, isopropyl methanesulfonate, methanesulfonate -N-butyl, isobutyl methanesulfonate, n-pentyl methanesulfonate, isopentyl methanesulfonate, n-hexyl methanesulfonate,
Isohexyl methanesulfonate, methanesulfonic acid-n
Heptyl, isoheptyl methanesulfonate, n-octyl methanesulfonate, isooctyl methanesulfonate, n-nonyl methanesulfonate, isononyl methanesulfonate, n-decyl methanesulfonate, isodecyl methanesulfonate, methanesulfonate -N-dodecyl, isododecyl methanesulfonate, -n-stearyl methanesulfonate, isostearyl methanesulfonate,
Methanesulfonic acid- (2-fluoroethyl), benzyl methanesulfonic acid, cyclohexyl methanesulfonic acid,
Cyclohexylmethyl methanesulfonate, cyclohexylethyl methanesulfonate, methanesulfonic acid- (4-
tert-butylcyclohexyl), methanesulfonic acid- (4-methyl-3-pentenyl), methanesulfonic acid- (2-hydroxyethyl), methanesulfonic acid- (2
-Methoxyethyl), methanesulfonic acid- (2-ethoxyethyl), methanesulfonic acid- (2-n-propoxyethyl), methanesulfonic acid- (2-isopropoxyethyl), methanesulfonic acid- (2-n- Butoxyethyl), methanesulfonic acid- (2-isobutoxyethyl), methanesulfonic acid- (2-isopentoxyethyl), methanesulfonic acid- (2-phenoxyethyl),
Methanesulfonic acid- (2-benzoxyethyl), methanesulfonic acid- (2-n-hexoxyethyl), methanesulfonic acid- (2-methoxymethoxyethyl), methanesulfonic acid- (2- (2-hydroxyethoxy) ethyl ), Methanesulfonic acid- (2- (2-methoxyethoxy) ethyl), methanesulfonic acid- (2- (2-ethoxyethoxy) ethyl), methanesulfonic acid- (2- (2
-N-butoxyethoxy) ethyl), methanesulfonic acid- (3-fluoropropyl), methanesulfonic acid- (3
-Hydroxypropyl), methanesulfonic acid- (3-methoxypropyl), methanesulfonic acid- (3-ethoxypropyl), methanesulfonic acid- (3-n-propoxypropyl), methanesulfonic acid- (3-isopropoxypropyl) ), Methanesulfonic acid- (3-n-butoxypropyl), methanesulfonic acid- (3-isobutoxypropyl), methanesulfonic acid- (3-isopentoxypropyl), methanesulfonic acid- (3-phenoxypropyl) Methanesulfonic acid- (3-benzoxypropyl), methanesulfonic acid- (3-n-hexoxypropyl), methanesulfonic acid- (3-methoxymethoxypropyl), methanesulfonic acid- (3- (2-hydroxy Ethoxy) propyl), methanesulfonic acid- (3- (2-
Methoxyethoxy) propyl), methanesulfonic acid-
(3- (2-ethoxyethoxy) propyl), methanesulfonic acid- (3- (2-n-butoxyethoxy) propyl), methanesulfonic acid- (3- (3-hydroxypropoxy) propyl), methanesulfonic acid- (4-fluorobutyl), methanesulfonic acid- (4-hydroxybutyl), methanesulfonic acid- (4-methoxybutyl), methanesulfonic acid- (4-ethoxybutyl), methanesulfonic acid- (4-n-propoxy) Butyl), methanesulfonic acid- (4-isopropoxybutyl), methanesulfonic acid- (4-n-butoxybutyl), methanesulfonic acid-
(4-isobutoxybutyl), methanesulfonic acid- (4
-Isopentoxybutyl), methanesulfonic acid- (4-
Phenoxybutyl), methanesulfonic acid- (4-benzoxybutyl), methanesulfonic acid- (4-n-hexoxybutyl), methanesulfonic acid- (4-methoxymethoxybutyl), methanesulfonic acid- (4- (2- (Hydroxyethoxy) butyl), methanesulfonic acid- (4- (2
-Methoxyethoxy) butyl), methanesulfonic acid-
(4- (2-ethoxyethoxy) butyl),-(4- (2-n-butoxyethoxy) butyl) methanesulfonate,-(4- (3-n-butoxypropoxy) butyl) methanesulfonate, methanesulfone Acid- (4- (4-
methanesulfonic acid ester compounds such as n-butoxybutoxy) butyl), methyl ethanesulfonate, ethyl ethanesulfonate, n-propyl ethanesulfonate, isopropyl ethanesulfonate, n-butyl ethanesulfonate, isobutyl ethanesulfonate N-pentyl ethanesulfonate, isopentyl ethanesulfonate, n-hexyl ethanesulfonate, isohexyl ethanesulfonate, n-heptyl ethanesulfonate, isoheptyl ethanesulfonate, n-octyl ethanesulfonate, ethanesulfone Acid isooctyl, ethanesulfonic acid-n-nonyl, ethanesulfonic acid isononyl, ethanesulfonic acid-n-decyl, ethanesulfonic acid isodecyl,
N-dodecyl ethanesulfonate, isododecyl ethanesulfonate, n-stearyl ethanesulfonate, isostearyl ethanesulfonate, ethanesulfonic acid- (2
-Fluoroethyl), benzyl ethanesulfonate, cyclohexyl ethanesulfonate, cyclohexylmethyl ethanesulfonate, cyclohexylethyl ethanesulfonate,-(4-tert-butylcyclohexyl) ethanesulfonate, ethanesulfonic acid- (4-methyl-3) -Pentenyl), ethanesulfonic acid- (2-hydroxyethyl), ethanesulfonic acid- (2-methoxyethyl), ethanesulfonic acid- (2-ethoxyethyl), ethanesulfonic acid- (2-n-propoxyethyl), Ethanesulfonic acid- (2-isopropoxyethyl), ethanesulfonic acid- (2-n-butoxyethyl), ethanesulfonic acid-
(2-isobutoxyethyl), ethanesulfonic acid- (2
-Isopentoxyethyl), ethanesulfonic acid- (2-
Phenoxyethyl), ethanesulfonic acid- (2-benzoxyethyl), ethanesulfonic acid- (2-n-hexoxyethyl), ethanesulfonic acid- (2-methoxymethoxyethyl), ethanesulfonic acid- (2- (2- (2- (Hydroxyethoxy) ethyl), ethanesulfonic acid- (2- (2
-Methoxyethoxy) ethyl), ethanesulfonic acid-
(2- (2-ethoxyethoxy) ethyl), ethanesulfonic acid- (2- (2-n-butoxyethoxy) ethyl), ethanesulfonic acid- (3-fluoropropyl),
Ethanesulfonic acid- (3-hydroxypropyl), ethanesulfonic acid- (3-methoxypropyl), ethanesulfonic acid- (3-ethoxypropyl), ethanesulfonic acid- (3-n-propoxypropyl), ethanesulfonic acid- (3-isopropoxypropyl), ethanesulfonic acid- (3-n-butoxypropyl), ethanesulfonic acid-
(3-isobutoxypropyl), ethanesulfonic acid-
(3-isopentoxypropyl), ethanesulfonic acid-
(3-phenoxypropyl), ethanesulfonic acid- (3
-Benzoxypropyl), ethanesulfonic acid- (3-n
