JP6280919B2 - Thioxanthene compound, base proliferating agent, and base-reactive resin composition containing the base proliferating agent - Google Patents

Description

  The present invention relates to a thioxanthene compound, a base proliferating agent, and a base-reactive resin composition containing the base proliferating agent. More specifically, the present invention relates to a thioxanthene compound capable of decomposing by the action of a base to generate a new base, a base proliferating agent, and a base-reactive resin composition containing the base proliferating agent.

  A photosensitive resin composition containing an acid generator that generates an acid upon irradiation with light is applied as a photoresist material, a photocuring material, or the like. The acid generated from the acid generator acts as a catalyst or a polymerization initiator. When a photosensitive resin composition containing an acid generator or the like is used as a photoresist material to form a pattern, for example, acid generation The agent is irradiated with light to generate a strong acid serving as a catalyst, and the resin component is chemically modified. Then, a pattern is formed by the change in solubility of the chemically modified resin component.

  Such a photoresist material is required to have a high resolution and sensitivity and to be able to form a pattern having high etching resistance. In particular, as a deep ultraviolet resist material, a pattern having resistance to oxygen plasma etching is formed. There is a need for materials to obtain. Various photoresist materials comprising a photosensitive resin composition containing an acid generator have been provided for the purpose of high sensitivity, high resolution, etc., but a combination of a photoacid generator and a resin material is provided. Since the types are limited to some extent, a new photosensitive system that does not use an acid generator has been demanded.

  In addition, various studies have been made to improve the photocuring speed of monomers, oligomers, or polymers, and radical photopolymerization systems that polymerize many vinyl monomers using radical species generated by the action of light as initiators. These materials have been widely targeted for development. In addition, active studies have been made on cationic polymerization materials that generate an acid by the action of light and use this acid as a catalyst. However, in the case of radical photopolymerization-type materials, since the polymerization reaction is inhibited and the curing reaction is suppressed by oxygen in the air, a special device for blocking oxygen has been required. In addition, in the case of a cationic polymerization material, there is no oxygen inhibition like a radical photopolymerization material, but the strong acid generated from the photoacid generator remains after curing, which causes the presence of the strong acid. The corrosivity and the possibility of denaturation of the resin have been problems.

  Against this background, in order to obtain a resist material that can form a pattern with high resolution and sensitivity and high etching resistance, the curing technology that rapidly solidifies the liquid material using active energy rays is further improved in performance. Therefore, there is a strong demand for a photosensitive resin composition using a new photosensitive system that is not affected by oxygen in the air and that does not contain corrosive substances such as strong acids that are generated and the reaction proceeds with high efficiency. It was rare.

  As one of the means for overcoming the above problems, a method using a polymerization reaction or chemical reaction by a base catalyst, for example, a method of generating a base by the action of light and chemically denaturing a resin using this as a catalyst, A means for applying a photosensitive resin composition using a base generated by the above as a catalyst to a photoresist material, a photocuring material or the like has been studied. The compound having an epoxy group is cured by causing a crosslinking reaction by the action of a base to generate amines as initiators or catalysts in the epoxy resin layer by the action of light or heat, and then heated. Methods of curing by processing are provided. However, even when amines are used as initiators or catalysts, it has been a problem that the curing rate of epoxy compounds is slow. That is, in order to fully cure the epoxy compound, it takes a long time, and it is necessary to perform a heat treatment at a high temperature in order to further increase the curing rate, so that it has not been put into practical use.

  In order to solve these problems, a base proliferating agent that secondarily amplifies a base generated by the action of light has been proposed. When the base proliferating agent is combined with a photobase generator and a base-reactive compound, a photosensitive resin is proposed. A composition is obtained. In addition, a resin composition that is improved in performance by adding a base proliferating agent that increases the base in a proliferative manner is also known, and contains a base proliferating agent that is a urethane compound that causes a base proliferating reaction. A photosensitive resin composition is disclosed (see, for example, Patent Document 1 and Patent Document 2).

JP 2000-330270 A JP 2002-128750 A

  However, in the conventionally provided methods, the base proliferating agent has low sensitivity, and has poor solubility in organic solvents and low compatibility with base-reactive compounds. It was difficult to make the proliferation reaction proceed efficiently.

  The present invention has been made in view of the above problems, and can be used for, for example, a crosslinking reaction of an epoxy compound, can generate a new base by the presence of a base, and can be dissolved in an organic solvent. Since it is highly heat-resistant and has higher heat resistance than conventional base proliferating agents, when it is contained in a base-reactive compound, the compound, base proliferating agent, and the base proliferating agent that efficiently undergo a base proliferating reaction It is in providing the base reactive resin composition containing this.

  In order to solve the above problems, the compound according to the present invention is represented by the following formula (A).

（式（Ａ）中、Ｒ_１、Ｒ_２及びＲ_３はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、Ｑは水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基、炭素数７〜１５のアリールアルキル基、下記式（Ｂ_１）で表される基または下記式（Ｂ_２）で表される基を示し、Ｒ_３及びＱは互いに結合して環構造を形成してもよい。Ｘ_１はＳＯまたはＳＯ_２を示し、Ｙ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｚ_１、Ｚ_２、Ｚ_３及びＺ_４はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基、炭素数７〜１５のアリールアルキル基、炭素数１〜１２のハロアルキル基、ハロゲン原子またはニトロ基を示す。ただし、Ｙ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｚ_１、Ｚ_２、Ｚ_３及びＺ_４がすべて水素原子である場合を除く。）

(In the formula _{(A), R 1, R} 2 and _{R 3} are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, aryl having 6 to 14 carbon atoms Or an arylalkyl group having 7 to 15 carbon atoms, Q is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 7 carbon atoms. To 15 arylalkyl groups, a group represented by the following formula (B ₁ ) or a group represented by the following formula (B ₂ ), and R ₃ and Q may be bonded to each other to form a ring structure. X ₁ represents SO or SO ₂ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently a hydrogen atom or an alkyl having 1 to 12 carbon atoms. Group, cycloalkyl group having 5 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms , An arylalkyl group having 7 to 15 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, a halogen atom or a nitro group, provided that Y ₁ , Y ₂ , Y ₃ , Y ₄ , Z ₁ , Z ₂ , Z ₃ And Z ₄ are all hydrogen atoms.)

（式（Ｂ_１）中、Ｄ_１は下記式（Ｖ_１）または下記式（Ｖ_２）を示し、Ｄ_２は下記式（Ｖ_１）または下記式（Ｖ_３）を示す。Ｒ_８、Ｒ_９及びＲ_１０はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示す。前記式（Ａ）のＲ_３、Ｄ_１が下記式（Ｖ_２）である場合のｍ_１個のＲ_４及びＲ_５、Ｄ_２が下記式（Ｖ_３）である場合のｍ_２個のＲ_６及びＲ_７、並びにＲ_８は、これらのＲのうち、少なくとも２つのＲが互いに結合して環構造を形成してもよい。ｎ_１は０〜２０の整数を示し、Ｘ_２はＳＯまたはＳＯ_２を示し、Ｙ_５、Ｙ_６、Ｙ_７、Ｙ_８、Ｚ_５、Ｚ_６、Ｚ_７及びＺ_８はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基、炭素数７〜１５のアリールアルキル基、炭素数１〜１２のハロアルキル基、ハロゲン原子またはニトロ基を示す。）

(In formula (B ₁ ), D ₁ represents the following formula (V ₁ ) or the following formula (V ₂ ), and D ₂ represents the following formula (V ₁ ) or the following formula (V ₃ ): R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. it is shown. formula _R 3 of (a), _{D 1} is represented by the following formula _{(V 2) R 4 m 1} pieces of when it is and _R 5, _{D 2} is _{m 2} when it is the following formula _{(V 3)} R ₆ and R ₇ , and R ₈ may form a ring structure by combining at least two of these Rs, and n ₁ represents an integer of 0 to 20, and X ₂ represents SO or _{SO 2, Y 5, Y 6} , Y 7, Y 8, Z 5, Z 6, Z 7 and _{Z 8} are each And a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, and 1 to 12 carbon atoms. Represents a haloalkyl group, a halogen atom or a nitro group.)

（式（Ｂ_２）中、Ｄ_１は下記式（Ｖ_１）または下記式（Ｖ_２）を示し、Ｄ_２は下記式（Ｖ_１）または下記式（Ｖ_３）を示し、Ｄ_３は下記式（Ｖ_１）または下記式（Ｖ_４）を示す。Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１３、Ｒ_１４及びＲ_１５はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示す。前記式（Ａ）のＲ_３、Ｄ_１が下記式（Ｖ_２）である場合のｍ_１個のＲ_４及びＲ_５、Ｄ_２が下記式（Ｖ_３）である場合のｍ_２個のＲ_６及びＲ_７、Ｒ_８、Ｄ_３が下記式（Ｖ_４）である場合のｍ_３個のＲ_１１及びＲ_１２、並びにＲ_１３は、これらのＲのうち、少なくとも２つのＲが互いに結合して環構造を形成してもよい。ｎ_１、ｎ_２及びｎ_３はそれぞれ独立して、０〜２０の整数を示し、ｗは０または１を示し、Ｘ_２及びＸ_３はそれぞれ独立して、ＳＯまたはＳＯ_２を示し、Ｙ_５、Ｙ_６、Ｙ_７、Ｙ_８、Ｙ_９、Ｙ_１０、Ｙ_１１、Ｙ_１２、Ｚ_５、Ｚ_６、Ｚ_７、Ｚ_８、Ｚ_９、Ｚ_１０、Ｚ_１１及びＺ_１２はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基、炭素数７〜１５のアリールアルキル基、炭素数１〜１２のハロアルキル基、ハロゲン原子またはニトロ基を示す。）

(In the formula (B ₂ ), D ₁ represents the following formula (V ₁ ) or the following formula (V ₂ ), D ₂ represents the following formula (V ₁ ) or the following formula (V ₃ ), and D ₃ represents Formula (V ₁ ) or the following formula (V ₄ ) is shown: R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms, wherein R ₃ and D _{1 in} the formula (A) are represented by the following formula (V ₂ ): In a case where m ₁ R ₄ and R ₅ and D ₂ are the following formula (V ₃ ), m ₂ R ₆ and R ₇ , R ₈ and D ₃ are the following formula (V ₄ ) _{m 3} pieces of _{R 11} and _{R 12} when and _{R 13,} are, among these R, bonded at least two R are mutually May be formed structure _.n 1, _{n 2} and _{n 3} are each independently an integer of 0 to 20, w represents 0 or 1, _{X 2} and _{X 3} are each independently, SO Or SO ₂ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ And Z ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, A haloalkyl group having 1 to 12 carbon atoms, a halogen atom or a nitro group is shown.)

