JP2017149702A - Method for producing carboxylic acid ester, esterifying agent, and ring-opening addition catalyst - Google Patents

Abstract

An object of the present invention is to provide a method for producing a carboxylic acid ester using a catalyst compound which is easy to handle and has high activity, and an esterifying agent and a ring-opening addition catalyst suitably used in the production method. (A) At least one electrophile selected from the group consisting of at least one hydroxy group-providing compound selected from the group consisting of a phenol compound and an alcohol and an epoxy group-providing compound consisting of an epoxy compound. And (B) at least one nucleophile selected from the group consisting of a carboxylic acid, a carboxylic acid halide, a carboxylic acid ester, and a carboxylic acid anhydride, to produce a carboxylic acid ester. Sometimes an imidazole compound of a specific structure is present. [Selection diagram] None

Description

  The present invention relates to a method for producing a carboxylic acid ester, an esterifying agent, and a ring-opening addition catalyst.

  Carboxylic acid esters such as oils and fats, surfactants, pharmaceuticals, organic solvents, and monomer compounds for functional polymer synthesis are used in a wide range of fields. For this reason, the esterification reaction is an industrially very important reaction.

  In the esterification reaction, in general, a strong acid or a strong base such as sulfuric acid, sodium hydroxide, and potassium hydroxide is often used as a catalyst. However, many of these strong acids and strong bases are deleterious substances, and sufficient caution is required for their use. There is also a problem in that it causes corrosion of a reaction apparatus made of metal or glass.

  On the other hand, solid acid catalysts such as an ion exchange resin catalyst (see Patent Document 1) and hydrous zirconium oxide (see Patent Document 2) are easy to handle and less likely to cause corrosion of the reactor. Are known.

International Publication No. 98/25876 Pamphlet Japanese Examined Patent Publication No. 4-28250

However, the ion exchange resin catalyst as disclosed in Patent Document 1 is likely to decrease in strength due to use at a high temperature or due to swelling by a solvent, and there are many restrictions in use conditions.
Further, the hydrous zirconium oxide as disclosed in Patent Document 2 has a low activity, and there is a problem that it is necessary to use a large amount of catalyst or to perform a reaction at a high temperature.

  The present invention has been made in view of the above-described problems, and is easy to handle, and a method for producing a carboxylic acid ester using a highly active catalyst compound, and an esterifying agent suitably used in the production method And a ring-opening addition catalyst.

  The inventors of the present invention have made extensive studies to achieve the above object. As a result, (A) at least one hydroxy group-providing compound selected from the group consisting of a phenol compound and an alcohol; an epoxy group-providing compound consisting of an epoxy compound; and at least one electrophile selected from the group consisting of: (B) when producing a carboxylic acid ester by reacting at least one nucleophile selected from the group consisting of carboxylic acid, carboxylic acid halide, carboxylic acid ester, and carboxylic anhydride, The inventors have found that the above problems can be solved by the presence of an imidazole compound having a specific structure, and have completed the present invention. Specifically, the present invention provides the following.

（式（１）中、Ｒ^１はそれぞれ独立に水素原子もしくは１価の有機基を表し、Ｒ^２は置換基を有してもよい芳香族基を表し、Ｒ^３はそれぞれ独立にハロゲン原子、ヒドロキシ基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基を表し、ｎは０〜３の整数を表す。前記Ｒ^１は他方のＲ^１又はＲ^２と結合して環状構造を形成してもよい。）
で表されるイミダゾール化合物の存在下に反応させることを含む、カルボン酸エステルの製造方法である。 The first aspect of the present invention is:
(A) at least one hydroxy group-providing compound selected from the group consisting of a phenol compound and an alcohol; and an epoxy group-providing compound consisting of an epoxy compound; and at least one electrophile selected from the group consisting of:
(B) at least one nucleophile selected from the group consisting of carboxylic acid, carboxylic acid halide, carboxylic acid ester, and carboxylic acid anhydride,
Following formula (1):

(In Formula (1), R ¹ each independently represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic group which may have a substituent, and R ³ each independently represents a halogen atom, A hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n represents an integer of 0 to 3. R ¹ may combine with the other R ¹ or R ² to form a cyclic structure.)
It is a manufacturing method of carboxylic acid ester including making it react in presence of the imidazole compound represented by these.

（式（１）中、Ｒ^１はそれぞれ独立に水素原子もしくは１価の有機基を表し、Ｒ^２は置換基を有してもよい芳香族基を表し、Ｒ^３はそれぞれ独立にハロゲン原子、ヒドロキシ基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基を表し、ｎは０〜３の整数を表す。前記Ｒ^１は他方のＲ^１又はＲ^２と結合して環状構造を形成してもよい。）
で表されるイミダゾール化合物を含有する、エステル化剤である。 The second aspect of the present invention is the following formula (1):

(In Formula (1), R ¹ each independently represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic group which may have a substituent, and R ³ each independently represents a halogen atom, A hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n represents an integer of 0 to 3. R ¹ may combine with the other R ¹ or R ² to form a cyclic structure.)
It is an esterifying agent containing the imidazole compound represented by these.

（式（１）中、Ｒ^１はそれぞれ独立に水素原子もしくは１価の有機基を表し、Ｒ^２は置換基を有してもよい芳香族基を表し、Ｒ^３はそれぞれ独立にハロゲン原子、ヒドロキシ基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基を表し、ｎは０〜３の整数を表す。前記Ｒ^１は他方のＲ^１又はＲ^２と結合して環状構造を形成してもよい。）
で表されるイミダゾール化合物を含有する、開環付加触媒である。 The third aspect of the present invention is the following formula (1):

(In Formula (1), R ¹ each independently represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic group which may have a substituent, and R ³ each independently represents a halogen atom, A hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n represents an integer of 0 to 3. R ¹ may combine with the other R ¹ or R ² to form a cyclic structure.)
It is a ring-opening addition catalyst containing the imidazole compound represented by these.

  According to the present invention, it is possible to provide a method for producing a carboxylic acid ester that uses a catalyst compound that is easy to handle and has high activity, and an esterifying agent and a ring-opening addition catalyst that are preferably used in the production method. it can.

≪Method for producing carboxylate ester≫
In the method for producing a carboxylic acid ester,
(A) At least one electrophile selected from the group consisting of at least one hydroxy group-providing compound selected from the group consisting of a phenol compound and an alcohol and an epoxy group-providing compound consisting of an epoxy compound (hereinafter referred to as “( A) Electrophile ")),
(B) at least one nucleophile selected from the group consisting of a carboxylic acid, a carboxylic acid halide, a carboxylic acid ester, and a carboxylic acid anhydride (hereinafter also referred to as “(B) nucleophile”);
To produce a carboxylic acid ester.

（式（１）中、Ｒ^１はそれぞれ独立に水素原子もしくは１価の有機基を表し、Ｒ^２は置換基を有してもよい芳香族基を表し、Ｒ^３はそれぞれ独立にハロゲン原子、ヒドロキシ基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基を表し、ｎは０〜３の整数を表す。前記Ｒ^１は他方のＲ^１又はＲ^２と結合して環状構造を形成してもよい。）
で表されるイミダゾール化合物の存在下に行われる。 The reaction of the above (A) electrophile and (B) nucleophile is represented by the following formula (1):

(In Formula (1), R ¹ each independently represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic group which may have a substituent, and R ³ each independently represents a halogen atom, A hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n represents an integer of 0 to 3. R ¹ may combine with the other R ¹ or R ² to form a cyclic structure.)
It is carried out in the presence of an imidazole compound represented by:

(A) The electrophile and (B) the nucleophile are reacted in the presence of the imidazole compound represented by the formula (1), so that the esterification reaction can proceed well even at a low temperature or desired. The time required for the reaction to proceed to the extent can be shortened.
Moreover, since the imidazole compound represented by the formula (1) is not a strong acid or a strong base such as sulfuric acid, sodium hydroxide, and potassium hydroxide, it hardly corrodes the reaction apparatus used for the production of the carboxylic acid ester. .

<Imidazole compound>
Hereinafter, the imidazole compound used in the manufacturing method of an ester compound is demonstrated. The imidazole compound is a compound represented by the following formula (1). Hereinafter, the compound represented by the following formula (1) is also simply referred to as “imidazole compound”.

（式（１）中、Ｒ^１はそれぞれ独立に水素原子もしくは１価の有機基を表し、Ｒ^２は置換基を有してもよい芳香族基を表し、Ｒ^３はそれぞれ独立にハロゲン原子、ヒドロキシ基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基を表し、ｎは０〜３の整数を表す。前記Ｒ^１は他方のＲ^１又はＲ^２と結合して環状構造を形成してもよい。）

(In Formula (1), R ¹ each independently represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic group which may have a substituent, and R ³ each independently represents a halogen atom, A hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n represents an integer of 0 to 3. R ¹ may combine with the other R ¹ or R ² to form a cyclic structure.)

In addition, the imidazole compound represented by Formula (1) may be, for example, a compound having a hydroxy group or a carboxy group, or a carboxylic acid ester. That is, the imidazole compound represented by the formula (1) may be a compound corresponding to (A) an electrophile or (B) a nucleophile.
However, since the amount of the imidazole compound represented by the formula (1) is usually small with respect to the amount of the (A) electrophile and (B) nucleophile, it is represented by the formula (1). Even if the imidazole compound is a compound corresponding to (A) an electrophile or (B) a nucleophile, there is little or no adverse effect on the target esterification reaction.
When the imidazole compound represented by the formula (1) corresponding to (A) an electrophile or (B) a nucleophile is used, depending on the amount of the imidazole compound used, a carboxylic acid ester derived from the imidazole compound is an impurity. May be generated.
However, in this case, the content of the carboxylic acid ester derived from the imidazole compound can be reduced by purifying the target carboxylic acid ester by a conventional method such as distillation, recrystallization, column purification or the like.

Moreover, when the carboxylic acid ester that is the target of synthesis is a carboxylic acid ester derived from the imidazole compound represented by the formula (1) corresponding to (A) an electrophile or (B) a nucleophile, The reaction between the (A) electrophile and the (B) nucleophile proceeds well in an autocatalytic manner even when no imidazole compound is added separately from the (A) electrophile and (B) nucleophile. .
Such a case naturally corresponds to a method for producing a carboxylic acid ester by a reaction between (A) a spherical electron body and (B) a nucleophile in the presence of an imidazole compound represented by the formula (1).

In Formula (1), R ¹ is a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, and may be, for example, an alkyl group that may have a substituent, an aromatic group that may have a substituent, or the like. When R ¹ is an alkyl group, the alkyl group may have an ester bond or the like in the chain.

The alkyl groups may be the same as R ⁴ or the like for example in the below equation (1a). 1-40 are preferable, as for the carbon atom number of an alkyl group, 1-30 are more preferable, 1-20 are especially preferable, and 1-10 are the most preferable.
Examples of the substituent that the alkyl group may have may be the same as the substituent that the alkylene group that is R ⁵ in formula (1a) described later may have.

The aromatic group that may have a substituent is the same as R ² in formula (1a) described later, and is preferably an aryl group, more preferably a phenyl group. The aromatic group which may have a substituent as R ¹ may be the same as or different from R ² .
In formula (1), one R ¹ is preferably a hydrogen atom, ^one R ¹ is a hydrogen atom, and the other R ¹ has an alkyl group or a substituent which may have a substituent. It is more preferable that it is a good aromatic group.
In formula (1), R ¹ may be bonded to the other R ¹ or R ² to form a cyclic structure. For example, if at least one R ¹ is an alkyl group which may have a substituent, R ¹ may form a cyclic structure in combination with the other of R ¹ or R ^2.