-Hexoxypropyl), ethanesulfonic acid- (3-methoxymethoxypropyl), ethanesulfonic acid- (3-
(2-hydroxyethoxy) propyl), ethanesulfonic acid- (3- (2-methoxyethoxy) propyl), ethanesulfonic acid- (3- (2-ethoxyethoxy) propyl), ethanesulfonic acid- (3- (2 -N-butoxyethoxy) propyl), ethanesulfonic acid- (3- (3
-Hydroxypropoxy) propyl), ethanesulfonic acid- (4-fluorobutyl), ethanesulfonic acid- (4
-Hydroxybutyl), ethanesulfonic acid- (4-methoxybutyl), ethanesulfonic acid- (4-ethoxybutyl), ethanesulfonic acid- (4-n-propoxybutyl), ethanesulfonic acid- (4-isopropoxybutyl) ), Ethanesulfonic acid- (4-n-butoxybutyl), ethanesulfonic acid- (4-isobutoxybutyl), ethanesulfonic acid- (4-isopentoxybutyl), ethanesulfonic acid- (4-phenoxybutyl) ,
Ethanesulfonic acid- (4-benzoxybutyl), ethanesulfonic acid- (4-n-hexoxybutyl), ethanesulfonic acid- (4-methoxymethoxybutyl), ethanesulfonic acid- (4- (2-hydroxyethoxy) butyl ), Ethanesulfonic acid- (4- (2-methoxyethoxy) butyl), ethanesulfonic acid- (4- (2-ethoxyethoxy) butyl), ethanesulfonic acid- (4- (2
-N-butoxyethoxy) butyl),-(4- (3-n-butoxypropoxy) butyl) ethanesulfonic acid,-(4- (4-n-butoxybutoxy) ethanesulfonic acid)
Butyl) and other ethanesulfonic acid ester compounds, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, trifluoromethanesulfonic acid-n-
Propyl, isopropyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, isobutyl trifluoromethanesulfonate, n-pentyl trifluoromethanesulfonate, isopentyl trifluoromethanesulfonate, n-hexyl trifluoromethanesulfonate, trifluoromethanesulfone Isohexyl acid, n-heptyl trifluoromethanesulfonate, isoheptyl trifluoromethanesulfonate, n-octyl trifluoromethanesulfonate, isooctyl trifluoromethanesulfonate, n-nonyl trifluoromethanesulfonate, isononyl trifluoromethanesulfonate, trifluoromethane N-decyl sulfonate, isodecyl trifluoromethanesulfonate, trifluoromethanesulfo Acid-n-dodecyl, isododecyl trifluoromethanesulfonate, n-stearyl trifluoromethanesulfonate, isostearyl trifluoromethanesulfonate, 2- (2-fluoroethyl) trifluoromethanesulfonate, benzyl trifluoromethanesulfonate, trifluoromethanesulfonate Cyclohexyl, cyclohexylmethyl trifluoromethanesulfonate, cyclohexylethyl trifluoromethanesulfonate, trifluoromethanesulfonic acid- (4-ter
t-butylcyclohexyl), trifluoromethanesulfonic acid- (4-methyl-3-pentenyl), trifluoromethanesulfonic acid- (2-hydroxyethyl), trifluoromethanesulfonic acid- (2-methoxyethyl),
Trifluoromethanesulfonic acid- (2-ethoxyethyl), trifluoromethanesulfonic acid- (2-n-propoxyethyl), trifluoromethanesulfonic acid- (2
-Isopropoxyethyl), trifluoromethanesulfonic acid- (2-n-butoxyethyl), trifluoromethanesulfonic acid- (2-isobutoxyethyl), trifluoromethanesulfonic acid- (2-isopentoxyethyl), trifluoromethanesulfone Acid- (2-phenoxyethyl), trifluoromethanesulfonic acid- (2-benzoxyethyl), trifluoromethanesulfonic acid-
(2-n-hexoxyethyl), trifluoromethanesulfonic acid- (2-methoxymethoxyethyl), trifluoromethanesulfonic acid- (2- (2-hydroxyethoxy) ethyl), trifluoromethanesulfonic acid- (2-
(2-methoxyethoxy) ethyl), trifluoromethanesulfonic acid- (2- (2-ethoxyethoxy) ethyl), trifluoromethanesulfonic acid- (2- (2-n
-Butoxyethoxy) ethyl), trifluoromethanesulfonic acid- (3-fluoropropyl), trifluoromethanesulfonic acid- (3-hydroxypropyl), trifluoromethanesulfonic acid- (3-methoxypropyl),
Trifluoromethanesulfonic acid- (3-ethoxypropyl), trifluoromethanesulfonic acid- (3-n-propoxypropyl), trifluoromethanesulfonic acid-
(3-isopropoxypropyl), trifluoromethanesulfonic acid- (3-n-butoxypropyl), trifluoromethanesulfonic acid- (3-isobutoxypropyl), trifluoromethanesulfonic acid- (3-isopentoxypropyl), trifluoro Romethanesulfonic acid-
(3-phenoxypropyl), trifluoromethanesulfonic acid- (3-benzoxypropyl), trifluoromethanesulfonic acid- (3-n-hexoxypropyl), trifluoromethanesulfonic acid- (3-methoxymethoxypropyl), trifluoromethane Sulfonic acid- (3-
(2-hydroxyethoxy) propyl), trifluoromethanesulfonic acid- (3- (2-methoxyethoxy) propyl), trifluoromethanesulfonic acid- (3- (2
-Ethoxyethoxy) propyl), trifluoromethanesulfonic acid- (3- (2-n-butoxyethoxy) propyl), trifluoromethanesulfonic acid- (3- (3-
(Hydroxypropoxy) propyl), trifluoromethanesulfonic acid- (4-fluorobutyl), trifluoromethanesulfonic acid- (4-hydroxybutyl), trifluoromethanesulfonic acid- (4-methoxybutyl), trifluoromethanesulfonic acid- (4- Ethoxybutyl), trifluoromethanesulfonic acid- (4-n-propoxybutyl), trifluoromethanesulfonic acid- (4
-Isopropoxybutyl), trifluoromethanesulfonic acid- (4-n-butoxybutyl), trifluoromethanesulfonic acid- (4-isobutoxybutyl), trifluoromethanesulfonic acid- (4-isopentoxybutyl), trifluoromethanesulfone Acid- (4-phenoxybutyl), trifluoromethanesulfonic acid- (4-benzoxybutyl), trifluoromethanesulfonic acid-
(4-n-hexoxybutyl), trifluoromethanesulfonic acid- (4-methoxymethoxybutyl), trifluoromethanesulfonic acid- (4- (2-hydroxyethoxy) butyl), trifluoromethanesulfonic acid- (4-
(2-methoxyethoxy) butyl), trifluoromethanesulfonic acid- (4- (2-ethoxyethoxy) butyl), trifluoromethanesulfonic acid- (4- (2-n
-Butoxyethoxy) butyl), trifluoromethanesulfonic acid- (4- (3-n-butoxypropoxy) butyl), trifluoromethanesulfonic acid- (4- (4-n
-Butoxybutoxy) butyl) and the like.