（式（Ｖ_２）中、ｍ_１個のＲ_４及びＲ_５はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、ｍ_１は１〜７の整数を示す。）

(In the formula (V ₂ ), m ₁ R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. And an arylalkyl group having 7 to 15 carbon atoms, and m ₁ represents an integer of ₁ to 7.)

（式（Ｖ_３）中、ｍ_２個のＲ_６及びＲ_７はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、ｍ_２は１〜７の整数を示す。）

(In the formula (V ₃ ), m ₂ R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. Or an arylalkyl group having 7 to 15 carbon atoms, and m ₂ represents an integer of 1 to 7.)

（式（Ｖ_４）中、ｍ_３個のＲ_１１及びＲ_１２はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、ｍ_３は１〜７の整数を示す。）

(In the formula (V ₄ ), m ₃ R ₁₁ and R ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. Or an arylalkyl group having 7 to 15 carbon atoms, and m ₃ represents an integer of 1 to 7.)

The compound according to the present invention is characterized in that, in the above-described present invention, the compound represented by the formula (A) is represented by the following formula (A ₁ ).

（式（Ａ_１）中、Ｒ_１、Ｒ_２及びＲ_３、Ｘ_１、Ｙ_１、Ｙ_２、Ｙ_３及びＹ_４、並びにＺ_１、Ｚ_２、Ｚ_３及びＺ_４は前記式（Ａ）と同様であり、Ｒ_３’は水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、Ｒ_３及びＲ_３’は互いに結合して環構造を形成してもよい。）

(In the formula (A ₁ ), R ₁ , R ₂ and R ₃ , X ₁ , Y ₁ , Y ₂ , Y ₃ and Y ₄ , and Z ₁ , Z ₂ , Z ₃ and Z ₄ are the same as those in the formula (A). R ₃ ′ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. R ₃ and R ₃ ′ may be bonded to each other to form a ring structure.)

In the above-described present invention, the compound according to the present invention is characterized in that the compound represented by the formula (A) is represented by the following formula (A ₂ ).

（式（Ａ_２）中、Ｄ_１及びＤ_２、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_８、Ｒ_９及びＲ_１０、ｎ_１、Ｘ_１及びＸ_２、Ｙ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｙ_５、Ｙ_６、Ｙ_７及びＹ_８、並びにＺ_１、Ｚ_２、Ｚ_３、Ｚ_４、Ｚ_５、Ｚ_６、Ｚ_７及びＺ_８は、前記式（Ａ）及び前記式（Ｂ_１）と同様である。）

(In the formula (A ₂ ), D ₁ and D ₂ , R ₁ , R ₂ , R ₃ , R ₈ , R ₉ and R ₁₀ , n ₁ , X ₁ and X ₂ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ and Y ₈ , and Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ and Z ₈ are defined by the above formula (A) and the above formula ( Same as B ₁ ).

The compound according to the present invention is characterized in that, in the above-described present invention, the compound represented by the formula (A) is represented by the following formula (A ₃ ).

（式（Ａ_３）中、Ｄ_１、Ｄ_２及びＤ_３、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１３、Ｒ_１４及びＲ_１５、ｎ_１、ｎ_２及びｎ_３、ｗ、Ｘ_１、Ｘ_２及びＸ_３、Ｙ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｙ_５、Ｙ_６、Ｙ_７、Ｙ_８、Ｙ_９、Ｙ_１０、Ｙ_１１及びＹ_１２、並びにＺ_１、Ｚ_２、Ｚ_３、Ｚ_４、Ｚ_５、Ｚ_６、Ｚ_７、Ｚ_８、Ｚ_９、Ｚ_１０、Ｚ_１１及びＺ_１２は、前記式（Ａ）及び前記式（Ｂ_２）と同様である。）

(In the formula (A ₃ ), D ₁ , D ₂ and D ₃ , R ₁ , R ₂ , R ₃ , R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ and R ₁₅ , n ₁ , n ₂ and n ₃ , w, X ₁ , X ₂ and X ₃ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ , Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ and Z ₁₂ are the same as those in the above formula (A) and the above formula (B ₂ ). Is the same.)

  The base proliferating agent according to the present invention is characterized by comprising the aforementioned compound of the present invention.

  The base-reactive resin composition according to the present invention includes the above-described base proliferating agent according to the present invention and a base-reactive compound.

  The base-reactive resin composition according to the present invention comprises the above-described base proliferating agent according to the present invention, a base generator and a base-reactive compound.

  The base-reactive resin composition according to the present invention is characterized in that, in the above-described present invention, the base generator is a photobase generator.

  The base-reactive resin composition according to the present invention is characterized in that, in the above-described present invention, the base-reactive compound is at least one selected from the group consisting of an epoxy compound, a silicon compound, and an oxetane compound. And

  The compound and the base proliferating agent according to the present invention have high sensitivity, can be decomposed by the action of a base to generate a base in a chain, and have a heterocycle (heterocycle). By changing the above, the base growth reaction rate can be freely controlled, and a compound capable of generating bases in a chain and a base proliferating agent are obtained. In addition, since it has good solubility in organic solvents and high compatibility with base-reactive compounds, and further has higher heat resistance than conventional base proliferating agents, the compounds of the present invention, base proliferating agents, Coexisting with a base-reactive compound such as an epoxy compound that reacts with the base enables the base-reactive compound to be efficiently cured by the base generated by growth.

  In addition, the base-reactive compound according to the present invention contains the base proliferating agent of the present invention or the base proliferating agent of the present invention and a base generating agent, thereby generating a base generated from the base proliferating agent and a base such as an epoxy compound. The reaction with the reactive compound proceeds in a chain, resulting in an excellent curing rate and reaction efficiency, resulting in a base-reactive resin composition that is rapidly cured and sufficiently cured. In addition, the base-reactive resin composition of the present invention that exhibits this effect can be suitably used for, for example, a highly sensitive photocuring material, resist material (pattern forming material), and the like.

It is a diagram showing a reaction scheme for the formula (A _1). It is a diagram showing a reaction scheme for the formula (A _2). It is a diagram showing a reaction scheme for the formula (A _3). It is a diagram showing a reaction scheme for the formula (A _3). It is a diagram showing a reaction scheme for the formula (A _3). It is a diagram illustrating a synthetic scheme for formula (A _1). It is a diagram illustrating a synthetic scheme for formula (A _2). It is a figure which showed the synthetic scheme about the formula (A2) at the time of making a base part into 1, ₂ -bis (4-piperidyl) ethane. For formula _{(A 2),} a diagram showing a synthesis scheme when the base portion is isophorone diamine (1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane). It is a diagram illustrating a synthetic scheme for formula (A _3). It is the figure which showed the relationship between a heating time, the conversion rate of a base growth agent, and the production | generation rate of an olefin. It is the figure which showed the relationship between a heating time and the production rate of an olefin. It is the figure which showed the relationship between a heating time, the conversion rate of a base growth agent, and the production | generation rate of an olefin. It is the figure which showed the solubility with respect to the organic solvent of a base growth agent. It is the figure which showed the relationship between exposure amount and pencil hardness. It is the figure which showed the relationship between exposure amount and pencil hardness. It is the figure which showed the relationship between exposure amount and pencil hardness. It is the figure which showed the relationship between exposure amount and pencil hardness.

  Hereinafter, one embodiment of the present invention will be described. The base proliferating agent according to the present invention is a compound represented by the following formula (A).

（式（Ａ）中、Ｒ_１、Ｒ_２及びＲ_３はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、Ｑは水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基、炭素数７〜１５のアリールアルキル基、下記式（Ｂ_１）で表される基または下記式（Ｂ_２）で表される基を示し、Ｒ_３及びＱは互いに結合して環構造を形成してもよい。Ｘ_１はＳＯまたはＳＯ_２を示し、Ｙ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｚ_１、Ｚ_２、Ｚ_３及びＺ_４はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基、炭素数７〜１５のアリールアルキル基、炭素数１〜１２のハロアルキル基、ハロゲン原子またはニトロ基を示す。ただし、Ｙ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｚ_１、Ｚ_２、Ｚ_３及びＺ_４がすべて水素原子である場合を除く。）

(In the formula _{(A), R 1, R} 2 and _{R 3} are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, aryl having 6 to 14 carbon atoms Or an arylalkyl group having 7 to 15 carbon atoms, Q is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 7 carbon atoms. To 15 arylalkyl groups, a group represented by the following formula (B ₁ ) or a group represented by the following formula (B ₂ ), and R ₃ and Q may be bonded to each other to form a ring structure. X ₁ represents SO or SO ₂ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently a hydrogen atom or an alkyl having 1 to 12 carbon atoms. Group, cycloalkyl group having 5 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms , An arylalkyl group having 7 to 15 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, a halogen atom or a nitro group, provided that Y ₁ , Y ₂ , Y ₃ , Y ₄ , Z ₁ , Z ₂ , Z ₃ And Z ₄ are all hydrogen atoms.)