  The imidazole compound may be a compound represented by the following formula (1a).

（式（１ａ）中、Ｒ^４は水素原子又はアルキル基であり、Ｒ^２は置換基を有してもよい芳香族基であり、Ｒ^５は置換基を有してもよいアルキレン基であり、Ｒ^３は、ハロゲン原子、ヒドロキシ基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基であり、ｎは０〜３の整数である。Ｒ^５はＲ^２と結合して環状構造を形成してもよい。）

(In Formula (1a), R ⁴ is a hydrogen atom or an alkyl group, R ² is an aromatic group that may have a substituent, and R ⁵ is an alkylene group that may have a substituent. , R ³ is a halogen atom, a hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is 0 (It is an integer of ˜3. R ⁵ may combine with R ² to form a cyclic structure.)

In formula (1a), R ⁴ represents a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group may be a linear alkyl group or a branched alkyl group. Although the carbon atom number of the said alkyl group is not specifically limited, 1-20 are preferable, 1-10 are preferable and 1-5 are more preferable.

Specific examples of an alkyl group suitable as R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group.

In Formula (1a), R ² is an aromatic group that may have a substituent. The aromatic group that may have a substituent may be an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group that may have a substituent.

  The type of the aromatic hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. The aromatic hydrocarbon group may be a monocyclic aromatic group, may be formed by condensation of two or more aromatic hydrocarbon groups, and may be two or more aromatic hydrocarbon groups. May be formed by a single bond. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable.

  The kind of the aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. As the aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group are preferable.

  Examples of the substituent that the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group may have include a halogen atom, a hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, and a nitroso group. Groups, sulfino groups, sulfo groups, sulfonate groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonate groups, amino groups, ammonio groups, and organic groups. When a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

  When the substituent that the aromatic group has is an organic group, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a heteroatom in the organic group. The organic group may be any of linear, branched, cyclic, and a combination of these structures. This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.

  When the aromatic group has a substituent on the adjacent carbon atom, the two substituents bonded on the adjacent carbon atom may combine to form a cyclic structure. Examples of the cyclic structure include an aliphatic hydrocarbon ring and an aliphatic ring containing a hetero atom.

  When the substituent that the aromatic group has is an organic group, the bond contained in the organic group is not particularly limited as long as the effect of the present invention is not impaired, and the organic group includes an oxygen atom, a nitrogen atom, a silicon atom, and the like. A bond containing a hetero atom may be included. Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (—R) —, —C (= NR)-: R represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like.

  As the bond containing a hetero atom that the organic group may have, from the viewpoint of heat resistance of the imidazole compound represented by the formula (1) or the formula (1a), an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond , Ester bond, amide bond, amino bond (—NR—: R represents a hydrogen atom or a monovalent organic group) urethane bond, imino bond (—N═C (—R) —, —C (═NR) — : R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

  When the organic group is a substituent other than a hydrocarbon group, the type of substituent other than the hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. Specific examples of substituents other than hydrocarbon groups include halogen atoms, hydroxy groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups, silanol groups, alkoxy groups. Group, alkoxycarbonyl group, amino group, monoalkylamino group, dialkylaluminum group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, Examples thereof include a sulfino group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, an alkyl ether group, an alkenyl ether group, an alkyl thioether group, an alkenyl thioether group, an aryl ether group, and an aryl thioether group. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

  Examples of the substituent that the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group has include an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. Are preferably an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, an arylamino group having 1 to 12 carbon atoms, and a halogen atom.

As R ² , an imidazole compound represented by the formula (1) or the formula (1a) can be synthesized inexpensively and easily, and the solubility of the imidazole compound in water or an organic solvent is good. Preferred are a phenyl group, a furyl group, and a thienyl group.

In formula (1a), R ⁵ is an alkylene group which may have a substituent. The substituent which the alkylene group may have is not particularly limited as long as the object of the present invention is not impaired. Specific examples of the substituent that the alkylene group may have include a hydroxy group, an alkoxy group, an amino group, a cyano group, and a halogen atom. The alkylene group may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferred. The number of carbon atoms of the alkylene group is not particularly limited, preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The number of carbon atoms of the alkylene group does not include the carbon atom of the substituent that is bonded to the alkylene group.

  The alkoxy group as a substituent bonded to the alkylene group may be a linear alkoxy group or a branched alkoxy group. The number of carbon atoms of the alkoxy group as a substituent is not particularly limited, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3.

  The amino group as a substituent bonded to the alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or dialkylamino group may be a linear alkyl group or a branched alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or dialkylamino group is not particularly limited, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3.

Specific examples of the alkylene group suitable as R ⁵ include methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-propane-2,2-diyl group, and n-butane. -1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptane-1,7-diyl group, n-octane-1,8-diyl Group, n-nonane-1,9-diyl group, n-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tridecane- 1,13-diyl group, n-tetradecane-1,14-diyl group, n-pentadecane-1,15-diyl group, n-hexadecane-1,16-diyl group, n-heptadecane-1,17-diyl group N-octadecane-1,18-diyl group, n -Nonadecane-1,19-diyl group and n-icosane-1,20-diyl group are mentioned.

R ³ is a halogen atom, a hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n is 0 to 0 It is an integer of 3. When n is an integer of 2 to 3, the plurality of R ³ may be the same or different.

When R ³ is an organic group, the organic group is the same as the organic group that the aromatic group may have as a substituent for R ² .

When R ³ is an organic group, the organic group is preferably an alkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group. As the alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable. As the aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group are preferable. A furyl group and a thienyl group are more preferable.

When R ³ is an alkyl group, the bonding position of the alkyl group on the imidazole ring is preferably any of the 2-position, 4-position, and 5-position, and more preferably the 2-position. When R ³ is an aromatic hydrocarbon group or an aromatic heterocyclic group, the bonding position of these groups on imidazole is preferably the 2-position.

  Among the imidazole compounds represented by the above formula (1), a compound represented by the following formula (1-1a) is preferable because it can be synthesized inexpensively and easily.

（式（１−１ａ）中、Ｒ^１、Ｒ^３及びｎは、式（１）と同じであり、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。ただし、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０のうち少なくとも１つは水素原子以外の基である。Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０のうち少なくとも２つが結合して環状構造を形成してもよい。Ｒ^１はＲ^８と結合して環状構造を形成してもよい。）

(In formula (1-1a), R ¹ , R ³ and n are the same as in formula (1), and R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom. , Halogen atom, hydroxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio A group or an organic group, provided that at least one of R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ is a group other than a hydrogen atom R ⁶ , R ⁷ , R ⁸ , R ⁹ , And R ¹⁰ may combine to form a cyclic structure, and R ¹ may combine with R ⁸ to form a cyclic structure.)

R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are the same as those in formula (1-1) described later. In formula (1-1a), R ¹ may be bonded to R ⁸ to form a cyclic structure. For example, when R ¹ is an alkyl group which may have a substituent, R ¹ is R ⁸ may form a ring structure.

Among the imidazole compounds represented by the above formula (1a) or formula (1-1a), they can be synthesized inexpensively and easily, and are excellent in solubility in water and organic solvents. A compound represented by formula (1-1) is preferred, and a compound in which R ³ is a methylene group is more preferred.

（式（１−１）中、Ｒ^３、Ｒ^４、Ｒ^５、及びｎは、式（１ａ）と同様であり、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。ただし、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０のうち少なくとも１つは水素原子以外の基である。Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０のうち少なくとも２つが結合して環状構造を形成してもよい。Ｒ^５はＲ^８と結合して環状構造を形成してもよい。）

(In Formula (1-1), R ³ , R ⁴ , R ⁵ , and n are the same as in Formula (1a), and R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independent. , Hydrogen atom, halogen atom, hydroxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, An amino group, an ammonio group, or an organic group, provided that at least one of R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ is a group other than a hydrogen atom, R ⁶ , R ⁷ , R ^And at least two of R ⁸ , R ⁹ and R ¹⁰ may be bonded to form a cyclic structure, and R ⁵ may be bonded to R ⁸ to form a cyclic structure.)

When R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are organic groups, the organic group is the same as the organic group that R ² in Formula (1a) has as a substituent. R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably hydrogen atoms from the viewpoint of solubility of the imidazole compound in the solvent.

Among them, at least one of R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ is preferably the following substituent, and R ¹⁰ is particularly preferably the following substituent. When R ¹⁰ is the following substituent, R ⁶ , R ⁷ , R ⁸ , and R ⁹ are preferably hydrogen atoms.
-O-R ¹¹
(R ¹¹ is a hydrogen atom or an organic group.)

When R ¹¹ is an organic group, the organic group is the same as the organic group that R ² in Formula (1a) has as a substituent. R ¹¹ is preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

（式（１−１−１）において、Ｒ^３、Ｒ^４、及びｎは、式（１ａ）と同様であり、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、及びＲ^１６は、それぞれ独立に、水素原子、ヒドロキシ基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。ただし、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、及びＲ^１６のうち少なくとも１つは水素原子以外の基である。） Among the compounds represented by the formula (1-1), a compound represented by the following formula (1-1-1) is preferable.

(In Formula (1-1-1), R ³ , R ⁴ , and n are the same as in Formula (1a), and R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently , Hydrogen atom, hydroxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio A group or an organic group, provided that at least one of R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ is a group other than a hydrogen atom.)

Among the compounds represented by formula (1-1-1), at least one of R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ is a group represented by the aforementioned —O—R ^11. It is preferable that R ¹⁶ is a group represented by —O—R ¹¹ . When R ¹⁶ is a group represented by —O—R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are preferably hydrogen atoms.

The method for synthesizing the imidazole compound represented by the above formula (1) is not particularly limited. For example, a halide represented by R ² CR ¹ (Hal) R ¹ (R ¹ and R ² are the same as those in formula (1), Hal is a halogen atom), and formula (II) described below. The imidazole compound represented by the above formula (1) can be synthesized by reacting with the imidazole compound represented by the formula (I) and performing imidazolylation according to a conventional method.

  The method for synthesizing the imidazole compound represented by the above formula (1a) is not particularly limited. For example, by reacting a halogen-containing carboxylic acid derivative represented by the following formula (I) with an imidazole compound represented by the following formula (II) according to a conventional method, imidazolylation is carried out, whereby the above formula (1a) The imidazole compound represented by can be synthesized.

（式（Ｉ）及び式（ＩＩ）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びｎは、式（１ａ）と同様である。式（Ｉ）において、Ｈａｌはハロゲン原子である。）

(In formula (I) and formula (II), R ² , R ³ , R ⁴ , R ⁵ and n are the same as in formula (1a). In formula (I), Hal is a halogen atom.)

When the imidazole compound is a compound represented by the formula (1a) and R ⁵ is a methylene group, that is, when the imidazole compound is a compound represented by the following formula (1-2), The imidazole compound can also be synthesized by the method using the Michael addition reaction described.

（式（１−２）中、Ｒ^２、Ｒ^３、Ｒ^４及びｎは、式（１ａ）と同様である。）

(In formula (1-2), R ² , R ³ , R ⁴ and n are the same as in formula (1a).)

  Specifically, for example, the Michael addition reaction is caused by mixing a 3-substituted acrylic acid derivative represented by the following formula (III) and an imidazole compound represented by the above formula (II) in a solvent. The imidazole compound represented by the above formula (1-2) is obtained.