When a sulfate compound is obtained by synthesis, a method in which silver sulfate acts on an iodine compound having an iodine atom at a terminal, a method in which sodium alkoxide acts on sulfonyl chloride, and a method in which sodium alkoxide acts on chlorosulfonic acid ester A method of heating a mixture of sulfuric acid and alcohol, a method of heating alkyl sulfuric acid, a method of reacting a sulfite with a sulfonyl chloride, and the like.

Specific examples of the sulfate compound represented by the formula (5) include, for example, dimethyl sulfate, diethyl sulfate,
Di-n-propyl sulfate, diisopropyl sulfate, di-sulfate
n-butyl, diisobutyl sulfate, di-n-pentyl sulfate, diisopentyl sulfate, di-n-hexyl sulfate, diisohexyl sulfate, di-n-heptyl sulfate, diisoheptyl sulfate, di-n-octyl sulfate, diisooctyl sulfate,
Di-n-nonyl sulfate, diisononyl sulfate, di-n- sulfate
Decyl, diisodecyl sulfate, di-n-dodecyl sulfate, diisododecyl sulfate, di-n-stearyl sulfate, diisostearyl sulfate, di- (2-fluoroethyl) sulfate, dibenzyl sulfate, dicyclohexyl sulfate, dicyclohexylmethyl sulfate, dicyclohexylethyl sulfate , Di-sulfate
(4-tert-butylcyclohexyl), di-sulfate
(4-methyl-3-pentenyl), di- (2-hydroxyethyl) sulfate, di- (2-methoxyethyl) sulfate, di- (2-ethoxyethyl) sulfate, di- (2-n-propoxyethyl sulfate) ), Di- (2-isopropoxyethyl) sulfate, di- (2-n-butoxyethyl) sulfate, di-sulfate
(2-isobutoxyethyl), di- (2-isopentoxyethyl) sulfate, di- (2-phenoxyethyl) sulfate,
Di- (2-benzoxyethyl) sulfate, di- (2-n
-Hexoxyethyl), di- (2-methoxymethoxyethyl) sulfate, di- (2- (2-hydroxyethoxy) ethyl) sulfate, di- (2- (2-methoxyethoxy) ethyl) sulfate, di- (2 -(2-ethoxyethoxy) ethyl), di- (2- (2-n-butoxyethoxy) ethyl) sulfate, di- (3-fluoropropyl) sulfate,
Di- (3-hydroxypropyl) sulfate, di- (3-hydroxypropyl sulfate)
Methoxypropyl), di- (3-ethoxypropyl) sulfate, di- (3-n-propoxypropyl) sulfate, di- (3-isopropoxypropyl) sulfate, di- (3-ethoxypropyl) sulfate
n-butoxypropyl), di- (3-isobutoxypropyl) sulfate, di- (3-isopentoxypropyl) sulfate, di- (3-phenoxypropyl) sulfate, di-sulfate
(3-benzoxypropyl), di- (3-n-hexoxypropyl) sulfate, di- (3-methoxymethoxypropyl) sulfate, di- (3- (2-hydroxyethoxy) sulfate
Propyl), di- (3- (2-methoxyethoxy) sulfate
Propyl), di- (3- (2-ethoxyethoxy) sulfate
Propyl), di- (3- (2-n-butoxyethoxy) propyl) sulfate, di- (3- (3-hydroxypropoxy) propyl) sulfate, di- (4-fluorobutyl) sulfate, di- (4 -Hydroxybutyl), di-sulfate-
(4-methoxybutyl), di- (4-ethoxybutyl) sulfate, di- (4-n-propoxybutyl) sulfate, di- (4-isopropoxybutyl) sulfate, di- (4-n-butyl sulfate)
Butoxybutyl), di- (4-isobutoxybutyl) sulfate, di- (4-isopentoxybutyl) sulfate, di- (4-phenoxybutyl) sulfate, di- (4-benzoxybutyl) sulfate, di-sulfate -(4-n-hexoxybutyl),
Di- (4-methoxymethoxybutyl) sulfate, di-sulfate
(4- (2-hydroxyethoxy) butyl), di-sulfate
(4- (2-methoxyethoxy) butyl), di-sulfate
(4- (2-ethoxyethoxy) butyl), di-sulfate
(4- (2-n-butoxyethoxy) butyl), di- (4- (3-n-butoxypropoxy) butyl) sulfate, di- (4- (4-n-butoxybutoxy) butyl) sulfate and the like. be able to.

Next, the photopolymerizable resin composition of the present invention will be described. The photopolymerizable resin composition of the present invention comprises a cationic polymerizable compound, an energy ray-sensitive cationic polymerization initiator, and a photosensitizer of the present invention as essential components.
-It contains one or more dietherified anthracene compounds and can be used for all purposes. Specifically, for example, printing inks, paints, various coating agents, semiconductor sealants, solder resist inks, color resists for producing color filters, liquid crystal sealants, liquid crystal cell spacer resins, DVD adhesives, stereolithography Resin, resin for various castings, etc.

The cationically polymerizable compound used in the photopolymerizable resin composition of the present invention is a compound which undergoes a polymerization or a crosslinking reaction by an energy-sensitive cationic polymerization initiator activated by irradiation with energy rays. For example,
Epoxy compounds, cyclic ether compounds such as oxetane,
Examples thereof include a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, and a vinyl compound, and one or more of these can be used. Particularly, an epoxy compound which is easily available and easy to handle is suitable.

The epoxy compound may be any one as long as it is a compound usually used as an epoxy resin composition. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, Cresol novolak type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanate and hydantoin epoxy, hydrogenated bisphenol A type epoxy resin, aliphatic such as propylene glycol diglycidyl ether and pentaerythritol polyglycidyl ether Epoxy resins, epoxy resins obtained by reacting aromatic, aliphatic or alicyclic carboxylic acids with epichlorohydrin, spiro ring-containing epoxy resins, and the like.

As the cationic photopolymerization initiator used in the photopolymerizable resin composition of the present invention, JP-B-53-3283 can be used.
No. 1, JP-B-52-14277, JP-B-52-142
No. 78, JP-B 52-14279, JP-B 52-25
686, JP-B-61-34752, JP-A-54-5
No. 3181, JP-A-54-95686, JP-B-61-
36530, JP-B-59-19581, JP-B-63
-65688, JP-A-55-164204, JP-B-60-30690, JP-B-63-36332, JP-B1-39423, JP-B2-10171, JP-B5-15721, and JP-B-4. No.-62310, Tokiko Sho 6
No. 2-57653, No. 3-12081, No. 3
No. -12082, Tokuho 3-16361, Tokubo 63
-12092 JP-B 63-12093, JP-B 63
-12095, JP-B-63-12094, JP-B2
-37924, JP-B-2-35764, JP-B-4-
No. 13374, No. 4-75908, No. 4-7
3428, JP-A-2-150848, JP-A 2-2
96514, JP-A-7-61964, JP-A-8-16
No. 5290, JP-A-6-184170, JP-A-6-1
No. 57624, JP-A-5-222112, U.S. Pat. No. 4,069,055, U.S. Pat. No. 4,069,056
No. 3,703,296, U.S. Pat.
No. 231,951, U.S. Pat. No. 4,256,828, and the like, and sulfonium salts, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, pyridinium salts, iron / allene complexes and the like can be exemplified. Particularly, a diphenylalkylsulfonium salt, a dinaphthylalkylsulfonium salt, a triphenylsulfonium salt, a diphenyliodonium salt, a phenylnaphthyliodonium salt, a dinaphthyliodonium salt compound or a derivative thereof is preferable.