（式（Ｂ_１）中、Ｄ_１は下記式（Ｖ_１）または下記式（Ｖ_２）を示し、Ｄ_２は下記式（Ｖ_１）または下記式（Ｖ_３）を示す。Ｒ_８、Ｒ_９及びＲ_１０はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示す。前記式（Ａ）のＲ_３、Ｄ_１が下記式（Ｖ_２）である場合のｍ_１個のＲ_４及びＲ_５、Ｄ_２が下記式（Ｖ_３）である場合のｍ_２個のＲ_６及びＲ_７、並びにＲ_８は、これらのＲのうち、少なくとも２つのＲが互いに結合して環構造を形成してもよい。ｎ_１は、０〜２０の整数を示し、Ｘ_２はＳＯまたはＳＯ_２を示し、Ｙ_５、Ｙ_６、Ｙ_７、Ｙ_８、Ｚ_５、Ｚ_６、Ｚ_７及びＺ_８はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基、炭素数７〜１５のアリールアルキル基、炭素数１〜１２のハロアルキル基、ハロゲン原子またはニトロ基を示す。）

(In formula (B ₁ ), D ₁ represents the following formula (V ₁ ) or the following formula (V ₂ ), and D ₂ represents the following formula (V ₁ ) or the following formula (V ₃ ): R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. it is shown. formula _R 3 of (a), _{D 1} is represented by the following formula _{(V 2) R 4 m 1} pieces of when it is and _R 5, _{D 2} is _{m 2} when it is the following formula _{(V 3)} R ₆ and R ₇ , and R ₈ may form a ring structure by bonding at least two of these Rs, and n ₁ represents an integer of 0 to 20, ₂ represents SO or _{SO 2, Y 5, Y 6} , Y 7, Y 8, Z 5, Z 6, Z 7 and _{Z 8} it Independently, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, and 1 to 12 carbon atoms Represents a haloalkyl group, a halogen atom or a nitro group.)

（式（Ｂ_２）中、Ｄ_１は下記式（Ｖ_１）または下記式（Ｖ_２）を示し、Ｄ_２は下記式（Ｖ_１）または下記式（Ｖ_３）を示し、Ｄ_３は下記式（Ｖ_１）または下記式（Ｖ_４）を示す。Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１３、Ｒ_１４及びＲ_１５はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示す。前記式（Ａ）のＲ_３、Ｄ_１が下記式（Ｖ_２）である場合のｍ_１個のＲ_４及びＲ_５、Ｄ_２が下記式（Ｖ_３）である場合のｍ_２個のＲ_６及びＲ_７、Ｒ_８、Ｄ_３が下記式（Ｖ_４）である場合のｍ_３個のＲ_１１及びＲ_１２、並びにＲ_１３は、これらのＲのうち、少なくとも２つのＲが互いに結合して環構造を形成してもよい。ｎ_１、ｎ_２及びｎ_３はそれぞれ独立して、０〜２０の整数を示し、ｗは０または１を示し、Ｘ_２及びＸ_３はそれぞれ独立して、ＳＯまたはＳＯ_２を示し、Ｙ_５、Ｙ_６、Ｙ_７、Ｙ_８、Ｙ_９、Ｙ_１０、Ｙ_１１、Ｙ_１２、Ｚ_５、Ｚ_６、Ｚ_７、Ｚ_８、Ｚ_９、Ｚ_１０、Ｚ_１１及びＺ_１２はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基、炭素数７〜１５のアリールアルキル基、炭素数１〜１２のハロアルキル基、ハロゲン原子またはニトロ基を示す。）

(In the formula (B ₂ ), D ₁ represents the following formula (V ₁ ) or the following formula (V ₂ ), D ₂ represents the following formula (V ₁ ) or the following formula (V ₃ ), and D ₃ represents Formula (V ₁ ) or the following formula (V ₄ ) is shown: R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms, wherein R ₃ and D _{1 in} the formula (A) are represented by the following formula (V ₂ ): In a case where m ₁ R ₄ and R ₅ and D ₂ are the following formula (V ₃ ), m ₂ R ₆ and R ₇ , R ₈ and D ₃ are the following formula (V ₄ ) _{m 3} pieces of _{R 11} and _{R 12} when and _{R 13,} are, among these R, bonded at least two R are mutually May be formed structure _.n 1, _{n 2} and _{n 3} are each independently an integer of 0 to 20, w represents 0 or 1, _{X 2} and _{X 3} are each independently, SO Or SO ₂ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ And Z ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, A haloalkyl group having 1 to 12 carbon atoms, a halogen atom or a nitro group is shown.)

（式（Ｖ_２）中、ｍ_１個のＲ_４及びＲ_５はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、ｍ_１は、１〜７の整数を示す。）

(In the formula (V ₂ ), m ₁ R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. And an arylalkyl group having 7 to 15 carbon atoms, m ₁ represents an integer of 1 to 7.)

（式（Ｖ_３）中、ｍ_２個のＲ_６及びＲ_７はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、ｍ_２は、１〜７の整数を示す。）

(In the formula (V ₃ ), m ₂ R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. Or an arylalkyl group having 7 to 15 carbon atoms, and m ₂ represents an integer of 1 to 7.)

（式（Ｖ_４）中、ｍ_３個のＲ_１１及びＲ_１２はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、ｍ_３は、１〜７の整数を示す。）

(In the formula (V ₄ ), m ₃ R ₁₁ and R ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. And an arylalkyl group having 7 to 15 carbon atoms, m ₃ represents an integer of 1 to 7.)

Formula (A) has a Q group as described above, and the Q group is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. In the case of an arylalkyl group having 7 to 15 carbon atoms, the Q group is the following R ₃ ′ group (A ₁ ), and the Q group is a group represented by the formula (B ₁ ) When the following formula (A ₂ ) is obtained and the Q group is a group represented by the formula (B ₂ ), the following formula (A ₃ ) is obtained.

Hereinafter, Formula (A ₁ ), Formula (A ₂ ), and Formula (A ₃ ) are given as specific embodiments of Formula (A). In the formula (A ₂ ), m when R ₃ and D ₁ are the formula (V ₂ ) m ₁ when R _4, R ₅ and D ₂ are the formula (V ₃ ) _Two of R _6, R ₇ , and R ₈ may be bonded to each other to form a ring structure. Similarly, in the formula (A ₃ ), when R ₃ and D ₁ are the formula (V ₂ ), m ₁ R ₄ and R ₅ and D ₂ are the formula (V ₃ ). m ₂ pieces of _{R 6} and _{R 7,} R 8, _{D 3} is _{m 3} pieces of _{R 11} and _{R 12} in the case where formula _{(V 4),} and _{R 13,} of these R, at least two R May be bonded to each other to form a ring structure.

（式（Ａ_１）中、Ｒ_１、Ｒ_２及びＲ_３、Ｘ_１、Ｙ_１、Ｙ_２、Ｙ_３及びＹ_４、並びにＺ_１、Ｚ_２、Ｚ_３及びＺ_４は前記式（Ａ）と同様であり、Ｒ_３’は水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、Ｒ_３及びＲ_３’は互いに結合して環構造を形成してもよい。）

(In the formula (A ₁ ), R ₁ , R ₂ and R ₃ , X ₁ , Y ₁ , Y ₂ , Y ₃ and Y ₄ , and Z ₁ , Z ₂ , Z ₃ and Z ₄ are the same as those in the formula (A). R ₃ ′ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. R ₃ and R ₃ ′ may be bonded to each other to form a ring structure.)

（式（Ａ_２）中、Ｄ_１及びＤ_２、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_８、Ｒ_９及びＲ_１０、ｎ_１、Ｘ_１及びＸ_２、Ｙ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｙ_５、Ｙ_６、Ｙ_７及びＹ_８、並びにＺ_１、Ｚ_２、Ｚ_３、Ｚ_４、Ｚ_５、Ｚ_６、Ｚ_７及びＺ_８は、前記式（Ａ）及び前記式（Ｂ_１）と同様である。）

(In the formula (A ₂ ), D ₁ and D ₂ , R ₁ , R ₂ , R ₃ , R ₈ , R ₉ and R ₁₀ , n ₁ , X ₁ and X ₂ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ and Y ₈ , and Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ and Z ₈ are defined by the above formula (A) and the above formula ( Same as B ₁ ).

（式（Ａ_３）中、Ｄ_１、Ｄ_２及びＤ_３、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１３、Ｒ_１４及びＲ_１５、ｎ_１、ｎ_２及びｎ_３、ｗ、Ｘ_１、Ｘ_２及びＸ_３、Ｙ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｙ_５、Ｙ_６、Ｙ_７、Ｙ_８、Ｙ_９、Ｙ_１０、Ｙ_１１及びＹ_１２、並びにＺ_１、Ｚ_２、Ｚ_３、Ｚ_４、Ｚ_５、Ｚ_６、Ｚ_７、Ｚ_８、Ｚ_９、Ｚ_１０、Ｚ_１１及びＺ_１２は、前記式（Ａ）及び前記式（Ｂ_２）と同様である。）

(In the formula (A ₃ ), D ₁ , D ₂ and D ₃ , R ₁ , R ₂ , R ₃ , R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ and R ₁₅ , n ₁ , n ₂ and n ₃ , w, X ₁ , X ₂ and X ₃ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ , Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ and Z ₁₂ are the same as those in the above formula (A) and the above formula (B ₂ ). Is the same.)

Further, the formula _{(A 3),} what was w = 1 formula _{(A 3} '), placed below those with w = 0 as an expression _(A 3 "). In addition, the formula _{(A 3')} and In formula (A ₃ ″), D ₁ , D ₂ and D ₃ , R ₁ , R ₂ , R ₃ , R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ and R ₁₅ , n ₁ , n ₂ and n ₃ , X ₁ , X ₂ and X ₃ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ , and Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ and Z ₁₂ (formula (A ₃ ″) are represented by D ₃ , R ₁₃ , n ₃ does not exist.) is the same as the formula (A) and the formula (B ₂ ).