（式（ＩＩＩ）中、Ｒ^２、及びＲ^４は、式（１ａ）と同様である。）

(In formula (III), R ² and R ⁴ are the same as in formula (1a).)

  Moreover, the imidazole compound represented by a following formula (1-3) is obtained by adding the 3-substituted acrylic acid derivative containing the imidazolyl group represented by the following formula (IV) in the solvent containing water. .

（式（ＩＶ）及び式（１−３）中、Ｒ^２、Ｒ^４及びｎは、式（１）と同様である。）

(In formula (IV) and formula (1-3), R ² , R ⁴ and n are the same as in formula (1).)

  In this case, by hydrolysis of the 3-substituted acrylic acid derivative represented by the above formula (IV), the imidazole compound represented by the above formula (II) and the 3-substituted acrylic acid represented by the following formula (V) And generate. A Michael addition reaction occurs between the 3-substituted acrylic acid represented by the following formula (V) and the imidazole compound represented by the above formula (II), and is represented by the above formula (1-3). An imidazole compound is formed.

（式（Ｖ）中、Ｒ^２は、式（１ａ）と同様である。）

(In formula (V), R ² is the same as in formula (1a).)

Preferable specific examples of the imidazole compound represented by the formula (1) or the formula (1a) include the following.

  The amount of the imidazole compound used in the production of the carboxylic acid ester is not particularly limited, and is appropriately determined in consideration of reaction conditions such as (A) the type of electrophile, (B) the type of nucleophile, and reaction temperature. It is done. For example, the usage-amount of an imidazole compound is 0.00001 mol-0.3 mol with respect to 1 mol of (A) electrophiles, Preferably, it is 0.00005-0.03 mol.

The imidazole compound described above is suitably used as a component of an esterifying agent for reacting the aforementioned electrophile (A) and (B) nucleophile to produce a carboxylic acid ester.
In particular, the above-mentioned imidazole compound is a ring-opening addition catalyst for producing a carboxylic acid ester by ring-opening addition of an epoxy group to (B) a nucleophile and ring-opening addition of a cyclic acid anhydride to (A) an electrophile. It is preferably used as a component of

<(A) Electrophile>
(A) The electrophile is selected from the group consisting of at least one (A1) hydroxy group-providing compound selected from the group consisting of phenolic compounds and alcohols, and (A2) an epoxy group-providing compound consisting of epoxy compounds. At least one compound is used.

In addition, (A) electrophile may have the property as (B) nucleophile mentioned later. In this case, the electrophile (A) and the nucleophile (B) may be the same compound. Examples of the electrophile (A) include hydroxycarboxylic acids.
Specific examples of suitable hydroxycarboxylic acids include lactic acid, hydroxybutyric acid, 5-hydroxypentanoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-hydroxy-4′-carboxybiphenyl, and the like. And acid halides of these, C ₁ -C ₆ alkyl esters thereof, and the like.
When a compound having the properties of (A) an electrophile and (B) a nucleophile is reacted in the presence of the imidazole compound, an oligoester compound or a polyester can be produced by self-polycondensation.
Further, when the compound having the properties of (A) electrophile and (B) nucleophile is an aliphatic hydroxycarboxylic acid such as hydroxybutyric acid or 5-hydroxypentanoic acid, the reaction is carried out in a dilute system. By doing so, a lactone can be produced by a self-ring closure reaction.

[(A1) Hydroxy group-providing compound]
(A1) The hydroxy group-providing compound is at least one compound selected from the group consisting of a phenol compound and an alcohol.
These compounds may be monofunctional hydroxy group-providing compounds having one hydroxy group, and may be polyfunctional hydroxy group-providing compounds having two or more hydroxy groups.
The compound having a polyfunctional hydroxy group may be a compound having a combination of a phenolic hydroxy group and an alcoholic hydroxy group.

When the polyfunctional hydroxy group-providing compound is reacted with the polyfunctional (B) nucleophile, a polyester can be formed by so-called polycondensation.
The produced polyester may be a linear polyester, a branched polyester, or a network polyester, and a linear polyester is preferable.
When at least one of the polyfunctional hydroxy group-providing compound and the polyfunctional (B) nucleophile is trifunctional or more, a branched polyester or a network polyester is formed.
Typical examples of reactions that can be produced by polyester include diols such as ethylene glycol and 1,4-butanediol, terephthalic acid, terephthalic acid dichloride, terephthalic acid dimethyl ester, 2,6-naphthalenedicarboxylic acid, 2,6- Reaction with (B) nucleophiles such as naphthalenedicarboxylic acid dichloride and 2,6-naphthalenedicarboxylic acid dimethyl ester can be mentioned. By this reaction, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) can be produced.

[Phenol compound]
The phenol compound is not particularly limited as long as it is a compound having a phenolic hydroxy group.
Preferable examples of the phenol compound include, for example, phenol; cresols such as o-cresol, m-cresol, p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 -Xylenols such as xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4 -Alkylphenols such as isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as diol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, alkylkylhydroquinone (all the above alkyl groups have 1 to 4); naphthols such as α-naphthol, β-naphthol, 2,6-naphthalenediol, 1,4-naphthalenediol; and hydroxydiphenyl.

  Moreover, the polyhydric phenol which gives group Z in the formula (A1-4) mentioned later is also used suitably as a phenol compound.

  The phenol compound may be a polymer. Examples of such a polymer include a novolak resin derived from the above phenol compound, a homopolymer of a compound having an unsaturated bond and a phenolic hydroxy group, such as p-hydroxystyrene, and an unsaturated bond and a phenolic hydroxy group. The copolymer of a compound and another monomer is mentioned.

Although it does not specifically limit as novolak resin, Condensation agents, such as formaldehyde and paraformaldehyde, are made into the condensation reaction in the ratio of 0.5-1.0 mol with an acidic catalyst with respect to 1 mol of said phenols. What is obtained is preferred.
Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid, organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, paratoluenesulfonic acid, and metal salts such as zinc acetate. Is mentioned. These acidic catalysts can be used alone or in combination of two or more.
Among the phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. Various characteristics such as heat resistance can be adjusted by adjusting the blending ratio of the two. The blending ratio of m-cresol and p-cresol is not particularly limited, but m-cresol / p-cresol = 3/7 to 8/2 (mass ratio) is preferable.

〔alcohol〕
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxy group. The alcohol may be an aliphatic alcohol or an alcohol containing an aromatic group such as benzyl alcohol, phenoxyethanol, or xylylene glycol. When the alcohol includes an aromatic group, the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group.

Among the (A1) hydroxy group-providing compounds, suitable examples of alcohol include
(A1-1) an alcohol having a (meth) acryloyloxy group,
(A1-2) an alcohol having a saturated hydrocarbon group which may have a substituent, or
(A1-3) a saturated heterocycle-containing group which may have a substituent, wherein the heteroatom constituting the saturated heterocycle is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom An alcohol having

((A1-1) Alcohol having (meth) acryloyloxy group)
(A1-1) The alcohol having a (meth) acryloyloxy group is not particularly limited as long as it is a compound having an alcoholic hydroxy group and a (meth) acryloyloxy group.

(A1-1) As alcohol which has a (meth) acryloyloxy group, the mono (meth) acrylate of aliphatic diol is mentioned, for example.
When an aliphatic diol mono (meth) acrylate is esterified by, for example, reacting with a carboxy group in a resin having a carboxy group as an alkali-soluble group according to a conventional method, an unsaturated double bond is introduced into the alkali-soluble resin. And polymerizability is imparted.
Such esterification reaction may be carried out in the presence of the aforementioned imidazole compound.

  Specific examples of aliphatic diol mono (meth) acrylates include ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, 1,3-propanediol mono (meth) acrylate, and 1,4-butanediol mono (Meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and dipropylene glycol mono (Meth) acrylate etc. are mentioned.

  There is no particular limitation on the method for producing alcohols having (A1) (meth) acryloyloxy groups derived from these aliphatic diols. Alcohols having a (A1) (meth) acryloyloxy group derived from an aliphatic diol can be obtained by, for example, reacting an excess amount of an aliphatic diol and (meth) acrylic acid in the presence of the imidazole compound. It can manufacture suitably.

Moreover, as alcohol which has (A1-2) (meth) acryloyloxy group, the alcohol represented by a following formula (y0) is preferable.

Wherein (y0), ^{Z 1} is, _{s +} a j 1 + _{k 1} monovalent organic group, an aromatic hydrocarbon ring 1-4 having group which may having 6 to 10 carbon atoms which may have a substituent , An aliphatic group having a terminal consisting of an unsaturated double bond and optionally containing an ester bond (—CO—O—), an ether bond or a carbonyl group (—CO—), an aromatic having 6 to 10 carbon atoms It is a saturated aliphatic group having 5 to 30 carbon atoms which may be substituted with an aliphatic group and may have a hetero atom.
R ^a1 is a hydrogen atom or a methyl group.
Y ^x and Y ^y are each independently a linear or branched alkylene group.
p and r are integers of 0 to 4, and q + j ₁ + k ₁ is an integer of ₁ to 6.
Y ^{2 to} Y ³ , p _{2 to} p ₃ , j1, and k1 are the same as those in the formula (A1).

式（ｙ）中、Ｚ^１は、ｑ価の有機基であって、置換基を有していてもよい炭素原子数６〜１０の芳香族炭化水素環を１〜４個有する基、不飽和二重結合からなる末端を有しエステル結合（−ＣＯ−Ｏ−）、エーテル結合又はカルボニル基（−ＣＯ−）を含んでいてもよい脂肪族基、炭素原子数６〜１０の芳香族基で置換されていてもよくヘテロ原子を有していてもよい炭素原子数５〜３０の飽和脂肪族基である。
Ｒ^ａ１は、水素原子又はメチル基である。
Ｙ^ｘ及びＹ^ｙは、それぞれ独立して直鎖又は分岐鎖のアルキレン基である。
ｐは０〜４の整数であり、ｑは１〜６の整数であり、ｒは０〜４の整数である。 Since j ₁ + k ₁ is preferably 0 in the formula (y0), the alcohol represented by the following formula (y) is preferable as the alcohol having (A1-1) (meth) acryloyloxy group.

In the formula (y), Z ¹ is a q-valent organic group, a group having 1 to 4 aromatic hydrocarbon rings having 6 to 10 carbon atoms which may have a substituent, unsaturated An aliphatic group having a terminal consisting of a double bond and optionally containing an ester bond (—CO—O—), an ether bond or a carbonyl group (—CO—), or an aromatic group having 6 to 10 carbon atoms; A saturated aliphatic group having 5 to 30 carbon atoms which may be substituted or may have a hetero atom.
R ^a1 is a hydrogen atom or a methyl group.
Y ^x and Y ^y are each independently a linear or branched alkylene group.
p is an integer of 0 to 4, q is an integer of 1 to 6, and r is an integer of 0 to 4.

Y ^x and Y ^y are linear or branched alkylene groups, preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 6 carbon atoms. Particularly preferred are ethane-1,2-diyl, propane-1,2-diyl, and propane 1,3-diyl.