The counter anion of these salt compounds is a non-nucleophilic counter anion such as B (C6F5) 4, S
Examples thereof include bF6, AsF6, PF6, and BF4. Specific examples of the cationic photopolymerization initiator include the following compounds. Examples of the sulfonium salt include triphenylsulfonium-hexafluorophosphate, bis (4- (diphenylsulfonio)-
Phenyl) sulfide-bis-hexafluorophosphate, bis (4- (diphenylsulfonio) -phenyl) sulfide-bis-hexafluoroantimonate, 4-di (p-toluyl) sulfonio-4′-ter
t-butylphenylcarbonyl-diphenylsulfide-hexafluorophosphate, 4-di (p-toluyl) sulfonio-4'-tert-butylphenylcarbonyl-diphenylsulfide-hexafluoroantimonate, 7-di (p-toluyl) sulfonio- 2-isopropyl-thioxanthone-hexafluorophosphate, 7-di (p-toluyl) sulfonio-2-isopropyl-thioxanthone-hexafluoroantimonate and the like can be mentioned. Examples of the iodonium salt include diphenyliodonium-hexafluorophosphate, diphenyliodonium-hexafluoroantimonate, and bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate. As the phosphonium salt, for example, tetraphenylphosphonium-
Hexafluorophosphate, tetraphenylphosphonium-tetrafluoroantimomate and the like can be mentioned.

In the photopolymerizable resin composition of the present invention, the compounding ratio of the novel 9,10-dietherified anthracene compound of the present invention useful as a cationic polymerizable compound, a photocationic polymerization initiator and a sensitizer can be arbitrarily determined. Although it can be set, preferably 0.01 to 50 parts by weight of a cationic photopolymerization initiator, 0.01 to 50 parts by weight of a novel anthracene compound, more preferably 100 to 100 parts by weight of a photopolymerizable compound 0.1 to 30 parts by weight of a cationic photopolymerization initiator and 0.1 to 30 parts by weight of a novel anthracene compound are used per 100 parts by weight of the compound.

The photopolymerizable resin composition of the present invention may optionally contain a radical polymerization resin and an initiator. The term “radical polymerizable resin” as used herein refers to a compound having at least one ethylenically unsaturated bond capable of undergoing radical polymerization in a molecule, and specific compounds include, for example, 2-ethylhexyl (meth ) Acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, bis (4- (Meth) acryloxypolyethoxyphenyl) propane, neopentyl glycol di (meth) acrylate, 1,6
-Hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth)
(Meth) such as acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, and oligoester (meth) acrylate Acrylate monomer, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, (meth) acrylate oligomer such as polyether (meth) acrylate, allyl glycidyl ether, diallyl phthalate, triallyl trimellit Examples include allyl compounds such as tate and vinyl compounds such as styrene. When these radical polymerizable compounds are used, it is preferable to use a radical polymerization initiator such as 1-hydroxycyclohexyl phenyl ketone, acetophenone dimethyl ketal, and benzoyl methyl ether.

Further, the photopolymerizable resin composition of the present invention may be prepared by using an organic carboxylic acid or an acid anhydride for the purpose of improving electrical properties, or by using a polymer or other polymer for the purpose of imparting rubber elasticity. Flexible prepolymers can be mixed. Further, the photopolymerizable composition of the present invention, depending on the use, inorganic pigments such as inactive titanium oxide that does not affect the curability, organic pigments, dyes, fillers,
An antistatic agent, a flame retardant, an antifoaming agent, a flow controlling agent, a light stabilizer and the like can be added and used.

The photopolymerizable resin composition of the present invention can be easily cured by light. As a light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, or the like is used. In addition, laser light such as a semiconductor laser, an argon laser, and a He-Cd laser can be used. Further, the photopolymerizable resin composition of the present invention, α-ray,
It can be easily cured by ionizing radiation such as β-ray, γ-ray, neutron beam, X-ray and accelerating electron beam. They can be used alone or arbitrarily mixed.

[0045]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to only the following.

Example 1 215.0 g of a 30% aqueous sodium hydroxide solution was added to a 500 mL four-necked flask, and ethanol 40
mL and 23.6 g of 2-ethylanthraquinone were added and dispersed by stirring in a nitrogen stream. Further, 10.5 g of 80% hydrazine hydrate was added to this solution, and the temperature was raised to 7
The reaction was performed at 5 ° C. for 2 hours. The solution in which the yellow powder was dispersed turned into a dark red clear solution. Then add p
-130.2 g of methyl toluenesulfonate was added dropwise, and the mixture was stirred and reacted at 75 ° C for 2 hours. After cooling, the reaction solution was added to a 10 w% hydrosulfite solution 300
The mixture was poured into mL with stirring, and unreacted leuco body was removed by filtration. The obtained cake was added to 300 mL of water while stirring, and after filtering, the cake was further added to 30 mL of water.
After washing with 0 mL and drying, the desired 2-ethyl-9,
18.2 g of 10-dimethoxyanthracene (yield: 68.
4%). The obtained 2-ethyl-9,10-dimethoxyanthracene was a yellow powder having fluorescence, the purity was 98.1% (high-performance liquid chromatograph: 100% in area), and the melting point was 118 ° C. The analysis data of the obtained compound are shown below.

(A) Mass * 1: m / e = 266 (b) NMR * 2: (a) 4.13 ppm 6H (b) 2.86-2.93 ppm 2 H (c) 1.37-1. 42 ppm 3 H (c) UV-Vis * 3 (λmax * 4): 425 nm (ε * 5): Table 1 (d) Elemental analysis: Table 2 * 1: Mass is an abbreviation of mass spectrum. The same applies to the following embodiments. * 2: NMR is an abbreviation for proton nuclear magnetic resonance spectrum. CDCl3 solvent tetramethylsilane standard. * 3: UV-Vis is an abbreviation for ultraviolet-visible absorption spectrum. * 4: λ is the wavelength, λmax is the abbreviation of the maximum absorption wavelength. * 5: ε is an abbreviation for molar extinction coefficient.

Table 1 Peak wavelength (nm) ε 221 14260 252 66790 258 67410 342 2660 360 5230 379 7180 400 6010

Table 2 Element Actual value (% by weight) Calculated value (% by weight) C 81.21 81.16 H 6.81 6.83

Example 2 215.0 g of a 30% aqueous sodium hydroxide solution was added to a 500 mL four-necked flask, and ethanol 50
mL and 37.8 g of 2-ethylanthraquinone were added, and the mixture was stirred and dispersed in a nitrogen stream. Further, 22.0 g of 80% hydrazine hydrate was added to this solution, and the temperature was raised to 7
The reaction was performed at 5 ° C. for 2 hours. The solution in which the yellow powder was dispersed turned into a dark red clear solution. Then add p
-147.3 g of methoxyethyl toluenesulfonate was added dropwise, and then reacted by stirring at 75 ° C for 2 hours. After cooling, the reaction solution was added to a 5 w% hydrosulfite solution 300
The mixture was poured into mL with stirring, and unreacted leuco body was removed by filtration. The obtained cake was added to 300 mL of water while stirring, and after filtering, the cake was further added to 30 mL of water.
After washing with 0 mL and drying, the desired 2-ethyl-9,
10-di (methoxyethoxyethoxy) anthracene 3
6.5 g (yield 64.4%) was obtained. The obtained 2-ethyl-9,10-di (methoxyethoxy) anthracene is a yellow powder having fluorescence, the purity is 99.1% (high-performance liquid chromatography: 100% in area), and the melting point is 53 ° C.
Met. The analysis data of the obtained compound are shown below.