The difference between the formula (A ₃ ′) and the formula (A ₃ ″) is the presence of the following structure. When w = 1, the following group is present, and when w = 0, the following structure is present. It does not exist, and the nitrogen atom between — (CH ₂ ) n ₁ — and — (CH ₂ ) n ₂ — is directly bonded to the carbon atom on the carbonyl group in the vicinity of the thioxanthene ring containing X ₃ . Also, D ₃ , R ₁₃ and n ₃ are considered only when w = 1.

In R ₁ , R ₂ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ in the above formula, the alkyl group preferably has 1 to 6 carbon atoms, and the cycloalkyl group has carbon atoms. Is preferably 6-8, and when it is an aryl group, the carbon number is preferably 6-10, and when it is an arylalkyl group, the carbon number is preferably 7-11. Specific examples of R ₁ , R ₂ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ include, for example, methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, phenyl group, tolyl group, naphthyl group, benzyl Group, phenethyl group, naphthylmethyl group and the like.

When R ₃ , R ₃ ′, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₁₁ , R ₁₂ , R ₁₃ and Q in the above formula are alkyl groups, the number of carbon atoms is 2 to 2. 6 is preferable, and examples thereof include an ethyl group, a propyl group, a butyl group, and a hexyl group. In the case of a cycloalkyl group, the number of carbon atoms is preferably 6 to 8, and examples thereof include a cyclohexyl group and a cyclooctyl group. In the case of an aryl group, the carbon number is preferably 6 to 10, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group. In the case of an arylalkyl group, the carbon number is preferably 7 to 11, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ in the above formula, and Z ₁ , Z ₂ , Z ₃ , Z ₄ , when Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ and Z ₁₂ are alkyl groups, the number of carbon atoms is preferably 1-6, and when it is a cycloalkyl group The number of carbon atoms is preferably 6-8. When an aryl group is used, the number of carbon atoms is preferably 6-10. When the arylalkyl group is used, the number of carbon atoms is preferably 7-11. In this case, the number of carbon atoms is preferably 1 to 6, and when a halogen atom is used, a fluorine atom or a chlorine atom is preferable. Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ , and Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z Specific examples of ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ and Z ₁₂ include, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a phenyl group. , Tolyl group, naphthyl group, benzyl group, phenethyl group, naphthylmethyl group, perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, fluorine atom, chlorine atom, nitro group and the like.

  The above alkyl group, cycloalkyl group, aryl group, arylalkyl group and haloalkyl group may have a substituent. In this case, examples of the substituent include an amino group, an alkoxy group, an alkoxycarbonyl group, an acyl group. Group, acyloxy group, hydroxy group and the like.

In the above formula, “R ₃ and Q may be bonded to each other to form a ring structure” and “R ₃ and R ₃ ′ may be bonded to each other to form a ring structure”. The `` structure '' may be any ring structure such as a saturated aliphatic ring, an unsaturated aliphatic ring, and an aromatic ring. In addition, a hydrogen atom bonded to a carbon atom constituting these rings is, for example, Ring structure substituted with alkyl group such as methyl group, ethyl group, propyl group, hydroxy group, mercapto group, cyano group, nitro group, for example, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom In addition, a ring structure having a hetero atom (oxygen atom, sulfur atom, etc.) other than a nitrogen atom in the chain is also included in the concept of “ring structure” in the above formula. Specific examples of these ring structures include, for example, aziridine ring (3-membered ring), azetidine ring (4-membered ring), pyrrolidine ring (5-membered ring), piperidine ring (6-membered ring), hexamethyleneimine ring (azepane). Ring; 7-membered ring), heptamethyleneimine ring (azocan ring; 8-membered ring), octamethyleneimine ring (azonan ring; 9-membered ring), nonamethyleneimine ring (azecan ring; 10-membered ring), decamethyleneimine ring A nitrogen-containing saturated aliphatic ring having 2 to 10 carbon atoms such as (11-membered ring); for example, 2-methylaziridine ring (3-membered ring), 2-methylazetidine ring (4-membered ring), 3-methylazetidine Ring (4-membered ring), 2,5-dimethylpyrrolidine ring (5-membered ring), 2,5-diethylpyrrolidine ring (5-membered ring), 2,5-dipropylpyrrolidine ring (5-membered ring), 2,6 -Dimethylpiperidine ring (6-membered ring), 2 6-diethylpiperidine ring (6-membered ring), 2,4,6-trimethylpiperidine ring (6-membered ring), 4-hydroxypiperidine (6-membered ring), 4-mercaptopiperidine (6-membered ring), 4-cyanopiperidine (6-membered ring), 4-nitropiperidine (6-membered ring), 4-chloropiperidine (6-membered ring), 4-bromopiperidine (6-membered ring), etc., bonded to carbon atoms constituting the saturated aliphatic ring The hydrogen atom is, for example, an alkyl group such as a methyl group, an ethyl group, or a propyl group, a hydroxy group, a mercapto group, a cyano group, or a nitro group, such as a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Substituted nitrogen-containing saturated aliphatic ring having 2 to 10 carbon atoms; for example, oxazolidine ring (5-membered ring), thiazolidine ring (5-membered ring), morpholine ring (6-membered ring), thiomorpholine ring ( A nitrogen-containing saturated aliphatic ring having 3 to 10 carbon atoms and having a hetero atom other than the nitrogen atom (oxygen atom, sulfur atom, etc.) in the chain, such as a 2,6-dimethylmorpholine ring (6-membered ring) ), 2,6-diethylmorpholine ring (6-membered ring), 2,6-dipropylmorpholine ring (6-membered ring), 2,6-dimethylthiomorpholine ring (6-membered ring), 2,6-diethylthiomorpholine Rings (6-membered rings), 2,6-dipropylthiomorpholine rings (6-membered rings) and other heteroatoms (oxygen atoms, sulfur atoms, etc.) other than nitrogen atoms in the chain, and saturated aliphatic rings The hydrogen atom bonded to the constituting carbon atom is, for example, an alkyl group such as a methyl group, an ethyl group, or a propyl group, a hydroxy group, a mercapto group, a cyano group, a nitro group, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine Substitution with halogen atoms such as atoms A nitrogen-containing saturated aliphatic ring having 3 to 10 carbon atoms, such as a pyrrole ring (5-membered ring), an imidazole ring (5-membered ring), a pyrazole ring (5-membered ring), etc. Nitrogen unsaturated aliphatic ring or aromatic ring, for example, 2,5-dimethylpyrrole ring (5-membered ring), 2,5-diethylpyrrole ring (5-membered ring), 2,5-dipropylpyrrole ring (5-membered ring) 2,5-dimethylimidazole ring (5-membered ring), 2,5-diethylimidazole ring (5-membered ring), 2,5-dipropylimidazole ring (5-membered ring), 3,5-dimethylpyrazole ring (5 Member), 3,5-diethylpyrazole ring (5-membered ring), 3,5-dipropylpyrazole ring (5-membered ring), etc., and hydrogen bonded to carbon atoms constituting the unsaturated aliphatic ring or aromatic ring Atom is alkyl such as methyl, ethyl, propyl , A hydroxy group, a mercapto group, a cyano group, a nitro group, for example, a nitrogen-containing unsaturated aliphatic ring having 3 to 10 carbon atoms substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom An aromatic ring etc. are mentioned.

Furthermore, n ₁ in formula (A ₂ ) and formula (B ₁ ), n ₁ , n ₂ and n ₃ in formula (A ₃ ) and formula (B ₂ ) are each independently an integer of 0 to 20. Is preferably an integer of 0 to 8.

Similarly, _{m 1} in Formula _{(V 2), m 2} in the formula _{(V 3), m 3} in the formula _{(V 4)} is each independently 1-7 integer, an integer of 1 to 3 and It is preferable to do.

Next, specific examples of the compound contained in the base proliferating agent represented by the formula (A), the formula (A ₁ ), the formula (A ₂ ), and the formula (A ₃ ) are shown.

In Formula (A) and Formula (A ₁ ), R ₃ is a hydrogen atom, and Q (R ₃ ′ in Formula (A ₁ )) is a cycloalkyl group having 5 to 10 carbon atoms (formula (G -1) and formula (G-2)).

In formulas (A) and (A ₁ ), R ₃ and Q (R ₃ ′ in formula (A ₁ )) are bonded to each other to form a ring structure (formula (G-3) , Formula (G-4) and Formula (G-5)).

In Formula (A) and Formula (A ₂ ), R ₃ and R ₈ are both hydrogen atoms, D ₁ is Formula (V ₂ ), and m ₁ in Formula (V ₂ ) is 1. R ₄ and R ₅ are both hydrogen atoms, D ₂ is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 1, and both R ₆ and R ₇ are hydrogen. A specific example in which n ₁ is 4 (or R ₃ and R ₈ are both hydrogen atoms, D ₁ is the formula (V ₂ ), and the formula (V ₂ ) m ₁ is 5, and all _five R ₄ and R ₅ are hydrogen atoms, D ₂ is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 1, and Specific examples in which R ₆ and R ₇ are both hydrogen atoms and n ₁ is 0.) (Formula (G-6)). In the formula (A), Q is the formula (B ₁ ).

In the above, D ₁ is the formula (V ₂ ), m ₁ in the formula (V ₂ ) is 1, and R ₄ and R ₅ are both hydrogen atoms, and D ₂ Is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 1, and R ₆ and R ₇ are both hydrogen atoms.

In formula (A) and formula (A ₂ ), R ₃ and R ₈ are both hydrogen atoms, D ₁ is formula (V ₁ ), D ₂ is (V ₃ ), and the formula ( A specific example in which m _{2 in} V ₃ ) is 1, R ₆ and R ₇ are both hydrogen atoms, and n ₁ is 0 (formula (G-7)). In the formula (A), Q is the formula (B ₁ ).