The method for producing the alcohol represented by the formula (y) is not particularly limited. For example, the alcohol represented by the formula (y) can be produced by the following method using a hydroxy group-providing compound represented by the following formula (x). Z ¹ , Y ^x , p, and q in the formula (x) are the same as those in the formula (y).
The hydroxy group-providing compound represented by formula (x) will be described in detail later.
^{Z 1 - (- O - [} - Y x -O-] p -H) q ··· (x)

First, the hydroxy group-providing compound represented by the above formula (x) is converted to glycidyl ether according to a conventional method to produce an epoxy compound represented by the following formula (x1). In the formula (x1), Z ¹ , Y ^x , p, and q are the same as in the formula (y), and Gly is a residue of the glycidyl group-containing compound used as a raw material.
^{Z 1 - (- O - [} - Y x -O-] p -Gly) q ··· (x1)

  As such a conventional method, after reacting the hydroxy group-providing compound represented by the formula (x) with a glycidyl group-containing compound having a halogen element at the terminal, such as epichlorohydrin, in the presence of a catalyst such as a phase transfer catalyst, The method of performing ring closure epoxidation with bases, such as sodium hydroxide, is mentioned.

Next, the epoxy compound represented by the formula (x1) and the glycol represented by HO — [— Y ^y —O—] _r —H are reacted to obtain an alcohol represented by the following formula (x1a). .

Next, (A) as an electrophile, an alcohol represented by the formula (x1a) is used as a hydroxy group-providing compound, and (B) as a nucleophile, (meth) acrylic acid, (meth) acrylic acid halide, (meta ) An esterification reaction is carried out using an acrylic ester or di (meth) acrylic anhydride to obtain an alcohol represented by the formula (y).
When performing this esterification reaction, it is preferable that the above-mentioned imidazole compound having a predetermined structure is present.

Moreover, the epoxy compound represented by the formula (x1) is represented by the formula (y) by reacting with the (meth) acrylic acid or the (meth) acrylic acid ester represented by the following formula (x2). Alcohol is produced.
CH = C (R ^a1 ) —CO — [— O—Y ^y —] _r —OH (x2)

In the case where r is 0 and the compound represented by the formula (x2) is (meth) acrylic acid, the epoxy compound represented by the formula (x1) and (meth) acrylic acid are mixed with the above-mentioned predetermined Even when the reaction is carried out in the presence of an imidazole compound having the structure: an alcohol represented by the formula (y) is obtained.
In this case, the epoxy compound represented by the formula (x1) is (A) an electrophile, and (meth) acrylic acid is (B) a nucleophile.

  Moreover, you may make the epoxy compound represented by Formula (x1) react with a lactone compound. Examples of lactone compounds include β-propiolactone, β-methyl-δ-valerolactone, δ-valerolactone, ε-caprolactone, 2-methyl-ε-caprolactone, 3-methyl-ε-caprolactone, 4-methyl-ε. -Caprolactone, 5-tertiarybutyl-ε-caprolactone, 7-methyl-4,4,6-trimethyl-ε-caprolactone, 4,6,6-trimethyl-ε-caprolactone and the like.

Further, as a glycidyl group-containing compound having a halogen element at the end of the raw material, a compound having a — [— Y ^y —O—] _r — group may be reacted with the compound of the formula (x).

As the alcohol represented by the formula (y), an alcohol represented by the following formula (y1) is preferable. In formula (y1), Z ¹ , R ^a1 , p, r, and q are the same as in formula (y).

In the formula (y1), p and r are preferably 0. In this case, the alcohol represented by the formula (y1) is represented by the following formula (y2). In formula (y2), Z ¹ , R ^a1 , and q are the same as in formula (y).

When an alcohol represented by the formula (y0) (when j ₁ + k ₁ is 1 to 5) is obtained as an alcohol having a (meth) acryloyloxy group, glycidyl having a halogen element at the end of the formula (x) What is necessary is just to adjust the molar ratio of a group containing compound suitably.

((A1-2) Alcohol having a saturated hydrocarbon group)
(A1-2) The alcohol having a saturated hydrocarbon group is an alcohol having a saturated hydrocarbon group which may have a substituent.
(A1-2) Alcohols having a saturated hydrocarbon group are particularly preferably used for the synthesis of unsaturated carboxylic acid esters.
Examples of the alcohol having a (A1-2) saturated hydrocarbon group include alcohols represented by the following formulas (A1-2-1a) to (A1-2-1d).

The alcohol represented by the formula (A1-2-1a) and the alcohol represented by the formula (A1-2-1b) give a carboxylic acid ester that is easily decomposed into a carboxy group by the action of an acid. In particular, the alcohol represented by the formula (A1-2-1a) is characterized by having a tertiary hydroxy group.
Derived from alcohol represented by formula (A1-2-1a) or alcohol represented by formula (A1-2-1b), unsaturated carboxylic acid such as (meth) acrylic acid, and unsaturated carboxylic acid Carboxylic acid ester obtained by reacting with an acid halide or acid anhydride is a unit that provides a resin blended in a photosensitive resin composition such as a photoresist so that it can be solubilized in an alkali by the action of an acid. It is useful as a monomer for introducing.

The alcohol represented by the formula (A1-2-1c) is an alcohol having a primary or secondary hydroxy group. Typical examples include methanol, ethanol, benzyl alcohol, and the like, which are suitable as raw materials for synthesizing various carboxylic acid esters used in a wide range of fields.
The alcohol represented by the formula (A1-2-1d) is an alkanol substituted with an alkoxy group, an alkoxyalkoxy group, or the like.
The alcohol represented by the formula (A1-2-1c) or the carboxylic acid ester derived from the alcohol represented by the formula (A1-2-1d) is not easily decomposed by the action of an acid.

In the above formula (A1-2-1a), R ^{q1 to} R ^q3 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched group having 1 to 6 carbon atoms, It represents a branched fluorinated alkyl group, and R ^q2 and R ^q3 may be bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which both are bonded. L ^q1 is an alkanediyl group having 1 to 6 carbon atoms; cyclopentane ring, cyclohexane ring, norbornane ring, perhydronaphthalene (decalin) ring, adamantane ring, tricyclo [5.2.1.02,6] decane ring , A divalent alicyclic hydrocarbon group corresponding to an alicyclic ring (monocyclic or bridged ring) such as tetracyclo [4.4.0.12, 5.17,10] dodecane ring; benzene ring, naphthalene ring A divalent aromatic hydrocarbon group corresponding to an aromatic hydrocarbon ring, such as a group in which a plurality of these groups are linked via or without an oxygen atom or an ester group. nq1 is 0 or 1.
In the above formula (A1-2-1b), R ^q4 and R ^q5 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched group having 1 to 6 carbon atoms, Represents a branched fluorinated alkyl group, Y ^q1 is an aliphatic cyclic group or an alkyl group which may have a substituent, nq1 is 0 or 1, and nq2 is an integer of 0 to 4. .
In the above formula (A1-2-1c), R ^q6 is a hydrocarbon group having 1 to 10 carbon atoms, and the carbon atom bonded to the hydroxy group in R ^q6 is a primary carbon atom or a secondary carbon atom. It is. L ^q1 is an alkanediyl group having 1 to 6 carbon atoms; cyclopentane ring, cyclohexane ring, norbornane ring, perhydronaphthalene (decalin) ring, adamantane ring, tricyclo [5.2.1.02,6] decane ring , A divalent alicyclic hydrocarbon group corresponding to an alicyclic ring (monocyclic or bridged ring) such as tetracyclo [4.4.0.12, 5.17,10] dodecane ring; benzene ring, naphthalene ring A divalent aromatic hydrocarbon group corresponding to an aromatic hydrocarbon ring, such as a group in which a plurality of these groups are linked via or without an oxygen atom or an ester group. nq1 is 0 or 1.
In the formula (A1-2-1d), R ^q7 and L ^q1 are each an alkanediyl group having 1 to 6 carbon atoms; a cyclopentane ring, a cyclohexane ring, a norbornane ring, a perhydronaphthalene (decalin) ring, an adamantane ring, 2 corresponding to alicyclic rings (monocyclic or bridged rings) such as tricyclo [5.2.1.02,6] decane ring and tetracyclo [4.4.0.12,5.17,10] dodecane ring A divalent alicyclic hydrocarbon group; a divalent aromatic hydrocarbon group corresponding to an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring; or a plurality of these groups via an oxygen atom or an ester group, or R ^q8 is an alkyl group having 1 to 6 carbon atoms, and nq3 is an integer of 0 to 30.

  Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, and the like. Can be mentioned. The fluorinated alkyl group is one in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

When R ^q2 and R ^q3 are not bonded to each other to form a hydrocarbon, the R ^q1 , R ^q2 , and R ^q3 are preferably linear or branched alkyl groups having 2 to 4 carbon atoms. . The ^{R q4,} and as ^{R q5} is a hydrogen atom or a methyl group is preferable.

R ^q2 and R ^q3 may form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which both are bonded. Specific examples of such an aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

Furthermore, the aliphatic cyclic group formed by R ^q2 and R ^q3 may have a substituent on the ring skeleton. Examples of the substituent include polar groups such as a hydroxy group, a carboxy group, and a cyano group, and linear or branched alkyl groups having 1 to 4 carbon atoms.

Y ^q1 is an aliphatic cyclic group or an alkyl group, and examples thereof include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. . Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups and the like. In particular, a group in which one or more hydrogen atoms are removed from adamantane (which may further have a substituent) is preferable.

Further, when the aliphatic cyclic group of Y ^q1 has a substituent on the ring skeleton, examples of the substituent include polar groups such as a hydroxy group, a carboxy group, and a cyano group, and one carbon atom. -4 linear or branched alkyl groups are mentioned.

Moreover, when ^Yq1 is an alkyl group, it is preferable that it is a linear or branched alkyl group having 1 to 20, preferably 6 to 15 carbon atoms. Such an alkyl group is particularly preferably an alkoxyalkyl group. Examples of the alkoxyalkyl group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxy group. Ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 -Ethoxy-1-methylethyl group etc. are mentioned.

  Preferable specific examples of the alcohol represented by the above formula (A1-2-1a) include the following compounds.

  Preferable specific examples of the alcohol represented by the above formula (A1-2-1b) include the following compounds.

In the above formula (A1-2-1c), R ^q6 is a hydrocarbon group having 1 to 10 carbon atoms, and the carbon atom bonded to the hydroxy group in R ^q6 is a primary carbon atom or a secondary carbon atom. It is.
Preferable specific examples of the alcohol represented by the formula (A1-2-1c) include methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, and n-octanol. 2-ethyl-n-hexanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-adamantanol, 2-adamantanol, benzyl alcohol, and phenethyltyl alcohol.

In the above formula (A1-2-1d), R ^q7 and L ^q1 are alkanediyl groups having 1 to 6 carbon atoms, R ^q8 is an alkyl group having 1 to 6 carbon atoms, and nq3 is 0 It is an integer of ~ 30.
Preferable specific examples of the alcohol represented by the formula (A1-2-1d) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl. Examples include ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, hexamethylene glycol monomethyl ether, nonaethylene glycol monomethyl ether, and octaethylene glycol monomethyl ether.

((A1-3) alcohol having a saturated heterocyclic group)
(A1-3) In the alcohol having a saturated heterocyclic ring-containing group, the hetero atom constituting the saturated heterocyclic ring is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom. The saturated heterocyclic ring-containing group may have a substituent.
(A1-3) In the alcohol having a saturated heterocyclic ring-containing group, the alcoholic hydroxy group may be bonded to the saturated heterocyclic ring or may not be bonded to the saturated heterocyclic ring.
When the alcoholic hydroxyl group is not bonded to the saturated heterocyclic ring, the alcoholic hydroxyl group and the saturated heterocyclic ring are linked with a divalent organic group.
As such a divalent organic group, at least a part of the methylene group may be substituted with a carbonyl group (—CO—), an ether bond (—O—) or an ester bond (—CO—O—). A hydrocarbon group is mentioned. Although the carbon atom number of a saturated hydrocarbon group is not specifically limited, 1-20 are preferable and 1-10 are more preferable.