(A) Mass m / e = 354 (B) NMR (a) 8.12 to 8.35 ppm 4 H (b) 7.32 to 7.47 ppm 3 H (c) 4.29 to 4.33 ppm 4 H (d) 3.84 to 3.88 ppm 4 H (e) 3.55 ppm 6 H (f) 2.82 to 2.90 ppm 2 H (g) 1.34 to 1.37 ppm 3 H (c) UV -Vis (λmax): 420 nm (ε): Table 3 (d) Elemental analysis: Table 4

Table 3 Peak wavelength (nm) ε 221 16200 252 74500 259 80600 360 6140 380 8120 401 7220

[0053]
Table 4 Element Measured value (% by weight) Calculated value (% by weight) C 74.50 74.54 H 7.43 7.41

The methoxyethyl p-toluenesulfonate used here was synthesized by the following method. That is, 114.2 g of 2-methoxyethanol was put into a 1 L four-necked flask, and 316.4 g of p-toluenesulfonic acid chloride was added with stirring. Further, 400.0 g of a 30 wt% aqueous sodium hydroxide solution was added dropwise to this solution at 0 to 20 ° C. over 2 hours, and the mixture was further reacted at 0 to 20 ° C. with stirring for 4 hours. Further, 120 g of water was added to the reaction solution,
Neutralized with hydrochloric acid and the aqueous layer was removed. The remaining organic layer is washed with water 10
After washing twice with 0 g, drying over anhydrous magnesium sulfate and filtering, 253. methoxyethyl p-toluenesulfonate.
5 g (73.4% yield) was obtained. The resulting methoxyethyl p-toluenesulfonate had a specific gravity of 1.205 (20
° C), and the purity was 98.6% (high-performance liquid chromatography: 100% in area).

Example 3 In the same manner as in Examples 1 and 2, 159.6 g of isobutyl p-toluenesulfonate was used in place of methoxyethyl p-toluenesulfonate or methyl p-toluenesulfonate, 21.1 g (yield 60.3%) of ethyl-9,10-diisobutoxyanthracene was obtained. The obtained 2-ethyl-9,10-diisobutoxyanthracene was a yellow powder having fluorescence, the purity was 98.3% (high-performance liquid chromatography: 100% in area), and the melting point was 96 ° C. . The λmax of this is 4
20 nm. Table 5 shows the results of elemental analysis of this product.

Table 5 Element Actual value (% by weight) Calculated value (% by weight) C 82.26 82.23 H 8.68 8.64

The isobutyl p-toluenesulfonate used here was synthesized by the following method. That is, 100.0 g of isobutyl alcohol was placed in a 2 L four-necked flask, and p-toluenesulfonic acid chloride 1 was added with stirring.
90.5 g were added. Further, 540.0 g of a 30% by weight aqueous sodium hydroxide solution was added dropwise to this solution at 0 to 10 ° C over 10 hours, and the mixture was further reacted at 0 to 10 ° C with stirring for 24 hours. Further, 300 g of water was added to the reaction solution, neutralized with an appropriate acid, and the aqueous layer was removed. The remaining organic layer was washed twice with 100 g of water, dried over anhydrous magnesium sulfate, filtered, and washed with isobutyl p-toluenesulfonate.
3.5 g (79.1% yield) was obtained. The obtained isobutyl p-toluenesulfonate has a specific gravity of 1.155 (20 ° C.).
And its purity was 98.1% (high-performance liquid chromatograph: 100% area). The results of the elemental analysis are as shown in Table 6.

Table 6 Element Actual value (% by weight) Calculated value (% by weight) C 57.94 57.86 H 7.02 7.08 S 14.07 14.04

Synthesis Examples of Other Anthracene Derivatives Using p-Toluenesulfonate Ester Compounds p-Toluenesulfonate compounds were synthesized by the method according to Examples 2 and 3, and The following anthracene derivative can be synthesized by reacting a p-toluenesulfonic acid ester compound with a compound obtained by reducing an anthraquinone derivative using hydrazine or a derivative thereof by a method according to 3.

2-ethyl-9,10-di (4-t-butylcyclohexyloxy) anthracene 2-ethyl-9,10-di (4-methyl-3-pentenyloxy) anthracene 2-ethyl-9 2,10-dibenzyloxyanthracene 2-phenylthio-9,10-dimethoxyanthracene 1-chloro-9,10-dimethoxyanthracene 2-dodecyl-9,10-dimethoxyanthracene 2-stearyl-9,10-dimethoxy 2,4-dimethyl-9,10-di (2-hydroxyethyloxy) anthracene 2-ethyl-9,10-di (2-n-butyloxyethyloxy) anthracene 2-ethyl-9,10 -Di (3-acetoxypropyloxy) anthracene

Example 4 To a 500 mL four-necked flask was added 215.0 g of a 30% aqueous sodium hydroxide solution, and the solution was added with ethanol 40%.
mL and 23.6 g of 2-ethylanthraquinone were added and dispersed by stirring in a nitrogen stream. Further, 10.5 g of 80% hydrazine hydrate was added to this solution, and the temperature was raised to 7
The reaction was performed at 0 ° C. for 2 hours. The solution in which the yellow powder was dispersed turned into a dark red clear solution. Next, 77.0 g of methyl methanesulfonate was added dropwise to the solution, and the mixture was stirred and reacted at 70 ° C. for 2 hours. After cooling, the reaction solution was poured into 300 mL of a 10 w% hydrosulfite solution with stirring, and the unreacted leuco body was removed by filtration. 300m of water while stirring the obtained cake
In addition to L, after filtration, the cake was further washed with 300 mL of water and dried to obtain 18.0 g (yield: 67.7%) of the target 2-ethyl-9,10-dimethoxyanthracene. The obtained 2-ethyl-9,10-dimethoxyanthracene is a fluorescent yellow powder having a purity of 9%.
8.1% (high-performance liquid chromatography: 100% area)
Melting point was 118 ° C. The analysis data of the obtained compound are shown below.

(B) Mass: m / e = 266 (b) NMR: (a) 4.13 ppm 6H (b) 2.86 to 2.93 ppm 2H (c) 1.37 to 1.42 ppm 3H (c) UV-Vis (λmax): 425 nm (ε): Table 7 (d) Elemental analysis: Table 8

Table 7 Peak wavelength (nm) ε 223 14360 250 66800 259 67470 342 2530 361 5240 379 7180 403 6000

[0064]
Table 8 Element Actual value (% by weight) Calculated value (% by weight) C 81.13 81.16 H 6.82 6.83

Example 5 In the same manner as in Example 4, methyl methanesulfonate 7
Instead of 7.0 g, n-butyl methanesulfonate 10
Using 6.5 g, 22.8 g (yield 65.1%) of 2-ethyl-9,10-di-n-butoxyanthracene was obtained. The obtained 2-ethyl-9,10-di-n-butoxyanthracene was a yellow powder having fluorescence, the purity was 98.3% (high performance liquid chromatography), and the melting point was 99 ° C. Its λmax was 420 nm. Table 9 shows the results of elemental analysis of this product.
The n-butyl methanesulfonate used here was synthesized and obtained by reacting n-butyl alcohol and methanesulfonyl chloride in the presence of diethylamine.