In the formulas (A) and (A ₂ ), D ₁ is the formula (V ₂ ), m ₁ in the formula (V ₂ ) is 3, and the formula in that case is the following formula (V _2A ) R _4a , R _4b , R _5a , R _5b and R _5c in the (V _2A ) are all hydrogen atoms, and R ₃ and R _4C are bonded via a dimethylene chain having 2 carbon atoms. Are bonded to each other to form a ring structure, D ₂ is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 3, and the formula in that case is represented by the following formula ( V _3A ), and R _6b , R _6c , R _7a , R _7b and R _{7c in the} formula (V _3A ) are all hydrogen atoms, and R _6a and R ₈ have 2 carbon atoms. and via a dimethylene chain be those which combine to form a ring structure, examples of when n ₁ is 2 (formula (G -8)). In the formula (A), Q is the formula (B ₁ ).

In the formulas (A) and (A ₂ ), D ₁ is the formula (V ₂ ), m ₁ in the formula (V ₂ ) is 3, and the formula in that case is the following formula (V _2A ) In the formula (V _2A ), R _4a , R _4b , R _5a , R _5b and R _5c are all hydrogen atoms, and R ₃ and R _4C represent a dimethylene chain having 2 carbon atoms. Are bonded to each other to form a ring structure, and D ₂ is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 3, and the formula in that case is the following formula are those represented by _{(V 3A), R} 6b in the formula _{(V 3A), R 6c,} R 7a, an _{R 7b} and _{R 7c} are all hydrogen _atoms, carbon atoms in the _{R 6a} and _{R 8} A specific example (Formula (G-8b)) in the case where they are bonded to each other via 2 dimethylene chains to form a ring structure. In the formula (A), Q is the formula (B ₁ ).

In Formula (A) and Formula (A ₂ ), D ₁ is Formula (V ₂ ), m ₁ in Formula (V ₂ ) is 1, and both R ₄ and R ₅ are hydrogen atoms. D ₂ is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 1, R ₆ and R ₇ are both hydrogen atoms, n ₁ is 0, A specific example in which R ₃ and R ₈ are bonded to each other via a dimethylene chain having 2 carbon atoms to form a ring structure (formula (G-9)). In the formula (A), Q is the formula (B ₁ ). The structure of the following formula is a specific example in which R ₃ and R ₈ jump over (CH ₂ ) _n1 and bond to form a ring structure.

In formula (A), formula (A ₃ ), and formula (A ₃ ′), R ₃ , R _8, and R ₁₃ are all hydrogen atoms, D ₁ is formula (V ₂ ), and the formula (V ₂ ) m ₁ is 1, R ₄ and R ₅ are both hydrogen atoms, D ₂ is the formula (V ₃ ), and m ₂ in the formula (V ₃ ) is 1. And R ₆ and R ₇ are both hydrogen atoms, D ₃ is the formula (V ₄ ), m ₃ in the formula (V ₄ ) is 1, and both R ₁₁ and R ₁₂ are hydrogen. A specific example in which n ₁ , n ₂ and n ₃ are all 1 and w is 1 (formula (G-10)). In the formula (A), Q is the formula (B ₂ ).

In Formula (A), Formula (A ₃ ), and Formula (A ₃ ″), R ₃ and R ₈ are all hydrogen atoms, D ₁ is Formula (V ₂ ), and in Formula (V ₂ ) M ₁ is 1 and R ₄ and R ₅ are both hydrogen atoms, D ₂ is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 1, and R 2 ₆ and R ₇ are both hydrogen atoms, n ₁ and n ₂ are all 1 and w is 0 (D ₃ , R ₁₃ and n ₃ do not exist) (formula (G-11 In addition, in Formula (A), Q becomes Formula (B ₂ ).

Such a base proliferating agent according to the present invention has a property of decomposing by the action of a base to generate a base (amine). Regarding the reaction behavior, the reaction scheme for the formula (A ₁ ) is shown in FIG. 1, the reaction scheme for the formula (A ₂ ) is shown in FIG. 2, the reaction scheme for the formula (A ₃ ) is shown in FIG. 3, FIG. Show. As shown in such a reaction scheme, the base proliferating agent of the present invention decomposes in a self-proliferating manner only by allowing a smaller equivalent amount of base to act on a certain amount, and finally the entire amount decomposes, A large amount of base corresponding to the amount of the base proliferating agent is generated. And when it coexists with a base-reactive compound (described later), the generated base (amine) acts on the base-reactive compound, and the base-reactive compound can be cross-linked with the generated base to be efficiently cured. Become. In the scheme, HNR′R ″ is an arbitrary base (amine).

The base proliferating agent represented by the formula (A) has high sensitivity and has a heterocycle (heterocycle). Therefore, the base proliferative reaction rate can be freely controlled by changing the oxidation number of the heteroatom. The X ₁ , X ₂ and X ₃ groups that are atoms are SO or SO ₂ , but the decomposition rate is faster when the hetero atom is SO ₂ . Therefore, the growth reaction rate can be easily adjusted by selecting such heteroatoms.

  Further, for example, a decomposition intermediate in the decomposition of the formula (A) is shown in the following formula. Since the base proliferating agent according to the present invention becomes a decomposition intermediate having the following structure, the stronger the electron withdrawing property of the X group, the more the anion is stabilized. That is, the ease with which anions are generated can be controlled by the oxidation number of heteroatoms.

Since the base proliferating agent according to the present invention is highly soluble in an organic solvent, when mixed with a base-reactive compound to form a base-reactive resin composition, it can be easily compatible with the base-reactive compound. it can. The base proliferating agent according to the present invention is such that Y ₁ , Y ₂ , Y ₃ , Y ₄ , Z ₁ , Z ₂ , Z _3, Z _4, etc., at least one of Y group and Z group is not a hydrogen atom. Therefore, the solubility in organic solvents is excellent. Among these, among the base proliferating agents according to the present invention, the base proliferating agent represented by the formula (A ₂ ) and the formula (A ₃ ) is a base proliferating agent in which all of the Y group and the Z group are hydrogen atoms. Compared with, it is a preferable base proliferating agent because of its excellent solubility in organic solvents. That is, since the base proliferating agent represented by the formula (A ₂ ) and the formula (A ₃ ) has two or more asymmetric points, it becomes a diastereomeric mixture, and thus has a higher solubility in organic solvents than the conventional one. It is thought that the price will rise dramatically.

  In addition, since the base proliferating agent according to the present invention has high heat resistance, when it is mixed with a base-reactive compound to form a base-reactive resin composition, it becomes a resin composition with high thermal stability. Therefore, when forming a pattern using the said resin composition, a favorable pattern can be formed. That is, the base proliferating agent according to the present invention has higher heat resistance than the base proliferating agent in which all of the Y group and the Z group are hydrogen atoms. Therefore, when the base proliferating agent according to the present invention is mixed with a base-reactive compound to form a base-reactive resin composition, the exposed portion is cured during baking in pattern formation, but the unexposed portion. Since is not cured, a good pattern can be formed.

  The base that acts on the base proliferating agent is not particularly limited, and conventionally known bases can be used. For example, amines such as primary amines, secondary amines, tertiary amines, and pyridyl groups can be used. A compound to be contained, a hydrazine compound, an amide compound, a quaternary ammonium hydroxide salt, a mercapto compound, a sulfide compound, a phosphine compound and the like can be used. In addition, for example, compounds containing amines and pyridyl groups, hydrazine compounds, amide compounds, quaternary ammonium hydroxide salts, mercapto compounds, sulfide compounds, phosphine compounds and the like disclosed in International Publication No. WO2009 / 19999 can be used. it can.

Examples of bases generated by decomposition of the base proliferating agent represented by the formula (A) (formula (A ₁ ), formula (A ₂ ) and formula (A ₃ )) include the following formulas (Am-1), (Am -2) or an amine represented by the formula (Am-3). In the formula, R ₃ , R ₃ ′, R ₈ , R ₁₃ , D ₁ , D ₂ , D ₃ , n ₁ , n _2, and n ₃ , and w are the formulas (A) and (A ₁ ), the formula (A ₂ ) and the formula (A ₃ ).

In order to synthesize a base proliferating agent represented by the formula (A ₁ ), the formula (A ₂ ), and the formula (A ₃ ), for example, using the thioxanthone as a starting material, the synthesis schemes shown in FIGS. What should I do? Figure 6 A synthetic scheme for formula _{(A 1),} formula _{(A 2)} 7 Synthesis scheme for, for formula _{(A 2),} the base portion of 1,2-bis (4-piperidyl) ethane (formula ( G-8) corresponds to the case where R ₁ , R ₂ , R ₉ , and R ₁₀ are hydrogen atoms.) The synthesis scheme is as shown in FIG. 8, the formula (A ₂ ), and the base moiety is isophoronediamine. When (1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane) is used (for formula (G-7), corresponding to the case where R ₁ , R ₂ , R ₉ and R ₁₀ are hydrogen atoms 9), and FIG. 10 shows a synthesis scheme for the formula (A ₃ ). In the synthesis scheme, for convenience, R ₁ , R ₂ , R ₉ , R ₁₀ , R ₁₄ , and R ₁₅ are sometimes shown as hydrogen atoms.

In addition, as basic operations in synthesis, for example, the following (1) to (4) or (1) to (3), (5) and (6) may be followed, but not particularly limited thereto. .
(1) A carbonyl group of a thioxanthone derivative is reduced with lithium aluminum hydride to obtain a 9H-thioxanthene derivative. In addition, when there is a commercially available 9H-thioxanthene derivative, such a commercially available product may be used as it is.
(2) The sulfur atom of the thioxanthene ring is oxidized with metachloroperbenzoic acid (mCPBA) to be converted into a sulfinyl group or a sulfonyl group.
(3) Hydroxymethylation using formaldehyde.
(4) An amide bond is formed by diisocyanic acid (limited to those in which R ₃ , R ₈ and R ₁₃ are hydrogen atoms).
(5) Reaction with chloroformate-4-nitrophenyl or triphosgene to activate the carbonyl group.
(6) The active carbonyl compound is reacted with an amine to obtain the target product.