（式（Ａ１−３−１）中、Ｌ^ｒ１及びＬ^ｒ２はそれぞれ独立に酸素原子又は硫黄原子を表し、
ｎｒ１は１〜３の整数を表し、
ｎｒ２は０〜３の整数を表し、
Ｚ^ｒ１は、単結合、又は＊−（ＣＨ_２）_ｎｒ３−ＣＯ−Ｌ^ｒ３−を表し、ｎｒ３は１〜４の整数を表し、＊は、酸素原子と結合する結合手の末端を表す。） As the alcohol having a saturated heterocyclic ring-containing group, for example, an alcohol represented by the following formula (A1-3-1) is preferable.

(In Formula (A1-3-1), L ^r1 and L ^r2 each independently represent an oxygen atom or a sulfur atom,
nr1 represents an integer of 1 to 3,
nr2 represents an integer of 0 to 3,
Z ^r1 represents a single bond or * — (CH ₂ ) _{nr 3} —CO—L ^{r 3} —, nr 3 represents an integer of 1 to 4, and * represents a terminal end of a bond to be bonded to an oxygen atom. )

Preferable specific examples of the alcohol represented by the formula (A1-3-1) include the following compounds.

  Further, the alcohol represented by the following formula (A1-3-2) is also (A1-3) at least one selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom as a heteroatom constituting the saturated heterocycle. Preferable as an alcohol having a saturated heterocycle-containing group which is an atom and may have a substituent.

A ^r1 —OH (A1-3-2)
(In the formula ^{(A1-3-2), A r1} is a saturated heterocyclic group, -CO-O-containing cyclic group, -SO ₂ - containing cyclic group, -O-CO-O- A containing cyclic group, a —NR ^r14 —SO ₂ — containing cyclic group, or a —NR ^r14 —CO— containing cyclic group, wherein R ^r14 is a hydrogen atom or a saturated hydrocarbon group.

^{A r1} in formula (A1-3-2) is preferably a saturated heterocyclic group represented by the following formula (A1-3-2a) ~ formula (A1-3-2i).

Wherein (A1-3-2a) ~ formula ^{(A1-3-2i), R r1, R} r2, R r3, R r4, R r5, R r6, R r7, R r8, R r9, R r10, R ^r12 , ^Rr13 , ^Rr15 , ^Rr16 , ^Rr18 , and ^Rr19 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyclic hydrocarbon group having 3 to 10 carbon atoms, or a carbon atom. An alkoxy group having 1 to 5 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 5 carbon atoms, —CO—O—R ^r11 , —O—CO—R ^r11 , or a cyano group;
R ^r11 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent.
R ^r8 and R ^r9 , or R ^r18 and R ^r19 may be connected to each other to form an alkylene group having 1 to 5 carbon atoms, —O—, or —S—.
X ^r1 is —O— or> N—R ^r14 , and R ^r14 is a hydrogen atom or a saturated hydrocarbon group.
X ^r2 is, -CO-, or -SO ₂ - is.
nr3 and nr4 are each independently 0 or 1.

Preferable specific examples of the groups represented by formula (A1-3-2a) to formula (A1-3-2i) include the following groups. In addition, * is the terminal of the bond hand couple | bonded with the oxygen atom in a hydroxy group.

(Particularly preferred examples of the hydroxy group-providing compound)
Particularly preferred examples of the hydroxy group-providing compound are summarized below. In addition, about the especially preferable example described below, it may overlap with the above-mentioned hydroxy group provision compound.
Specifically, a hydroxy group-providing compound represented by the following formula (A1-4) is particularly preferably used as the electrophile (A).
(H — [— O—Y—] _p —O—) _j —Z — [— O—Y—] _p —OH (A1-4)

The kind of (B) nucleophile to be reacted with the hydroxy group-providing compound represented by the formula (A1-4) is not particularly limited. As the (B) nucleophile to be reacted with the hydroxy group-providing compound represented by the formula (A1-4), polyhydric anhydrides of polycarboxylic acids such as tetracarboxylic dianhydrides are preferable.
The reaction product of the hydroxy group-providing compound represented by the formula (A1-4) and the polyhydric anhydride of the polyvalent carboxylic acid is an ester compound or a resin compounded as an alkali-soluble component in the photosensitive composition, It is preferably used as an intermediate thereof.
Preferable examples of the reaction product of the hydroxy group-providing compound represented by the formula (A1-4) and the polyhydric anhydride of polyvalent carboxylic acid include alkali-soluble components known as cardo resins and intermediates thereof. .

  In formula (A1-4), Y is a divalent organic group, Z is a j + 1 valent organic group, j is an integer of 0 to 7, and p is an integer of 0 to 4. 1-50 are preferable and, as for the carbon atom number of Y, 1-20 are more preferable.

Y is a divalent organic group having 1 to 20 carbon atoms, and may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. .
The aliphatic group contained in Y may be a saturated aliphatic group or an unsaturated aliphatic group, and is preferably a saturated aliphatic group.
The aromatic group contained in Y may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and is preferably an aromatic hydrocarbon group.
As preferable examples of Y, methylene group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, n-butane-1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, p-phenylene group, m-phenylene group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, And naphthalene-1,4-diyl group. Among these, an ethane-1,2-diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group are preferable.

Z is a j + 1 valent organic group. Z may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group.
The aliphatic group contained in Z may be a saturated aliphatic group or an unsaturated aliphatic group, and is preferably a saturated aliphatic group.
The aromatic group contained in Z may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and is preferably an aromatic hydrocarbon group.

式（Ｚ１）中、Ｒ^ｚ１は、単結合、又は−Ｃ（Ｒ^ｚ２）（Ｒ^ｚ３）−で表される２価の基である。Ｒ^ｚ２及びＲ^ｚ３は、それぞれ独立に、水素原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のハロゲン化アルキル基、炭素原子数４〜１０のシクロアルキル基、フェニル基、又はナフチル基である。
Ｒ^ｚ２及びＲ^ｚ３は、互いに結合して炭素原子数４〜２０の炭化水素環を形成してもよい。
Ｒ^ｚ４及びＲ^ｚ５は、それぞれ独立に、炭素原子数１〜６のアルキル基、炭素原子数１〜６のハロゲン化アルキル基、炭素原子数４〜１０のシクロアルキル基、フェニル基、ナフチル基、又はハロゲン原子である。Ｒ^ｚ４又はＲ^ｚ５が複数である場合、複数のＲ^ｚ４又はＲ^ｚ５は同一であっても異なっていてもよい。
ｎｚ１及びｎｚ２は、それぞれ独立に０〜４の整数である。 When Z is a divalent organic group, Z is preferably a residue obtained by removing two hydroxy groups from a bisphenol compound represented by the following formula (Z1).

In the formula (Z1), R ^z1 is a single bond or a divalent group represented by —C (R ^z2 ) (R ^z3 ) —. R ^z2 and R ^z3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, Or it is a naphthyl group.
R ^z2 and R ^z3 may be bonded to each other to form a hydrocarbon ring having 4 to 20 carbon atoms.
R ^z4 and R ^z5 are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, a naphthyl group, Or it is a halogen atom. If R ^z4 or ^{R z5} is plural, ^{R z4} or ^{R z5} may be different even in the same.
nz1 and nz2 are each independently an integer of 0 to 4.

Regarding R ^z2 and R ^z3 , the alkyl group having 1 to 6 carbon atoms is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a tert-butyl group, and more preferably a methyl group or an ethyl group. .
When R ^z2 and R ^z3 are halogenated alkyl groups, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable. As the halogenated alkyl group, a trifluoromethyl group is preferred.
Regarding R ^z2 and R ^z3 , the cycloalkyl group having 4 to 10 carbon atoms is preferably a cyclopentyl group or a cyclohexyl group.
When R ^z2 and R ^z3 are bonded to each other to form a hydrocarbon ring having 4 to 20 carbon atoms, suitable examples of the hydrocarbon ring include cycloalkane rings and fluorene rings having 4 to 10 carbon atoms. And a cyclopentane ring, a cyclohexane ring, and a fluorene ring are more preferable. When the ring formed by R ^z2 and R ^z3 is a fluorene ring, R ^z2 and R ^z3 form a 9H-fluorene-9,9-diyl group.

For R ^z4 and R ^z5 , preferred examples of the alkyl group having 1 to 6 carbon atoms, the halogenated alkyl group having 1 to 6 carbon atoms, and the cycloalkyl group having 4 to 10 carbon atoms include R ^z2 and R ^{z This} is the same as ^z3 .

Preferable examples of the bisphenol compound represented by the formula (Z1) include the following compounds.

When Z is a divalent organic group, a residue obtained by removing two hydroxy groups from the following aliphatic diol is also preferable as the group Z.

When Z is a trivalent organic group, a residue obtained by removing three hydroxy groups from a trisphenol compound represented by the following formula (Z2) is preferred as the group Z.

In formula (Z1), R ^z6 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a phenyl group, or a naphthyl group.
R ^z7 , R ^z8 , and R ^z9 are each independently an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, and naphthyl. A group or a halogen atom.
R ^z10 is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
nz3, nz4, and nz5 are each independently an integer of 0 to 4.
nz6 is 0 or 1.

For R ^z6 , R ^z7 , and R ^z8 , preferred examples of the alkyl group having 1 to 6 carbon atoms, the halogenated alkyl group having 1 to 6 carbon atoms, and the cycloalkyl group having 4 to 10 carbon atoms are as follows: The same as R ^z2 and R ^z3 described above.
When R ^z9 is an alkanediyl group having 1 to 4 carbon atoms, a methylene group, an ethane-1,2-diyl group, and a propane-2,2-diyl group are preferred.

Preferable specific examples of the trisphenol compound represented by the formula (Z2) include the following compounds.

When Z is a trivalent organic group, a residue obtained by removing three hydroxy groups from the following trisphenol compound is also preferable as the group Z.

When Z is a tetravalent or higher polyvalent organic group, a residue obtained by removing all hydroxy groups from the following polyphenol compound is preferred as the group Z.

The hydroxy group provides the compound represented by formula (A1-4), is preferably a compound represented by the following formula (x), and more preferably a compound represented by the following formula (A1-4-1) ^{Z 1} - _{^{(- [- Y x -O-]}} p -H) q ··· (x)

In the formula (x), Z ¹ is a q-valent organic group, a group having 1 to 4 aromatic hydrocarbon rings having 6 to 10 carbon atoms, which may have a substituent, unsaturated An aliphatic group having a terminal consisting of a double bond and optionally containing an ester bond (—CO—O—), an ether bond or a carbonyl group (—CO—), or an aromatic group having 6 to 10 carbon atoms; A saturated aliphatic group having 5 to 30 carbon atoms which may be substituted or may have a hetero atom.
Y ^x each independently represents a linear or branched alkylene group.
p is an integer of 0 to 4, and q is an integer of 1 to 6.

Z ¹ — (— [— CH ₂ CH ₂ —O—] _p —H) _q (A1-4-1)
In formula (A1-4-1), Z ¹ , p and q are the same as in formula (x). The
As an example of a group suitable as Z ¹ in formula (A1-4-1), an organic group having a cardo structure can be given. The organic group having a cardo structure is preferably a divalent group represented by the following formula (A1-4-1a).
In formula (A1-4-1a), R ^z11 each independently represents a hydrogen atom or a methyl group.