Table 9 Element Actual value (% by weight) Calculated value (% by weight) C 82.24 82.23 H 8.65 8.64

Synthesis Examples of Other Anthracene Derivatives Using Alkyl Sulfonate Ester Compounds An alkyl sulfonic acid ester compound was synthesized by the method according to Example 5, and the alkyl sulfonic acid compound and the anthraquinone derivative were converted to hydrazine or a derivative thereof. The anthracene derivative shown below can be synthesized by reacting the compound reduced using

2-ethyl-9,10-di (4-t-butylcyclohexyloxy) anthracene 2-ethyl-9,10-di (4-methyl-3-pentenyloxy) anthracene 2-ethyl-9 2,10-dibenzyloxyanthracene 2-phenylthio-9,10-dimethoxyanthracene 1-chloro-9,10-dimethoxyanthracene 2-dodecyl-9,10-dimethoxyanthracene 2-stearyl-9,10-dimethoxy Anthracene 2,4-dimethyl-9,10-di (2-hydroxyethyloxy) anthracene 2-Ethyl-9,10-di (2-n-butyloxyethyloxy) anthracene

Example 6 To a 500 mL four-necked flask was added 215.0 g of a 30 w% aqueous sodium hydroxide solution.
mL and 36.3 g of anthraquinone were added, and the mixture was stirred and dispersed in a nitrogen stream. Further, 20.6 g of 80% hydrazine hydrate was added to this solution, and the mixture was heated and reacted at 75 ° C. for 2 hours. The solution in which the yellow powder was dispersed turned into a dark red clear solution. Next, the solution was cooled to 30 ° C., 167.4 g of diethyl sulfate was added dropwise, and the mixture was stirred and reacted at 75 ° C. for 2 hours. After cooling, the reaction solution was poured into 300 mL of a 5 w% hydrosulfite solution with stirring, and the unreacted leuco body was removed by filtration.
The obtained cake was added to 300 mL of water while stirring, and after filtration, the cake was further washed with 300 mL of water and dried to obtain the desired 9,10-diethoxyanthracene 3
3.2 g (71.6% yield) was obtained. 9,10 obtained
-Diethoxyanthracene was a fluorescent yellow powder, having a purity of 98.7% (high performance liquid chromatograph: area percent) and a melting point of 149 ° C. The analysis data of the obtained compound are shown below.

(A) Mass: m / e = 266 (B) NMR: (a) 8.28 to 8.31 ppm 4H (b) 7.46 to 7.50 ppm 4H (c) 4.21 to 4.29 ppm 4H (d) 1.60 to 1.65 ppm 6H (c) UV-Vis (λmax): 420 nm (ε): Table 10 (d) Elemental analysis: Table 11

Table 10 Peak wavelength (nm) ε 218 15200 251 65000 361 6080 380 8960 402 7650

[0072]
Table 11 Element Actual measured value (% by weight) Calculated value (% by weight) C 81.20 81.16 H 6.78 6.83

Example 7 215.0 g of a 30% aqueous sodium hydroxide solution was added to a 500 mL four-necked flask, and ethanol 40
mL and 23.6 g of 2-ethylanthraquinone were added, and the mixture was stirred and dispersed under a nitrogen stream. Further, 10.5 g of 80% hydrazine hydrate was added to this solution, and the temperature was raised to 7
The reaction was performed at 5 ° C. for 2 hours. The solution in which the yellow powder was dispersed turned into a dark red clear solution. Then, add this solution to 3
After cooling to 0 ° C. and dropwise addition of 88.2 g of dimethyl sulfate, the mixture was stirred and reacted at 75 ° C. for 2 hours. After cooling, the reaction solution was poured into 300 mL of a 5 w% hydrosulfite solution with stirring, and the unreacted leuco body was removed by filtration. 300 mL of water while stirring the obtained cake
After filtration, the cake was further washed with 300 mL of water and dried to obtain 18.7 g of the desired 2-ethyl-9,10-dimethoxyanthracene (70.3% yield). The obtained 2-ethyl-9,10-dimethoxyanthracene is a fluorescent yellow powder having a purity of 98.
6% (high-performance liquid chromatograph: area percent), and the melting point was 119 ° C. The analysis data of the obtained compound are shown below.

(B) Mass: m / e = 266 (b) NMR: (a) 4.12 ppm 6H (b) 2.84 to 2.94 ppm 2H (c) 1.37 to 1.43 ppm 3H (c) UV-Vis (λmax): 425 nm (ε): Table 12 (d) Elemental analysis: Table 13

Table 12 Peak wavelength (nm) ε 221 14570 252 66660 258 68270 342 2670 360 5450 379 7230 400 6020

[0076]
Table 13 Element Actual value (% by weight) Calculated value (% by weight) C 81.23 81.16 H 6.83 6.83

Example 8 In the same manner as in Example 7, 2-ethyl-9,10-di-n-butoxyanthracene 22 was used, except that 147.1 g of di-n-butyl sulfate was used instead of 88.2 g of dimethyl sulfate. .
8 g (65.1% yield) was obtained. The obtained 2-ethyl-
9,10-di-n-butoxyanthracene was a yellow powder having fluorescence, the purity was 98.0% (high-performance liquid chromatography: 100% in area), and the melting point was 98 ° C.
The λmax of this product was 420 nm. The results of elemental analysis of this product are as shown in Table 14.

Table 14 Element Actual value (% by weight) Calculated value (% by weight) C 82.14 82.23 H 8.66 8.64

The di-n-butyl sulfate used here was synthesized by the following method. That is, 547.2 g of dried n-butyl alcohol was placed in a 2 L four-necked flask, and 400.0 g of thionyl chloride was slowly dropped over 2 hours while stirring. The temperature of the reaction solution was maintained at 35 to 40 ° C. in a water bath, and the temperature was slowly increased simultaneously with the generation of hydrogen chloride. After completion of the dropwise addition, the temperature was raised using an oil bath to complete the reaction, the remaining hydrogen chloride was expelled, and the residue was distilled under reduced pressure at a pressure of 15 mmHg to obtain 110 to 115
Di-n-butyl sulfite distilled at ℃ was recovered. 425.3 g of recovered di-n-butyl sulfite (yield: 65.2).
%) As a colorless transparent liquid. Further, 425.3 g of di-n-butyl sulfite thus obtained was placed in a 1-L four-necked flask, and sulfuryl chloride 14
After slowly dropping 7.8 g over 1 hour, 100
The reaction was carried out at ℃ 110 ° C. for 1 hour. During this time, the generated sulfur dioxide was connected to a gas absorption trap and removed. After the generation of sulfur dioxide was weakened, the mixture was heated at 130 to 135 ° C. for 3 hours to distill n-butyl chloride as a by-product. The remaining reaction solution was placed in a 300-mL separating funnel, washed with 50 mL of a saturated sodium carbonate aqueous solution, the organic layer was separated, anhydrous potassium carbonate was added, and the mixture was left overnight to dry. After drying,
The reaction solution was distilled off under reduced pressure, and was
172.6 g (yield, 75.0% from sulfuryl chloride) of di-n-butyl sulfate distilled at 13 ° C. were recovered. The obtained di-n-butyl sulfate was a colorless and transparent liquid, and the purity was 98.0% (gas chromatograph: area percent). The results of the elemental analysis are as shown in Table 15.

Table 15 Element Actual value (% by weight) Calculated value (% by weight) C 45.62 45.68 H 8.65 8.64 S 15.23 15.25

Synthesis Examples of Other Anthracene Derivatives Using Sulfuric Ester Compounds Sulfuric ester compounds were synthesized in the same manner as in Example 8 and further combined with the sulfuric acid ester compounds in the same manner as in Examples 7 and 8. By reacting a compound obtained by reducing an anthraquinone derivative with hydrazine or a derivative thereof, the following anthracene derivative can be synthesized.