  The base proliferating agent according to the present invention is preferably used as a base proliferating agent composition in combination with a base generator. Here, the base generator is generally a substance that generates a base when irradiated with active energy rays such as light or heated. The base generator is not particularly limited, but a photobase generator that generates a base upon irradiation with active energy rays such as light, or a thermal base generator (thermal latent base generator) that generates a base by heating is used. It is preferable to do. Among these, it is particularly preferable to use a photobase generator because it is not necessary to perform heat treatment at a high temperature in order to generate a base.

  The photobase generator is not particularly limited, but conventionally known o-nitrobenzyl photobase generator, (3,5-dimethoxybenzyloxy) carbonyl photobase generator, amyloxyimino group photobase generator. And dihydropyridine type photobase generators. Among these, an o-nitrobenzil type photobase generator is preferably used because of excellent base generation efficiency and ease of synthesis.

  As the photobase generator, for example, oxime ester compounds, ammonium compounds, benzoin compounds, dimethoxybenzyl urethane compounds, o-nitrobenzyl urethane compounds and the like disclosed in JP 2000-330270 A are used. You may do it.

  Moreover, as a photobase generator, the base generator etc. which are disclosed by Unexamined-Japanese-Patent No. 2009-280785, Unexamined-Japanese-Patent No. 2010-84144, and Unexamined-Japanese-Patent No. 2011-236416 etc. can also be used. These are carboxylates composed of carboxylic acids and bases that are decarboxylated by light irradiation.

Moreover, the photobase generator represented by the following formula | equation can also be used. Note that in the formula (E-3), —R— represents — (CH ₂ ) ₆ — or —CH ₂ CH ₂ CH ₂ CH (CH ₃ ) CH ₂ —. In Formula (E-4), the —OMe group represents —OCH ₃ (methoxy group).

  The thermal base generator is not particularly limited, but is decomposed by a salt of an organic acid and a base that is decarboxylated and decomposed by heating, an intramolecular nucleophilic substitution reaction, a Rossen rearrangement reaction, a Beckmann rearrangement reaction, etc. A compound to be released or a compound which causes some reaction by heating to release a base is preferably used. Especially, since it is excellent in base generation | occurrence | production efficiency, the salt of the organic acid and base which decarboxylates and decomposes | disassembles by heating is used preferably.

  Examples of the thermal base generator include salts of trichloroacetic acid described in British Patent No. 998949, salts of alphasulfonylsulfonyl described in US Pat. No. 4,060,420, salts of propylic acids described in JP-A-59-157737, 2 -Carboxyl carboxamide derivatives, salts of base components described in JP-A-59-168440 with thermally decomposable acids using an alkali metal or alkaline earth metal in addition to an organic base, described in JP-A-59-180537 Hydroxam carbamates utilizing the Lossen rearrangement, aldoxime carbamates described in JP-A-59-195237, which generate nitriles by heating, British Patent No. 998945, US Pat. No. 3,208,846, British Patent No. 279480, Japanese Utility Model Laid-Open Nos. 50-22625, 61-32844, 61- 1139, JP-A 61-52638, JP-A 61-51140, JP-A 61-53634, JP-A 61-53640, JP-A 61-55644, JP-A 61-55645 And the like. Moreover, you may make it use the compound which generate | occur | produces a base by the heating disclosed by Unexamined-Japanese-Patent No. 2000-330270.

  Specific examples of other thermal base generators include guanidine trichloroacetate, methylguanidine trichloroacetate, potassium trichloroacetate, guanidine phenylsulfonylacetate, guanidine p-chlorophenylsulfonylacetate, guanidine p-methanesulfonylphenylsulfonylacetate, phenylpropiol. Examples include potassium acid, guanidine phenylpropiolate, cesium phenylpropiolate, guanidine p-chlorophenylpropiolate, guanidine p-phenylene-bis-phenylpropiolate, tetramethylammonium phenylsulfonylacetate and tetramethylammonium phenylpropiolate.

  When a base proliferating agent and a base generator are used in combination as a base proliferating agent composition, the bases constituting the base proliferating agent and the bases constituting the base generating agent may be made common. Since the bases are common, the base proliferating agent is efficiently decomposed.

  When the base proliferating agent and the base generator are used in combination as a base proliferating agent composition, the mixing ratio of the base proliferating agent and the base generating agent is a mass ratio of base proliferating agent / base generating agent = 40/1 to 1 /. It is preferable to be within the range of 4. If the blending amount of the base proliferating agent is too small, base may not be generated efficiently and the base reactive compound may not be allowed to react rapidly. On the other hand, if the amount of the base proliferating agent is too large, the amount of base generator used increases, and the base generator itself may adversely affect the solubility of the base-reactive compound. It is not preferable. The mixing ratio of the base proliferating agent and the base generating agent is particularly preferably in the range of base proliferating agent / base generating agent = 20/1 to 1/1 by mass ratio.

  Moreover, you may use a base growth agent individually by 1 type or in combination of 2 or more types. Moreover, when using together a base growth agent and a base generator as a base growth agent composition, you may use a base generator individually by 1 type or in combination of 2 or more types.

Next, the base reactive resin composition of the present invention will be described. The base-reactive resin composition of the present invention is a base proliferating agent represented by at least one of the above formula (A), formula (A ₁ ), formula (A ₂ ), and formula (A ₃ ), or such a base. A proliferation agent and a base generator (base proliferation agent composition) and a base-reactive compound that undergoes a curing reaction in the presence of a base are contained as essential components.

  The base-reactive compound constituting the base-reactive resin composition of the present invention reacts with the action of a base generated by a base proliferating agent or a base proliferating agent and a base generator (base proliferating agent composition), and crosslinks. Can be used, and various compounds can be used. In particular, it is preferable to use, for example, an epoxy compound having at least one epoxy group, a silicon compound having at least one alkoxysilyl group or silanol group, an oxetane compound containing an oxetane ring, and the like. Such base-reactive compounds may be used alone or in combination of two or more.

  Usable epoxy compounds (epoxy resins) include, for example, diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol poly Glycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol jig Sidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, cresyl glycidyl ether, aliphatic diglycidyl ether, polyfunctional glycidyl ether, tertiary fatty acid monoglycidyl ether, spiroglycol diglycidyl ether, A glycidyl propoxy trimethoxysilane etc. are mentioned. These epoxy compounds may be halogenated or hydrogenated, and these epoxy compounds include derivatives. These epoxy compounds may be used alone or in combination of two or more.

  As the silicon-based compound (silicon-based resin), for example, an alkoxysilane compound or a silane coupling agent can be used. Examples of alkoxysilane compounds include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, phenyl Examples include trimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. These alkoxysilane compounds may be used alone or in combination of two or more.

  Examples of the silane coupling agent include vinyl silane, acrylic silane, epoxy silane, amino silane, and the like. Examples of the vinyl silane include vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane, vinyl triethoxysilane, and vinyl trimethoxysilane. Examples of the acrylic silane include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and the like. Examples of the epoxy silane include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. As aminosilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane and the like can be mentioned. Examples of other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

  As the oxetane compound (oxetane resin), a monomeric oxetane compound, a dimer oxetane compound, or the like can be used. Usable oxetane compounds include, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylic acid bis [(3-ethyl-3-oxetanyl) Methyl] ester, xylylene oxetane such as 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3-((((3-ethyloxetane-3-yl) methoxy) methyl ) Oxetane (or 3-(((3-ethyloxetane-3-yl) methoxy) methyl) -3-ethyloxetane), 3-ethylhexyloxetane, 3-ethyl-3-hydroxyoxetane, 3-ethyl- 3-hydroxymethyl oxetane, oxetated phenol novolak, etc. are mentioned. These oxetane compounds may be used alone or in combination of two or more.

  Hereinafter, the reaction behavior between the base and the epoxy compound will be described. In the following scheme, R and R ′ represent, for example, an alkyl group having 1 to 12 carbon atoms, but are not particularly limited thereto.

In the primary or secondary amine system, as shown in the scheme shown below, for example, when a primary amine is added to an epoxy group, it becomes an intermediate 1, but hydrogen that can be eliminated as H ⁺ Since there are two on the nitrogen atom, one H ⁺ is lost and changes to 2. On the other hand, since the changed 2 has a secondary amine structure, it can react with another epoxy compound once again to produce 3.

(scheme)

  Hereinafter, specific examples of the base-reactive compound will be given. The following No. 2-1. Among the polymer compounds (base reactive compounds) 2-8, No. 2-1. The polymer compound 2-5 undergoes elimination and decarboxylation by the action of a base. On the other hand, no. 2-6, No. 2 2-7 and no. The polymer compound 2-8 causes a elimination reaction by the action of a base to produce a carboxylic acid.

  The above-mentioned base reactive compound No. 2-1. 2-8 is a polymer group that undergoes elimination reaction by the action of a base and changes polarity, and is applied as a material (resist material) for patterning by utilizing the change in solubility before and after decomposition. can do.

  Other examples of base-reactive compounds are also given. In addition, among the base reactive compounds No. 3-1 to No. 3-4 below, the No. 3-1 substance (mixture) undergoes dehydration condensation and crosslinking reaction by the action of the base. No. The substance (mixture) 3-2 undergoes dehydration condensation and crosslinking reaction by the action of a base. No. 3-3 substance (polymer) undergoes decarboxylation by the action of a base. In the No. 3-4 substance, an imide formation reaction occurs due to the action of the base. In addition, No. 3-1. In 3-2, x represents a number exceeding 0 and 1 or less, and “x: 1-x” represents the abundance ratio of each unit to the last, and does not mean the number of molecules.