  Preferable specific examples of the hydroxy group-providing compound represented by the formula (A1-4) include phenols; cresols such as o-cresol, m-cresol, p-cresol; o-methoxyphenol, m-methoxyphenol, Methoxyphenols such as p-methoxyphenol; pyrogallol-1,3-dimethyl ether; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3, Xylenols such as 5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol P-Butylphenol Alkylphenols such as p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, pyrogallol monomethyl ether, Polyhydric phenols such as phlorogricinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, alkylkylhydroquinone (all the alkyl groups have 1 to 4 carbon atoms); α-naphthol, β-naphthol Naphthols such as 2,6-naphthalenediol and 1,4-naphthalenediol; hydroxydiphenyl; bisphenol A and the like.

  Moreover, the trisphenol compound itself represented by the above-mentioned formula (Z2) is also a suitable specific example of the hydroxy group-providing compound represented by the formula (A1-4).

  Furthermore, the following phenol compounds are also mentioned as a suitable specific example of the hydroxy group providing compound represented by Formula (A1-4). Specific examples of the phenol compound include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2 , 3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3 ′, 4,4 ′ , 6-pentahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2,2 ′, 3,4,5-pentahydroxybenzophenone, 2,3 ′, 4,4 ′, 5 ′ Polyhydrides such as 1,6-hexahydroxybenzophenone, 2,3,3 ′, and 4,4 ′, 5′-hexahydroxybenzophenone Xylbenzophenones; bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2 -(2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2', 3 ', 4'- Trihydroxyphenyl) propane, 4,4 ′-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol, and 3,3′-dimethyl- {1- [4 -[2- (3-Methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol and other bis [(poly) hydroxyphenyl] alka Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane Bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5 -Tris (hydroxyphenyl) methanes such as dimethylphenyl) -3,4-dihydroxyphenylmethane and bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane or methyl-substituted products thereof; Bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxy Phenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2) -Methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4 -Hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl) -4 Hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4- Hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, and bis (5-cyclohexyl) Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as -2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane or methyl-substituted products thereof.

  The following alcohol is also mentioned as a suitable specific example of the hydroxy group providing compound represented by the formula (A1-4). Specific examples of alcohols include ethylene glycol mono (meth) acrylate, 1,3-propanediol mono (meth) acrylate, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, and 2-hydroxy-3-methoxypropyl (meth) acrylate. Unsaturated alcohols such as 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate; 1-pentanol, 2-pentanol, 3-pentanol, neo Pentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether Tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, aliphatic or aromatic alcohols having 6 to 30 carbon atoms of 5 to 30 carbon atoms such as benzyl alcohol.

As described above, at least one hydroxy group in the compound described as a preferred specific example of the hydroxy group-providing compound represented by the formula (A1-4), preferably a hydrogen atom in all the hydroxy groups is represented by the following formula (y1a) A compound substituted with a group represented by the formula (A1-4) is also preferred as the hydroxy group-providing compound. In the formula (y1a), R ^a1 is a hydrogen atom or a methyl group, and p and r are integers of 0 to 4.

The group represented by the formula (y1a) is preferably a group represented by the following formula (y2a).

[(A2) Epoxy group-providing compound]
The imidazole compound described above also promotes the progress of the ester formation reaction between (A2) the epoxy group-providing compound and (B) the nucleophile.
For example, when (B) the nucleophile is a carboxylic acid, the following ester formation reaction proceeds.

In addition, when (B) the nucleophile is a carboxylic acid anhydride, an ester generation reaction or a polycondensation reaction including ester generation shown below proceeds according to the reaction conditions. In the following reaction formula, the reaction was described for a carboxylic acid anhydride in which two carboxy groups bonded to both ends of a C—C single bond were closed. The type of carboxylic acid anhydride is shown in the following reaction formula. It is not limited to what is.

  (A2) The epoxy group-providing compound is not particularly limited as long as it is a compound having an epoxy group. As the (A2) epoxy group-providing compound, various conventionally known epoxy compounds such as bisphenol-type epoxy resins and novolac-type epoxy resins derived from various bisphenols represented by bisphenol A can be used.

As the (A2) epoxy group-providing compound, for example, a glycidyl ether of a hydroxy group-providing compound represented by the above formula (A1-4) is preferable. That is, glycidyl ether represented by the following formula (A2-1) is preferable. In the formula (A2-1), Gly represents a glycidyl group, and Y, Z, p, and j are the same as in the formula (A1-4).
(Gly-[— O—Y—] _p —O—) _j —Z — [— O—Y—] _p —O—Gly
... (A2-1)

Among the (A2) epoxy group-providing compound represented by the formula (A2-1), a glycidyl ether represented by the following formula (A2-1-1) is preferable. The glycidyl ether represented by the following formula (A2-1-1) is a glycidyl ether of a hydroxy group-providing compound represented by the above formula (A1-4-1).
_{Z - (- O - [-} CH 2 CH 2 -O-] p -Gly) q ··· (A2-1-1)

  Preferable specific examples of the epoxy compound represented by the formula (A2-1) include glycidyl ethers of the compounds mentioned as preferred specific examples of the hydroxy group-providing compound represented by the formula (A1-4). It is done. That is, in all the hydroxy groups included in the compounds listed as preferred specific examples of the hydroxy group-providing compound represented by the formula (A1-4), the hydrogen atoms in the hydroxy groups are substituted with glycidyl groups. is there.

<(B) Nucleophile>
(B) As the nucleophile, at least one selected from the group consisting of carboxylic acid, carboxylic acid halide, carboxylic acid ester, and carboxylic acid anhydride is used.
(B) Carboxylic acid, carboxylic acid halide, carboxylic acid ester, and carboxylic acid anhydride used as the nucleophile are not particularly limited, and any of them can be appropriately selected from conventionally known compounds.

The carboxylic acid may be a monocarboxylic acid having one carboxy group or a polyvalent carboxylic acid having two or more carboxy groups.
The carboxylic acid halide may be a monocarboxylic acid halide having one halocarbonyl group or a polyvalent carboxylic acid halide having two or more halocarbonyl groups.
The carboxylic acid ester may be a monocarboxylic acid ester having a carboxylic acid ester group or a polyvalent carboxylic acid ester having two or more carboxylic acid groups.
The carboxylic anhydride may be a monoanhydride having one carboxylic anhydride group (—CO—O—CO—) in the molecule, and may be a polyanhydride having two or more carboxylic anhydride groups in the molecule. A hydride anhydride may also be used.

  A compound having two or more groups selected from the group consisting of a carboxy group, a halocarbonyl group, a carboxylic acid ester group, and a carboxylic anhydride group can also be used as the (B) nucleophile.

(B) Typical examples of compounds that can be used as nucleophiles include formic acid, acetic acid, propionic acid, n-butanoic acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n - and aliphatic carboxylic acids such as nonanoic acid, and n- decanoic acid, these acid halides, these C ₁ -C ₃ alkyl esters, their acid anhydrides.
Other typical examples include aromatic carboxylic acids such as benzoic acid, 1-naphthoic acid, and 2-naphthoic acid, acid halides thereof, C ₁ -C ₃ alkyl esters thereof, and acid anhydrides thereof. It is done.

  The following carboxylic acid anhydrides are also preferred as (B) nucleophiles. Specifically, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride Alicyclic dibasic acid anhydrides such as tetrabromophthalic anhydride; aliphatics such as succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride Or aromatic dibasic or tribasic acid anhydride, or biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride Acid, benzophenone tet Aliphatic or aromatic tetrabasic acid dianhydride such as dianhydrides may be mentioned, it is possible to use one or more of them. Among these, alicyclic dibasic acid anhydrides are particularly preferable.

A carboxylic acid having an unsaturated double bond or a derivative thereof is also preferably used as the (B) nucleophile. Examples of the compound suitable as the (B) nucleophile include compounds represented by the following formulas (x-1) to (x-13). In addition, acid anhydrides of carboxylic acids represented by the following formulas (x-1) to (x-13) where R ^x1 is a hydrogen atom are also preferably used as the (B) nucleophile.

In the following formulas (x-1) to (x-13), R ^x1 is a hydrogen atom or an organic group. As the organic group, an aliphatic hydrocarbon group is preferable, an aliphatic hydrocarbon group having 1 to 8 carbon atoms is more preferable, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is more preferable. As the aliphatic hydrocarbon group, an alkyl group is preferable. In addition, a compound in which the —OR ^x1 moiety is replaced with a halogen atom is also preferred. As a halogen atom, a chlorine atom or a bromine atom is preferable, and a chlorine atom is more preferable.
R ^x2 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a cyano group, or a group represented by —COOR ^x4 , and R ^x3 is a hydrogen atom or a methyl group.
R ^x4 is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and at least one methylene group contained in the aliphatic hydrocarbon group is an oxygen atom (—O—) or a carbonyl group (— CO-) may be substituted.
In addition, the compound represented by Formula (x-1) is (meth) acrylic acid or (meth) acrylic acid ester. The compound in which -ORx1 in the compound represented by the formula (x-1) is substituted with a halogen atom is (meth) acrylic acid halide.

In addition, polyhydric anhydrides of polycarboxylic acids such as tetracarboxylic dianhydrides are also preferably used as (B) nucleophiles. By reacting a polyhydric anhydride of a polyvalent carboxylic acid with, for example, a hydroxy group-providing compound represented by the aforementioned formula (A1-4), Resins and intermediates thereof can be produced.
As the polyhydric anhydride of the polyvalent carboxylic acid, tetracarboxylic dianhydride is preferable as the polyhydric anhydride.

  Suitable examples of tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic Acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, , 3,3a, 4,5,9b-Hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1, 3, 3 , 4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2 , 5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6- Tetracarboxylic dianhydride, bicyclo [2.1.2] -heptane-2,3,5,6-tetracarboxylic dianhydride, tetracyclo [2.1.1.0.2] -dodecane-2, Aliphatic or alicyclic tetracarboxylic dianhydrides such as 3,7,8-tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 3,3 ', 4,4'-biphenylsulfonate Lacarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ′, 4,4′-biphenyl ether Tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2 , 3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl Sulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic acid Water, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 '-Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride Products, aromatic tetracarboxylic dianhydrides such as bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, and the like. It is done.

（式（ｂ１）中、Ｒ^ｂ１、Ｒ^ｂ２、及びＲ^ｂ３は、それぞれ独立に、水素原子、炭素原子数１〜１０のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｍは０〜１２の整数を示す。） Moreover, since it is easy to obtain the ester compound excellent in heat resistance, norbornane-2-spiro-α-cycloalkanone-α′-spiro-2 ″ -norbornane-5,5 ′ represented by the following formula (b1) ', 6,6''-tetracarboxylic dianhydrides are also preferred as tetracarboxylic dianhydrides.

(In Formula (b1), R ^b1 , R ^b2 , and R ^b3 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom; Represents an integer of 0 to 12.)

The alkyl group that can be selected as R ^b1 in formula (b1) is an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms in the alkyl group exceeds 10, the resulting carboxylic acid ester may not have good heat resistance. When R ^b1 is an alkyl group, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, more preferably 1 to 6 from the viewpoint of easily obtaining a carboxylic acid ester having excellent heat resistance. 3 is particularly preferred.
When R ^b1 is an alkyl group, the alkyl group may be linear or branched.