2-ethyl-9,10-di (4-t-butylcyclohexyloxy) anthracene 2-ethyl-9,10-di (4-methyl-3-pentenyloxy) anthracene 2-ethyl-9 2,10-dibenzyloxyanthracene 2-phenylthio-9,10-dimethoxyanthracene 1-chloro-9,10-dimethoxyanthracene 2-dodecyl-9,10-dimethoxyanthracene 2-stearyl-9,10-dimethoxy Anthracene 2,4-dimethyl-9,10-di (2-hydroxyethyloxy) anthracene 2-Ethyl-9,10-di (2-n-butyloxyethyloxy) anthracene

Examples 9 to 11 The 9,10-dietherified anthracene derivative prepared in Examples 1 to 8 was dissolved by heating in Celloxide 2021 (Daicel Chemical Co., Ltd .: alicyclic epoxy resin).
Table 16 shows the results of confirming the state of crystal precipitation after storage in a refrigerator for one week. The novel anthracene compound of the present invention, 2-ethyl-9,10-di (methoxyethoxy) anthracene, is known as compared with the known anthracene compounds 2-ethyl-9,10-dimethoxyanthracene and 9,10-diethoxyanthracene. It is apparent that the solubility is clearly improved.

Table 16 Example No. Novelty of the name of the compound Novelty of the structure Concentration (outer part) Crystal precipitation 9 2-ethyl-9,10-di (methoxyethoxy) anthracene New 15% None 10 2-ethyl-9,10-dimene Toxianthracene Known 5% Available 11 9,10-Diethoxyanthracene Known 5% Available

When a coating film was formed using the resin composition containing the anthracene compound used in Examples 10 and 11, when the concentration relative to the resin was 5 wt%, the anthracene compound was added to the film surface. Crystals of the compound are precipitated, and the possibility of obtaining a uniform and flat film surface is extremely high.
When compared with the resin composition containing an anthracene compound having a novel structure used in Example 9, the coatability is very poor.

Example 12 An epoxy group-containing polycarboxylic acid resin was synthesized as follows. Phenol novolak type epoxy resin (Nippon Kayaku Co., Ltd., EPPN-503, epoxy equivalent 18)
0.5) 361.0 g (2 equivalents), 134.1 g (1 mol) dimethylolpropionic acid, 86.7 g of carbitol acetate and 37.1 g of solvent naphtha were charged.
The mixture was heated and stirred at 90 ° C. to dissolve the reaction mixture. The reaction was then cooled to 60 ° C. and triphenylphosphine 1.
86 g (0.007 mol) was charged, heated to 100 ° C., and reacted for about 20 hours. When the acid value became 0.7 mg KOH / g or less, the mixture was cooled to 50 ° C., and cumene hydroperoxide 1.07 g. (0.007 mol), 169.4 g of carbitol acetate and 72.6 g of solvent naphtha were charged and reacted for about 3 hours to oxidize triphenylphosphine as a reaction catalyst to deactivate the catalytic activity. Then, 184.2 g of tetrahydrophthalic anhydride
(1.21 mol), and reacted at 95 ° C. for 10 hours.
5%). The acid value of the product (solid content) is about 100 m
gKOH / g.

Using the epoxy group-containing polycarboxylic acid resin thus obtained, resin compositions shown in the following Table 17 were prepared.

Table 17 Example 12 Comparative Example Epoxy group-containing polycarboxylic acid resin 5 g 5 g CYRACURE UVI-6990 * 6 0.490 g 0.490 g 2-ethyl-9,10-di (methoxyethoxy) anthracene 0.245 g − Propylene glycol monomethyl ether acetate 3.860 g 3.860 g * 6 Union Carbide photocationic polymerization initiator (active ingredient 50 wt%)

The above resin composition was coated on a glass substrate at 1000
After spin-coating at 30 rpm for 30 seconds, pre-baking in an oven at 80 ° C. for 30 minutes, and using a high-pressure mercury lamp at 2000 mJ /
Step tablet (Kodak Co., Ltd.) with an exposure amount of cm ²
No. 2) was baked. Next, 3 in an oven at 90 ° C.
After baking for 0 minutes, development was performed with a 1% aqueous sodium carbonate solution, and the number of steps in which a cured film which was dissolved and not removed by development, ie, a residual film remained, was confirmed. As a result, 2-ethyl
In a comparative example in which -9,10-di (methoxyethoxy) anthracene was not added, a residual film remained only up to 5 steps (exposure amount: 315 mJ / cm ² ), whereas 2-ethyl-9,10-di ( In Example 12 in which (methoxyethoxy) anthracene was added, a residual film remained up to 9 steps (exposure amount: 79 mJ / cm ² ).
A clear sensitizing effect of ethyl-9,10-di (methoxyethoxy) anthracene was confirmed.

[0090]

As is apparent from the above results, the novel anthracene compound of the present invention has a higher solubility in various cationically polymerizable compounds than known anthracene compounds, and the cationic polymerizable compound as an essential component The photopolymerizable composition containing the linearly sensitive cationic polymerization initiator and the novel anthracene compound exhibits excellent curing performance. Further, by using hydrazines for reduction of anthraquinones and further reacting with an appropriate alkylating agent, it has become possible to produce an anthracene derivative having a desired structure in a short time with good yield, easily and inexpensively. Since this production method does not use a metal-based reducing agent, the step of recovering the catalyst can be omitted, which is industrially useful.

【wrap up】

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/028 G03F 7/028

Claims (13)