  As the base-reactive compound constituting the base-reactive resin composition of the present invention, an epoxy-based compound having at least one epoxy group can be used. Moreover, an epoxy compound can be made into a polymer by ring-opening polymerization of an epoxy group by allowing a base to act on an epoxy compound having at least two epoxy groups. Moreover, such an epoxy compound can be chemically modified by adding a base to the epoxy compound. An example of an epoxy compound showing polymerization reactivity is shown below.

  Other examples of the epoxy compound (polymer) exhibiting polymerization reactivity are shown below.

  In addition, as the base-reactive compound, a silicon compound having at least one silanol group or alkoxysilyl group can be used. Further, by causing a base to act on a silicon compound having at least two silanol groups or alkoxysilyl groups, such a silicon compound can be made into a polymer by condensation polymerization of silanol groups or alkoxysilyl groups. Specific examples of silicon compounds showing polymerization reactivity (No. 5-2 to No. 5-4 are polymers) are shown below.

The above-mentioned photobase generator, a base proliferator composition using the base proliferator and the photobase generator of the present invention in combination, a base reactive resin composition containing a base proliferator and a photobase generator (photosensitive resin composition) The range of the irradiation light wavelength and the exposure amount in the product) depends on the type and amount of the photobase generator and the type of the base reactive compound constituting the base reactive resin composition (photosensitive resin composition). For example, the wavelength may be selected from the range of 190 to 400 nm and the exposure amount may be selected from the range of 100 to 10000 mJ / cm ² , and the higher wavelength region can be obtained by using a sensitizer described later. Can also be used. Although irradiation time of irradiation light may be possible even for several seconds, it may be about 10 seconds or more, and preferably 1.5 to 20 minutes.

  On the other hand, the heating conditions in the case of using a thermal base generator may be appropriately determined according to the type and amount of the thermal base generator used, the type of the base reactive compound constituting the base reactive resin composition, and the like. However, the heating temperature may be about 50 to 150 ° C. and the heating time may be 1 to 1800 minutes.

  In addition, when a base-reactive resin composition is used with a base proliferating agent and a base-reactive compound without using a base generator, a desired base that can be decomposed by the base proliferating agent should be added. It is preferable to add a base common to the base proliferating agent.

  The content of the base proliferating agent in the base-reactive resin composition of the present invention is based on 100 parts by weight of the base-reactive compound in consideration of the case where the molecular weight of the base-reactive compound such as an epoxy compound is relatively low. It is desirable to select from the range of about 0.1 to 350 parts by mass, preferably 0.1 to 60 parts by mass. Further, the content of the base proliferating agent is preferably 1 to 60 parts by mass, more preferably 2 to 30 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the base-reactive compound. More preferably, it is 2-15 mass parts. Moreover, you may make it contain from the range of 0.1-50 mol per monomer unit of a base reactive compound (an epoxy-type compound or a silicon-type compound). The base proliferating agent may be selected from the range of 10 to 90 mol% in terms of the amine functional group ratio of the base proliferating agent to 100 mol of the epoxy group in the base-reactive compound, and should be 40 to 80 mol%. Is preferred. The amine functional group ratio is expressed as mol% of the number of amino groups in the base proliferating agent with respect to the number of epoxy groups in the epoxy compound when the target base reactive compound is an epoxy compound, for example. Yes, for example, an amine functional group ratio of 10 mol% (with respect to epoxy group) means that 10 amino groups (10 mol) are generated from the base proliferating agent with respect to 100 epoxy groups (100 mol) in the base-reactive compound. It refers to a base proliferating agent (the same applies to the amine functional group ratio for the base generator described later). In the above description, an epoxy compound having an epoxy group is taken as an example of the base-reactive compound, but the same applies to other base-reactive compounds such as silicon compounds.

  In the case where a base proliferating agent and a base generating agent are used in combination and the base reactive compound is contained as a base proliferating agent composition, the content of the base generating agent is the amount of the base proliferating agent and the base generating agent described above. It is preferable to include a base generator so as to correspond to the blending ratio (mass ratio). Moreover, it is preferable that content of a base generator shall be 0.5-40 mass parts with respect to 100 mass parts of base reactive compounds. If the content of the base generator is less than 0.5 parts by mass, it may not act on the base proliferating agent and the base reactive compound may not be allowed to react rapidly, whereas the content of the base generator is 40. Exceeding parts by mass, the presence of the base generator may adversely affect the solubility of the base-reactive compound in the solvent, as with the base proliferating agent, and the presence of an excessive amount of the base generator leads to high costs. It will be. The content of the base generator is preferably 0.5 to 35 parts by mass, more preferably 2 to 35 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the base-reactive compound. It is particularly preferable to do this. Moreover, you may make it contain from the range of 0.1-50 mol per monomer unit of a base reactive compound (an epoxy-type compound or a silicon-type compound). The base generator may be selected from the range of 5 to 90 mol% in terms of the amine functional group ratio of the base generator to 100 mol of the epoxy group in the base-reactive compound, and it should be 10 to 80 mol%. Is preferred.

  The base-reactive resin composition of the present invention has the above-described No. 1 as a base-reactive compound. 4-1. No. 4-14 and other epoxy compounds exhibiting polymerization reactivity (polymerizable epoxy compounds) 5-1 to No. It is preferable to use a silicon compound (polymerizable silicon compound) exhibiting polymerization reactivity such as 5-6. Such a base-reactive resin composition is polymerized by the action of light or heat to give a polymer. Especially, it is preferable to set it as the base reactive resin composition (photosensitive resin composition) containing the base reactive compound which starts a polymerization reaction with light.

  The base-reactive resin composition of the present invention preferably further contains a thiol compound. The thiol compound acts as a curing functional group such as epoxy when used in combination with an epoxy compound or the like. As the thiol compound, a polythiol compound having two or more thiol groups is preferably used. For example, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), dipentaerythritol hexakis. (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3 -Mercaptoisobutyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), tris [(3-mercaptopropionyloxy) Ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate) Pionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione and the like, and polythiol compounds having 2 to 5 thiol groups. Among these, in consideration of reactivity and ease of handling, pentaerythritol tetrakis (3-mercaptobutyrate), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate) ) Is preferably used. These thiol compounds may be used alone or in combination of two or more.

  The amount of the thiol compound used is, for example, thiol equivalent (SH equivalent) / epoxy equivalent (or oxetane equivalent) = 0.3 / 1.7 to 1.7 / 0.3 with respect to the epoxy compound or oxetane compound. Preferably, the ratio is 0.8 / 1.2 to 1.2 / 0.8. If this ratio is in the range of 0.3 / 1.7 to 1.7 / 0.3, a large amount of unreacted thiol group or epoxy group (or oxetane group) remains in the cured product. It can prevent and the tendency for the mechanical property of hardened | cured material to fall can be suppressed.

  In order to form a pattern using the base-reactive resin composition according to the present invention, for example, the resin composition is dissolved in an organic solvent to prepare a coating solution, and the prepared coating solution is used as a suitable substrate or the like. Apply to a solid surface and dry to form a coating. And after performing pattern exposure with respect to the formed coating film and generating a base, it heat-processes on predetermined conditions, The polymerization reaction of the base reactive compound contained in a base reactive resin composition To encourage. The pattern can be obtained by immersing this in a solvent that causes a difference in solubility between the exposed part and the unexposed part and developing.

  Since the base-reactive resin composition of the present invention contains the base proliferating agent of the present invention, the polymerization reaction proceeds even at room temperature, but it is preferable to perform a heat treatment in order to allow the polymerization reaction to proceed efficiently. The conditions for the heat treatment may be appropriately determined depending on the exposure energy, the type of base generated from the base proliferating agent to be used, and the type of base-reactive compound such as an epoxy-based compound or silicon-based compound. It is preferable to be in the range of 150 ° C, and it is particularly preferable to be in the range of 60 ° C to 130 ° C. The heating time is preferably 10 seconds to 60 minutes, particularly preferably 60 seconds to 30 minutes.

  When the base-reactive resin composition of the present invention is used as a photosensitive resin composition, a sensitizer can be added to expand the photosensitive wavelength region and increase the sensitivity. The sensitizer that can be used is not particularly limited. For example, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene. , Pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro -4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2 tert-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5 , 7-dimethoxycarbonylcoumarin) or coronene. You may make it use these sensitizers individually by 1 type or in combination of 2 or more types.

  When the base-reactive resin composition of the present invention is used as a photosensitive resin composition, the addition amount of the sensitizer is appropriately determined depending on the photobase generator and base-reactive compound used, the sensitivity required, and the like. However, it is preferably in the range of 1 to 30% by mass with respect to the entire base-reactive resin composition. If the sensitizer is less than 1% by mass, the sensitivity may not be sufficiently increased. On the other hand, if the sensitizer exceeds 30% by mass, the sensitivity may be excessive. The addition amount of the sensitizer is particularly preferably in the range of 5 to 20% by mass with respect to the whole base-reactive resin composition.

  When applying the base-reactive resin composition of the present invention to a predetermined base material, a solvent may be appropriately contained as necessary. By including a solvent in the base-reactive resin composition, the coating ability can be increased and workability is improved. The solvent is not particularly limited. For example, aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, and diethylbenzene; cyclohexane, methylcyclohexane, ethylcyclohexane, cyclohexene, dipentene, n-pentane, Isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane, p-menthane, o-menthane, m-menthane, etc. Saturated or unsaturated hydrocarbon compounds; diethyl ether, di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethylpropyl ether, diphenyl ether, diethylene glyco Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene Glycol dipropyl ether, ethylene glycol methyl ethyl ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoether Ethers such as ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, cycloheptanone; ethyl acetate, methyl acetate, butyl acetate, acetic acid Examples include propyl, cyclohexyl acetate, methyl cellosolve, ethyl acetate cellosolve, butyl acetate cellosolve, esters such as ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, and butyl stearate. These solvents may be used alone or in combination of two or more.