As R ^b1 in formula (b1), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more preferable independently from the viewpoint of easily obtaining an ester compound having excellent heat resistance. R ^b1 in the formula (b1) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.
A plurality of R ^b1 in the formula (b1) are preferably the same group because preparation of a highly pure tetracarboxylic dianhydride is easy.

M in the formula (b1) represents an integer of 0 to 12. When the value of m is more than 12, it is difficult to purify tetracarboxylic dianhydride.
In view of easy purification of tetracarboxylic dianhydride, the upper limit of m is preferably 5, and more preferably 3.
From the viewpoint of the chemical stability of tetracarboxylic dianhydride, the lower limit of m is preferably 1, and more preferably 2.
As for m in a formula (b1), 2 or 3 is especially preferable.

The alkyl group having 1 to 10 carbon atoms that can be selected as R ^b2 and R ^{b3 in} formula (b1) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R ^b1 .
R ^b2 and R ^b3 are each a hydrogen atom or a carbon atom number of 1 to 10 (preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 5, more preferably from the viewpoint of easy purification of tetracarboxylic dianhydride. The alkyl group is preferably 1 to 4, particularly preferably 1 to 3), and particularly preferably a hydrogen atom or a methyl group.

  Examples of the tetracarboxylic dianhydride represented by the formula (b1) include norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6, 6 ″ -tetracarboxylic dianhydride (also known as “norbornane-2-spiro-2′-cyclopentanone-5′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetra Carboxylic dianhydride "), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-(methylnorbornane) -5,5 '', 6,6 ''-tetracarboxylic acid Dianhydride, norbornane-2-spiro-α-cyclohexanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride (also known as “norbornane-2- Spiro-2'-cyclo Xanone-6′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride ”), methylnorbornane-2-spiro-α-cyclohexanone-α′-spiro- 2 ″-(methylnorbornane) -5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α′-spiro-2 ″ -norbornane -5,5 '', 6,6 ''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 '' -Tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride Product, norbornane-2-s Rho-α-cyclooctanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononanone-α ′ Spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone-α′-spiro-2 ″ -norbornane-5 , 5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 '' -Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride Product, norbornane-2-spiro- α-cyclotridecanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanone-α '-Spiro-2' '-norbornane-5,5' ', 6,6' '-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2' ' -Norbornane-5,5 ", 6,6" -tetracarboxylic dianhydride, norbornane-2-spiro- [alpha]-(methylcyclopentanone)-[alpha] '-spiro-2 "-norbornane-5 5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α- (methylcyclohexanone) -α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 '' -Tetracarboxylic dianhydride And the like.

（式（ｂ１−１）中、Ｒ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、ｍは、式（ｂ１）中のＲ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、ｍと同義である。）
で表される化合物（Ｂ１−１）及び下記式（ｂ１−２）：

（式（ｂ１−２）中、Ｒ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、ｍは、式（ｂ１）中のＲ^ｂ１、Ｒ^ｂ２、Ｒ^ｂ３、ｍと同義である。）
で表される化合物（Ｂ１−２）のうちの少なくとも１種を含有し、且つ、化合物（Ｂ１−１）及び化合物（Ｂ１−２）の総量が３０モル％以上であるものが好ましい。 Moreover, as a tetracarboxylic dianhydride represented by a formula (b1), from a viewpoint of adjustment of a film characteristic, a thermophysical property, a mechanical physical property, an optical characteristic, and an electrical property, following formula (b1-1):

(In the formula ^{(b1-1), R b1, R} b2, R b3, m have the same meanings as ^{R b1, R b2, R b3} , m in the formula (b1).)
Compound (B1-1) represented by the following formula (b1-2):

(In the formula ^{(b1-2), R b1, R} b2, R b3, m have the same meanings as ^{R b1, R b2, R b3} , m in the formula (b1).)
And the total amount of the compound (B1-1) and the compound (B1-2) is preferably 30 mol% or more.

In the compound (B1-1) represented by the formula (b1-1), two norbornane groups are in trans configuration, and the carbonyl group of cycloalkanone is in the endo configuration with respect to each of the two norbornane groups. It is an isomer of tetracarboxylic dianhydride represented by the formula (b1).
In the compound (B1-2) represented by the formula (b1-2), two norbornane groups are in a cis configuration, and the carbonyl group of cycloalkanone is in an endo configuration with respect to each of the two norbornane groups. It is an isomer of tetracarboxylic dianhydride represented by the formula (b1).
In addition, the manufacturing method of the tetracarboxylic dianhydride containing such an isomer in the above ratio is not particularly limited, and a known method can be appropriately employed. For example, it is described in International Publication No. 2014/034760. These methods may be appropriately adopted.

<Preferred reaction example>
As described above, the reaction between the electrophile (A) and the nucleophile (B) is not particularly limited as long as it is performed in the presence of an imidazole compound having a predetermined structure.
When synthesizing the ester compound, a solvent that does not inhibit the esterification reaction may be used. Further, when at least one of (A) the electrophile and (B) the nucleophile is liquid at the reaction temperature, a solvent is not necessarily required.

  Examples of the solvent that can be used for the reaction between the component (A) and the component (B) include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), and N, N-dimethylisobutyramide. N, N-diethylacetamide, N, N-dimethylformamide (DMF), N, N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone (DMI), pyridine, Nitrogen-containing polar solvents such as N, N ′, N′-tetramethylurea (TMU); β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, etc. Lactone polar solvents; dimethyl sulfoxide; hexamethylphosphoric triamide; acetonitrile; ethyl lactate And fatty acid esters such as butyl lactate; ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate, ethyl cellosolve acetate, glyme; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, (Poly) alkylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; aromatic solvents such as benzene, toluene and xylene .

The reaction temperature is appropriately selected so that the reaction proceeds well in consideration of (A) the type of electrophile, (B) the type of nucleophile, the boiling point of the solvent, and the like.
When the esterification reaction is a dehydration condensation reaction, it is preferable to proceed with the esterification reaction while removing water produced as a by-product from the reaction.
(B) When the nucleophile is an acid halide, a base such as triethylamine is added to the reaction system, the reaction is carried out under reflux, or an inert gas is bubbled in the reaction solution, so The generated hydrogen halide may be removed.

As an example of a suitable reaction, the above-mentioned (A) electrophile and reaction with the unsaturated compound represented by the formulas (x-1) to (x-13) described above for the (B) nucleophile Is mentioned. Preferable examples of the (B) nucleophile in such a reaction include (meth) acrylic acid, (meth) acrylic acid halide, (meth) acrylic acid ester, and di (meth) acrylic anhydride. Among these, (meth) acrylic acid, (meth) acrylic acid halide, and di (meth) acrylic anhydride are preferable, and (meth) acrylic acid halide and di (meth) acrylic anhydride are more preferable.
(A) As the electrophile, the aforementioned hydroxy group-providing compound can be preferably used.
The carboxylic acid ester having an unsaturated bond generated by such a reaction is suitably used as a resin synthesis monomer blended in the photosensitive resin composition or the like.

Moreover, the reaction which produces | generates alcohol represented by the following formula (y) is also preferable.

In the formula (y), Z ¹ is a q-valent organic group, a group having 1 to 4 aromatic hydrocarbon rings having 6 to 10 carbon atoms which may have a substituent, unsaturated An aliphatic group having a terminal consisting of a double bond and optionally containing an ester bond (—CO—O—), an ether bond or a carbonyl group (—CO—), or an aromatic group having 6 to 10 carbon atoms; A saturated aliphatic group having 5 to 30 carbon atoms which may be substituted or may have a hetero atom.
R ^a1 is a hydrogen atom or a methyl group.
Y ^x and Y ^y are each independently a linear or branched alkylene group.
p is an integer of 0 to 4, q is an integer of 1 to 6, and r is an integer of 0 to 4.

In this reaction, the alcohol represented by the formula (x1a) shown below is used as the (A) electrophile as the hydroxy group-providing compound, (B) (meth) acrylic acid, ( A (meth) acrylic acid halide, (meth) acrylic acid ester, or di (meth) acrylic anhydride is used. Among these, (meth) acrylic acid, (meth) acrylic acid halide, and di (meth) acrylic anhydride are preferable, and (meth) acrylic acid halide and di (meth) acrylic anhydride are more preferable.

For the alcohol represented by the formula (x1a), the epoxy compound represented by the above-described formula (x1) shown below is reacted with a glycol represented by HO — [— Y ^y —O—] _r —H. Is obtained.
^{Z 1 - (- O - [} - Y x -O-] p -Gly) q ··· (x1)

In addition, when r is 0, the epoxy compound represented by the formula (x1) and (meth) acrylic acid are reacted in the presence of the imidazole compound having the above-described predetermined structure. ) Is obtained.
In this case, the epoxy compound represented by the formula (x1) is (A) an electrophile, and (meth) acrylic acid is (B) a nucleophile.

As the epoxy compound represented by the formula (x1), a compound in which q is 2 is preferable. That is, a compound represented by the following formula (x1-1) is preferable.
_{^{Gly - (- O-Y x}} -) p -O-Z 1 -O - (- Y x -O-) p -Gly
... (x1-1)

In this case, an alcohol represented by the following formula (y1-1) is obtained as the alcohol represented by the formula (y).

As a particularly preferable ester forming reaction performed in the presence of an imidazole compound, a tetracarboxylic dianhydride represented by the following formula (Ba) and a hydroxy group represented by the following formula (A1-4) shown below: Reaction with a provided compound. In the formula (Ba), X is a tetravalent organic group.
(H — [— O—Y—] _p —O—) _j —Z — [— O—Y—] _p —OH (A1-4)
Suitable tetracarboxylic dianhydrides in this reaction include those described above for (B) nucleophiles, among which tetracarboxylic dianhydrides represented by the aforementioned formula (b1) are preferred.

When the tetracarboxylic dianhydride represented by the above formula (b1) is used as the tetracarboxylic dianhydride, the tetracarboxylic dianhydride is converted to (A) an electrophile such as a hydroxy group-providing compound and the like. In order to make it react, the temperature of 130 degreeC or more was required.
However, when the tetracarboxylic dianhydride represented by the formula (b1) is reacted with an electrophile (A) such as a hydroxy group-providing compound in the presence of the imidazole compound having the above-mentioned predetermined structure, it is less than 130 ° C. The reaction proceeds favorably at a temperature of preferably 100 ° C. or higher and lower than 130 ° C.
The effect of lowering the reaction temperature can also be obtained when the carboxylic acid anhydride other than the tetracarboxylic dianhydride represented by the formula (b1) is reacted with the electrophile (A).

According to the said reaction, it is an ester compound according to the ratio of the usage-amount of the hydroxy-group provision compound represented by Formula (A1-4), and the tetracarboxylic dianhydride represented by Formula (Ba). Various condensation products are produced.
In particular, when 2 mol or more of the hydroxy group-providing compound represented by the formula (A1-4) is used with respect to 1 mol of the tetracarboxylic dianhydride represented by the formula (Ba), the formula (AB1) is used. The ester compound produced is the main product. By reducing at least one of the carboxy groups in the ester compound according to a conventional method, it can be converted into an aldehyde group.
By the above method, the ester compound represented by the formula (AB2) having a carboxy group and / or an aldehyde group is obtained. In formula (AB2), R ^c1 and R ^c2 each independently represent a hydrogen atom or a hydroxy group.