[Claims] 1. A 9,10 dietherified anthracene compound represented by the formula (1): ## STR1 ## Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈
Hydrogen atoms are each independently an alkyl group of C ₁ -C _12,
Fluorine atom, chlorine atom, bromine atom, cyano group, phenyl group, cyclohexyl group, hydroxyl group, benzyl group, cyclohexylmethyl group, 1-naphthyl group, 2-naphthyl group,-
O-R _9, is either -CO-R ₉ or -S-R _9. R ₉ is a C ₁ -C ₈ alkyl group, phenyl group, benzyl group, cyclohexyl group, cyclohexylmethyl group, 1-naphthyl group or 2-naphthyl group. X _{is, - (CH 2) l Y} , - ((CH 2) m O)
_{n Z, - (CH (CH} 3) CH 2 O) n Z, - (CH 2)
_{m O (CH 2) n OZ} , allyl group, glycidyl group, a cyclohexyl group, a cyclohexylmethyl group, 1-naphthyl, 2-naphthyl, 3-hydroxypropyl group, 4
A hydroxybutyl group, a 4-tert-butylcyclohexyl group or a 4-methyl-3-pentenyl group, and Y is a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a cyclohexyl group, a 1-naphthyl group, A naphthyl group, and Z is C _1-
Linear or branched alkyl group, linear or branched, saturated or unsaturated acyl group of C ₁ -C _8, aryl group having C _8,
Glycidyl, phenyl, benzyl, cyclohexyl, 2-phenylethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, benzoyl, cyclohexylmethyl, 1-naphthyl or 2- Any one of naphthyl groups, 1 is an integer of 2 to 8, and m and n are integers of 1 to 4. ) 2. A formula (1), R _2, R _3, any one of a hydrogen atom of R ₆ or R _7, C ₁ -C ₁₂ 2 alkyl groups, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a phenyl group, a cyclohexyl group, a hydroxyl group, a benzyl group, a cyclohexylmethyl group, 1-naphthyl, _{2-naphthyl, -O-R 9, -CO-} R 9 or -S-R ₉ (R ₉ is C
_{1 to} C ₈ alkyl, phenyl, benzyl, cyclohexyl, cyclohexylmethyl, 1-naphthyl or 2-naphthyl, with the remainder being hydrogen atoms, R ₁ , R ₄ , R ₅ and R ₈ are hydrogen atoms, X _{is, - (CH 2) l Y} , - ((CH 2) m O) n
_{Z, - (CH (CH 3} ) CH 2 O) n Z, - (CH 2) m
O (CH ₂ ) _n OZ, allyl group, glycidyl group, cyclohexyl group, cyclohexylmethyl group, 1-naphthyl group, 2-naphthyl group, 3-hydroxypropyl group, 4-
A hydroxybutyl group, a 4-tert-butylcyclohexyl group or a 4-methyl-3-pentenyl group, and Y is a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a cyclohexyl group, a 1-naphthyl group, A naphthyl group, and Z is C _1-
Linear or branched alkyl group, linear or branched, saturated or unsaturated acyl group of C ₁ -C _8, aryl group having C _8,
Glycidyl, phenyl, benzyl, cyclohexyl, 2-phenylethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, benzoyl, cyclohexylmethyl, 1-naphthyl or 2- Any one of naphthyl groups, 1 is an integer of 2 to 8, and m and n are integers of 1 to 4. The anthracene compound according to claim 1, wherein the remaining substituent is a hydrogen atom. 3. In the formula (1), R_Two, R_Three, R₆There
Is R₇Any one of is a hydrogen atom or an ethyl group
And the remaining substituents are hydrogen atoms;₁, R_Four, R _FiveYou
And R₈Is a hydrogen atom, and X is-(CH_Two)_lY,-
((CH_Two)_mO)_nZ,-(CH (CH_Three) CH_TwoO)
_nZ,-(CH_Two)_mO (CH_Two)_nOZ, allyl group, group
Lysidyl group, cyclohexyl group, cyclohexylmethyl
Group, 1-naphthyl group, 2-naphthyl group, 3-hydroxy
Propyl group, 4-hydroxybutyl group, 4-tert-
Butylcyclohexyl group or 4-methyl-3-pen
Any one of a thenyl group, and Y is a fluorine atom, a salt,
Atom, bromine atom, phenyl group, cyclohexyl group, 1
-A naphthyl group or a 2-naphthyl group
And Z is C₁~ C₈A linear or branched alkyl group,
C₁~ C₈Linear or branched saturated or unsaturated acyl
Group, allyl group, glycidyl group, phenyl group, benzyl
Group, cyclohexyl group, 2-phenylethyl group, 2-
Droxyethyl group, 3-hydroxypropyl group, 4-h
Droxybutyl group, benzoyl group, cyclohexylmethyl
A 1-naphthyl group or a 2-naphthyl group
And l is an integer of 2 to 8, m and n are integers of 1 to 4.
The anthracene compound according to claim 1, which is represented by a number. 4. In the formula (1), any one of R ₂ , R ₃ , R _{6 and} R ₇ is an ethyl group, the remaining substituents are hydrogen atoms, and R ₁ , R ₄ , R ₅ The 9,10-dietherified anthracene compound according to claim 1, wherein R ₈ is a hydrogen atom, and X is a 2-methoxyethyl group. 5. An essential component comprising (1) a cationically polymerizable compound, (2) an energy ray-sensitive cationic polymerization initiator, and (3) a 9,10 dietherified anthracene compound according to claim 1. Characteristic photopolymerizable composition. 6. The photopolymerizable composition according to claim 5, wherein the anthracene compound is the 9,10 dietherified anthracene compound according to claim 2. 7. The photopolymerizable composition according to claim 5, wherein the 9,10-dietherified anthracene compound is the 9,10-dietherified anthracene compound according to claim 3. 8. A process for producing a 9,10-dietherified anthracene derivative, comprising reducing anthraquinones with hydrazines and then reacting with an alkylating agent. 9. An anthraquinone represented by the formula (2): (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom, a C1-C12 alkyl group, a fluorine atom, a chlorine atom, a bromine atom, Cyano group, phenyl group, cyclohexyl group, hydroxyl group, benzyl group, cyclohexylmethyl group, 1-naphthyl group, 2-naphthyl group,-
_{O-R 9, -CO-R} 9 or -S-R ₉ (R ₉ is C ₁ -C ₈
Or an alkyl group, a phenyl group, a benzyl group, a cyclohexyl group, a cyclohexylmethyl group, a 1-naphthyl group or a 2-naphthyl group. ). The method for producing a 9,10-dietherified anthracene derivative according to claim 7, which is a compound represented by the formula: 10. In the formula (2), any one of R ₂ , R ₃ , R _{6 and} R7 is a hydrogen atom, a C1-C12 alkyl group, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a phenyl group. , Cyclohexyl group, hydroxyl group, benzyl group, cyclohexylmethyl group, 1-naphthyl group, 2-naphthyl group, -OR ₉ , -CO-R ₉ or -SR
₉ (R ₉ is a C ₁ -C ₈ alkyl, phenyl, benzyl, cyclohexyl, cyclohexylmethyl, 1-
It is either a naphthyl group or a 2-naphthyl group. The remaining substituents are hydrogen atoms, and R ₁ , R ₄ , R ₅ and R ₈ are hydrogen atoms.
The method for producing a 9,10-dietherified anthracene described in (1). 11. The method according to claim 8, wherein in the formula (2), any one of R ₂ , R ₃ , R _{6 and} R ₇ is an ethyl group, and the remaining substituents are hydrogen atoms. -A process for the preparation of dietherified anthracene. 12. An alkylating agent represented by the following formula (3): A p-toluenesulfonic acid ester compound represented by the formula: or an alkylsulfonic acid ester compound represented by the formula: R ₁₀ SO ₂ OX ′ (4) or a sulfate ester represented by the formula (X′O) ₂ SO ₂ (5) Compound (wherein, R ₁₀ is any one of a methyl group, an ethyl group and a trifluoromethyl group, and X ′ is a C _{1 to} C ₁₈ linear or branched alkyl group, a benzyl group, α-methylbenzyl Group,-(C
_{H 2) l Y, - (} (CH 2) m O) n Z, - (CH (CH
_{3) CH 2 O) n Z} , - (CH 2) m O (CH 2) n OZ,
Allyl group, glycidyl group, cyclohexyl group, cyclohexylmethyl group, 1-naphthyl group, 2-naphthyl group, 2
-Hydroxyethyl group, 3-hydroxypropyl group, 4
-Hydroxybutyl group, 4-tert-butylcyclohexyl group or 4-methyl-3-pentenyl group, and Y is a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a cyclohexyl group, a 1-naphthyl group or Any one of 2-naphthyl groups, wherein Z is C ₁ -C ₈
Linear or branched alkyl group, linear or branched, saturated or unsaturated acyl group of C ₁ -C _8, an allyl group, a glycidyl group, a phenyl group, a benzyl group, a cyclohexyl group, a 2-phenylethyl group, 2-hydroxyethyl group,
3-hydroxypropyl group, 4-hydroxybutyl group,
A benzoyl group, a cyclohexylmethyl group, a 1-naphthyl group or a 2-naphthyl group;
An integer of 8, m and n are integers of 1 to 4. The method for producing a 9,10-dietherified anthracene derivative according to any one of claims 8, 9, 10, and 11. 13. An alkylating agent comprising a compound represented by the formula (3):
The method for producing a 9,10-dietherified anthracene derivative according to any one of claims 8, 9, 10, and 11, which is a toluenesulfonic acid ester.