The hydroxy group-providing compound represented by the formula (A1-4) and the tetracarboxylic dianhydride represented by the formula (Ba) are obtained by a conventional method using a catalyst such as a tetraalkylammonium halide. When the ester compound represented by the formula (AB1) is produced by condensation, the reaction at a low temperature tends to obtain a product having a narrow molecular weight distribution, but the reaction rate is slow.
On the other hand, even if the reaction rate is good in the reaction at a high temperature, it is difficult to control the reaction and it is difficult to obtain a product having a narrow molecular weight distribution.
On the other hand, when the compound represented by the formula (AB1) is produced in the presence of an imidazole compound having a predetermined structure, the desired reaction can proceed well regardless of the reaction temperature, and the molecular weight distribution is narrow. Easy to obtain product.

Moreover, the diol represented by the above formula (y1-1) is used as the hydroxy group-providing compound as the electrophile (A), and the tetra represented by the above formula (Ba) is used as the nucleophile (B). When carboxylic dianhydride is used, an ester compound represented by the following formula (AB3) is generated. By reducing at least one of the carboxy groups in the ester compound according to a conventional method, it can be converted into an aldehyde group.
By the above method, the ester compound represented by the formula (AB4) having a carboxy group and / or an aldehyde group is obtained. In formula (AB4), R ^c1 and R ^c2 each independently represent a hydrogen atom or a hydroxy group.

・・・（ＡＢ３）

・・・（ＡＢ４）

... (AB3)

... (AB4)

  The ester compound represented by Formula (AB2) or Formula (AB4) can be suitably used as an additive component for imparting alkali solubility or heat resistance to various compositions such as a photosensitive resin composition.

The hydroxy group may be blocked by reacting the hydroxy group contained in the ester compound represented by formula (AB3) or formula (AB4) with an acid anhydride. Such a blocking reaction of the hydroxy group is preferably performed in the presence of the imidazole compound having the above-mentioned predetermined structure.
Examples of acid anhydrides used for such blocking include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl Cycloaliphatic dibasic acid anhydrides such as endomethylenetetrahydrophthalic anhydride and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trihydric anhydride Aliphatic or aromatic dibasic or tribasic acid anhydrides such as merit acid, or biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic acid di Anhydrous, anhydrous pyrome Tsu DOO acid, aliphatic or aromatic tetracarboxylic acid dianhydride such as benzophenone tetracarboxylic acid dianhydride and the like, can be used one or two or more of these.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

  In Examples, Compound 1 and Compound 2 produced according to the following method were used as additives during the reaction.

<Compound 1>

<Compound 2>

1. Synthesis Example of Compound 1 First, 30 g of cinnamic acid derivative having the structure of the following formula was dissolved in 200 g of methanol, and then 7 g of potassium hydroxide was added to the methanol. The methanol solution was then stirred at 40 ° C. Methanol was distilled off and the residue was suspended in 200 g of water. To the obtained suspension, 200 g of tetrahydrofuran was mixed and stirred, and the aqueous phase was separated. Under ice cooling, 4 g of hydrochloric acid was added and stirred, and then 100 g of ethyl acetate was mixed and stirred. After allowing the mixture to stand, the oil phase was collected. The target product was crystallized from the oil phase, and the precipitate was collected to obtain an imidazole compound (compound 1) having the above structure.

The measurement results of ¹ H-NMR of Compound 1 are as follows.
¹ H-NMR (DMSO): 11.724 (s, 1H), 7.838 (s, 1H), 7.340 (d, 2H, J = 4.3 Hz), 7.321 (d, 1H, J = 7.2 Hz), 6.893 (d, 2H, J = 4.3 Hz), 6.876 (d, 1H, J = 6.1 Hz), 5.695 (dd, 1H, J = 4.3 Hz) 3.2 Hz), 3.720 (s, 3H), 3.250 (m, 2H)

2. Synthesis Example of Compound 2 Specifically, except that the raw material compound is changed to a cinnamic acid derivative having the structure of the following formula: In the same manner as in the synthesis example of Compound 1, Compound 2 described above was obtained.

[Example 1]
(Process 1)
In a 1500 mL four-necked flask, 235 g (0.5 mol, epoxy equivalent 235) of diglycidyl ether of 9,9-bis (4-hydroxyphenyl) -9H-fluorene and 0.24 g of compounds 1, 2, 6 -100 mg of di-tertbutyl-4-methylphenol and 72.0 g of acrylic acid were charged, and heated and dissolved at 90 to 100 ° C while blowing air at a rate of 25 mL / min.

(Process 2)
Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. Here, although the solution gradually became transparent and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature and obtained the bisphenol fluorene type | mold epoxy acrylate of the transparent and colorless solid structure of the following Formula.

(Process 3)
Next, after adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g (0.5 mol) of the above-obtained bisphenolfluorene type epoxy acrylate, 3,3 ′, 4,4′-biphenyl is dissolved. Tetracarboxylic dianhydride (0.3 mol) and 1.2 g of Compound 1 were mixed and gradually heated to react at 110 ° C. or 130 ° C. for 4 hours.

(Process 4)
After confirming the disappearance of the acid anhydride group, 30 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to produce from bisphenolfluorene type epoxy acrylate and acid anhydride. A carboxylic acid ester was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

The number average molecular weight and the mass average molecular weight of the carboxylic acid ester obtained by performing the reaction at 110 ° C. and the carboxylic acid ester obtained by performing the reaction at 130 ° C. were measured to determine the dispersity. It can be said that the lower the degree of dispersion, the smaller the amount of unreacted raw material remaining and the amount of high molecular weight product produced, and the desired reaction proceeded rapidly.
Regarding the degree of dispersion, 1.5 or less was determined as ◯, 1.5 to 2.5 or less was determined as Δ, and 2.5 was determined as ×. The evaluation results of the degree of dispersion of the obtained carboxylic acid ester are shown in Table 1.

[Examples 2 to 6 and Comparative Examples 1 to 6]
(Step 3) In the same manner as in Example 1, except that the amount (mole) and the type of acid anhydride described in Table 1 are used and the type of additive described in Table 1 is used. Reaction was performed at 110 ° C. and 130 ° C., and the degree of dispersion of the obtained carboxylic acid ester was evaluated. The evaluation results of the degree of dispersion are shown in Table 1. However, when 1,2,3,6-tetrahydrophthalic anhydride is used in (Step 3) (Examples 5 to 6, Comparative Example 1, Comparative Example 3, and Comparative Example 5), (Step 4) Without doing so, the degree of dispersion was evaluated.

In addition, the kind of acid anhydride in Table 1 is as follows.
(B) -1: 1,2,3,6-tetrahydrophthalic anhydride (B) -2: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (B) -3: Tetracarboxylic dianhydride represented (norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride object)

Regarding the additives in Table 1, compounds 3 to 5 are as follows.
Compound 3: benzyltriethylammonium chloride compound 4: 2-ethyl-4-imidazole compound 5: triphenylphosphine

According to Examples 1 to 6, in the presence of an imidazole compound represented by the formula (1) such as Compound 1 or Compound 2, (A) an epoxy acrylate that is a hydroxy group-providing compound as an electrophile, and (B ) When the carboxylic acid anhydride described in Table 1 is reacted as a nucleophile, the remaining reaction raw materials and excessive high molecular weight are suppressed, and the desired reaction proceeds well regardless of the reaction temperature. As a result, it is understood that a carboxylic acid ester having a low degree of dispersion was obtained.
On the other hand, it can be seen from the comparative example that when compounds 3 to 5 are used as additives during the reaction, it is difficult to obtain a carboxylic acid ester having a low degree of dispersion.

  In addition, according to Examples 2 and 4, in order to proceed the reaction by opening the carboxylic anhydride group of (B) -3, a temperature of 130 ° C. or higher is usually required. It can be seen that if the reaction is carried out in the presence of the imidazole compound represented, the reaction proceeds well even at a low temperature of about 110 ° C.

In addition, the imidazole compounds represented by the formula (1) such as the compound 1 and the compound 2 are advantageous in that they do not contain halide ions. When a conventionally used catalyst containing a halide ion such as Compound 3 (benzyltriethylammonium chloride) is used, halide ions remain in the resulting carboxylic acid ester.
On the other hand, in the photosensitive resin composition used for forming a transparent film, if the content of halide ions is large, the transparency of the formed film may be lowered. For this reason, in the ester compound mix | blended with the photosensitive resin composition, it is desirable for halide ion content to be very small.
In this respect, since the imidazole compound represented by the formula (1) does not contain halide ions, the photosensitive composition is used even if the ester compound obtained using the imidazole compound is blended with the photosensitive resin composition. It is easy to form a film with excellent transparency.

Example 8
In a glass flask equipped with a stirrer, a thermometer, a Dimroth cooling tank, and a dropping funnel, 5.55 g of toluene, 0.17 g (0.7 mmol) of Compound 1, 4,4′-butylidene-bis (6-tert -Butyl-3-methylphenol), 0.049 g of 6-tert-butyl-2,4-xylenol, and 1.50 g (14.7 mmol) of 3-hydroxy-γ-butyrolactone (the following alcohol compound). ) And stirred at 70 ° C. To the dropping funnel, 2.49 g (16.2 mmol) of methacrylic anhydride was added and dropped into the flask in 5 minutes. After completion of the dropping, the reaction was carried out while adjusting the reaction temperature to 70 ° C. Sampling is performed during the reaction, and the sample is analyzed by GC until 3-hydroxy-γ-butyrolactone disappears, and 3-hydroxy-γ-butyrolactone methacrylate (= γ-butyrolactone-3-yl methacrylate) is obtained. Obtained. Crotonolactone, a reaction byproduct (β-eliminated ester), was not detected. Further, when the reaction solution was analyzed by GPC (gel permeation chromatography), no oligomer component was detected.

[Comparative Example 7]
The reaction was conducted under the same conditions as in Example 8 except that the reaction temperature was changed to 50 ° C. and that Compound 1 was changed to 0.18 g (1.5 mmol) of 4-dimethylaminopyridine. -Butyrolactone methacrylate was obtained. The content of crotonolactone, a reaction by-product (β-eliminated ester), was observed.

  From the results of Example 8 and Comparative Example 7, it can be seen that the imidazole compound represented by Compound 1 not only replaces highly toxic 4-dimethylaminopyridine, but also has the effect of not producing a reaction byproduct. .

Claims (3)

(A) at least one hydroxy group-providing compound selected from the group consisting of a phenol compound and an alcohol; and an epoxy group-providing compound consisting of an epoxy compound; and at least one electrophile selected from the group consisting of:
(B) at least one nucleophile selected from the group consisting of carboxylic acid, carboxylic acid halide, carboxylic acid ester, and carboxylic acid anhydride,
Following formula (1):

(In Formula (1), R ¹ each independently represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic group which may have a substituent, and R ³ each independently represents a halogen atom, A hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n represents an integer of 0 to 3. R ¹ may combine with the other R ¹ or R ² to form a cyclic structure.)
The manufacturing method of carboxylic acid ester including making it react in presence of the imidazole compound represented by these. Following formula (1):

(In Formula (1), R ¹ each independently represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic group which may have a substituent, and R ³ each independently represents a halogen atom, A hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n represents an integer of 0 to 3. R ¹ may combine with the other R ¹ or R ² to form a cyclic structure.)
The esterifying agent containing the imidazole compound represented by these. Following formula (1):

(In Formula (1), R ¹ each independently represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic group which may have a substituent, and R ³ each independently represents a halogen atom, A hydroxy group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, or an organic group, and n represents an integer of 0 to 3. R ¹ may combine with the other R ¹ or R ² to form a cyclic structure.)
The ring-opening addition catalyst containing the imidazole compound represented by these.