  In the base-reactive resin composition of the present invention, the content of the solvent is uniform when, for example, the base-reactive resin composition is applied on a predetermined substrate to form a layer of the base-reactive resin composition. What is necessary is just to select suitably so that it may be applied to.

  In addition, you may make it add an additive suitably to the base reactive resin composition of this invention in the range which does not inhibit the objective and effect of this invention. Examples of additives that can be used include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, Examples thereof include a plasticizer, a plastic accelerator, an anti-sagging agent, and a curing accelerator. One of these may be used alone, or two or more may be used in combination.

  The base-reactive resin composition of the present invention described above is a base generated from a base proliferating agent by containing the base proliferating agent of the present invention or the base proliferating agent of the present invention, a base generator and a base-reactive compound. -Reactive resin composition in which the reaction between the compound and a base-reactive compound such as an epoxy-based compound proceeds in a chain, has excellent curing speed and reaction efficiency, is quickly cured, and is sufficiently cured It becomes. The base-reactive resin composition of the present invention exhibiting such effects can be suitably used for, for example, a highly sensitive photocuring material, resist material (pattern forming material), and the like.

  The molded body applied as a photo-curing material can be used as a member in a field where characteristics such as heat resistance, dimensional stability, and insulation are effective, for example, paint or printing ink, color filter, film for flexible display, semiconductor, etc. Widely used as equipment, electronic parts, interlayer insulation films, wiring coating films, optical circuits, optical circuit parts, antireflection films, holograms, optical members or building materials, printed materials, color filters, films for flexible displays, A semiconductor device, an electronic component, an interlayer insulating film, a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, a building member, or the like is provided. In addition, the formed pattern has heat resistance and insulation, for example, color filters, flexible display films, electronic components, semiconductor devices, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, reflective It can be advantageously used as a protective film, other optical member or electronic member.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example etc., this invention is not limited to this Example at all. In formulas (H-1) to (H-6), formula (H-7), formula (Aa) to formula (Ae), and formula (Af), the -Et group is It shows a -CH ₂ CH ₃ group.

[Production Example 1]
Production of intermediate (1):
100 mL of dehydrated tetrahydrofuran was placed in a 500 mL three-necked flask, and 3.2 g (50 × 10 ⁻³ mol) of lithium aluminum hydride was slowly added thereto while stirring. While this solution was stirred in an ice bath, a solution prepared by dissolving 11.2 g (168 × 10 ⁻³ mol) of aluminum chloride in 100 mL of dehydrated tetrahydrofuran was slowly added dropwise to this solution. Thereafter, 13.0 g (48 × 10 ⁻³ mol) of 2,4-diethylthioxanthone represented by the following formula (H-1) was added to the reaction system little by little and stirred at reflux for 30 minutes. After completion of the reaction, ethyl acetate was added to the flask, and 5% by mass HClaq was slowly injected to dissolve the residue, followed by extraction with dichloromethane. The organic layer was washed with NaHCO ₃ aq and NaClaq three times each and finally dried with magnesium sulfate. Next, the solvent was distilled off by an evaporator, and the obtained residue was dried under reduced pressure to obtain a yellow viscous liquid of a compound represented by the following formula (H-2) in a yield of 11.0 g (yield 92%). It was.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.21 (t, 3H, J = 7.4 Hz, CH ₃ ), 1.26 (t, 3H, J = 7.5 Hz, CH ₃ ) , 2.60 (q, 2H, J = 7.4 Hz, CH ₂ ), 2.80 (q, 2H, J = 7.5 Hz, CH ₂ ), 3.81 (s, 2H, CH ₂ ), 6 .9-7.4 (m, 6H, Ar—H), ¹³ C-NMR (75 MHz, CDCl ₃ ): d (ppm) 14.7, 15.7 (CH ₃ ), 27.4, 28.4 39.9 (CH ₂ ), 125.2, 126.0, 126.3, 126.5, 127.0, 127.6, 129.7, 134.3, 136.4, 137.0, 141 .1,142.7 (Ar)

[Production Example 2]
Intermediate production (2):
In a 500 mL eggplant flask, 11.0 g (44 × 10 ⁻³ mol) of an intermediate represented by the formula (H-2) was added and dissolved in 150 mL of dichloromethane. To this solution, 8.6 g (50.0 × 10 ⁻³ mol) of m-chloroperbenzoic acid was added and stirred at room temperature for 12 hours. After completion of the reaction, the reaction solution was washed three times each with saturated aqueous sodium hydrogen carbonate and saturated brine, and finally the organic layer was dried over magnesium sulfate. Next, the solvent was distilled off by an evaporator, and the obtained residue was dried under reduced pressure to obtain an intermediate yellow solid represented by the following formula (H-3) in a yield of 11.0 g (yield 95%). It was.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.23 (t, 3H, J = 7.6 Hz, CH ₃ ), 1.34 (t, 3H, J = 7.6 Hz, CH ₃ ) , 2.65 (q, 2H, J = 7.6 Hz, CH ₂ ), 3.12 (q, 2H, J = 7.6 Hz, CH ₂ ), 3.93 (d, 1H, J = 17.2 Hz) , CH ₂ ), 4.87 (d, 1H, J = 17.2 Hz, CH ₂ ), 7.0-7.8 (m, 6H, Ar—H), ¹³ C-NMR (75 MHz, CDCl ₃ ). : Δ (ppm) 15.3, 17.0 (CH ₃ ), 26.3, 28.7, 35.8 (CH ₂ ), 126.4, 126.8, 127.4, 127.5, 129 1, 129.3, 131.5, 139.4, 148.2 (Ar)

[Production Example 3]
Production of intermediate (3):
A 100 mL two-necked eggplant flask was charged with 1.0 g (3.7 × 10 ⁻³ mol) of an intermediate represented by the formula (H-3) and 0.47 g (15 × 10 ⁻³ mol) of p-formaldehyde and nitrogen. Under an atmosphere, 30 mL of dehydrated tetrahydrofuran was added and placed in an ice bath. A 1 mol / L potassium hydroxide methanol solution was slowly added dropwise thereto, and the mixture was refluxed and stirred for 20 minutes after the completion of the addition. After completion of the reaction, the reaction solution was extracted with dichloromethane, and the organic layer was washed with 5 mass% HClaq, NaHSO ₃ aq, and NaClaq three times each, and finally the organic layer was dried over magnesium sulfate. Subsequently, the solvent is distilled off by an evaporator, and the resulting residue is purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1), whereby the compound represented by the following formula (H-4) Was obtained in a yield of 0.75 g (yield 67%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.26 (t, 3H, J = 7.6 Hz, CH ₃ ), 1.37 (t, 3H, J = 7.5 Hz, CH ₃ ) , 2.69 (q, 2H, J = 7.6 Hz, CH ₂ ), 3.16 (m, 2H, CH ₂ ), 3.90 (t, 1H, J = 6.0 Hz, CH), 4. 18 (dd, 1H, J = 6.0, 6.0 Hz, CH ₂ ), 4.38 (t, 1H, J = 6.0 Hz, OH), 7.1-7.9 (m, 6H, Ar -H), ¹³ C-NMR (75 MHz, CDCl ₃ ): δ (ppm) 15.1, 16.8 (CH ₃ ), 26.3, 28.7, 51.7, 69.1 (CH ₂ ) , 127.8, 128.1, 128.2, 130.5, 130.7, 132.3, 134.3, 138.3, 140.6, 140. 8, 145.7, 148.9 (Ar)

[Production Example 4]
Production of intermediate (4):
In a 100 mL eggplant flask, 2.4 g (7.9 × 10 ⁻³ mol) of an intermediate represented by the formula (H-4) was added and dissolved in 15 mL of dichloromethane. M-Chloroperbenzoic acid 1.5g (8.7 * 10 < ^-3 > mol) was added here, and it stirred at room temperature for 12 hours. After completion of the reaction, saturated aqueous sodium hydrogen carbonate and saturated brine were added little by little to the reaction solution, extracted with dichloromethane, and finally the organic layer was dried over magnesium sulfate. Next, the solvent was removed by an evaporator, and the obtained residue was dried under reduced pressure to obtain an intermediate yellow solid represented by the following formula (H-5) in a yield of 2.3 g (yield 95%). It was.

¹ H-NMR (400 MHz, d-DMSO): δ (ppm) 1.20 (t, 3H, J = 7.6 Hz, CH ₃ ), 1.30 (t, 3H, J = 7.6 Hz, CH ₃ ), 2.69 (q, 2H, J = 7.6 Hz, CH ₂ ), 3.08-3.20 (m, 2H, CH ₂ ), 3.72 (t, 1H, J = 6.0 Hz, _{CH), 4.27 (dd, 1H} , J = 6.0,6.0Hz, CH 2), 5.20 (t, 1H, J = 6.0Hz, OH), 7.25-7.8 ( m, 6H, Ar-H)

[Production Example 5]
Production of intermediate (5):
Into a 200 mL eggplant flask, 2.0 g (6.3 × 10 ⁻³ mmol) of an intermediate represented by the formula (H-5) and 0.51 g (6.4 × 10 ⁻³ mmol) of pyridine are added, and 15 mL of dehydrated tetrahydrofuran is added. Was added. While stirring, 1.7 g (6.4 × 10 ⁻³ mmol) of chloroformate-4-nitrophenyl (NP-Cl) dissolved in 15 mL of dehydrated tetrahydrofuran was slowly added dropwise and stirred at room temperature for 6 hours. After completion of the reaction, the solvent of the reaction solution was distilled off, and chloroform was added for extraction. The organic layer was washed with 5% by mass HClaq, NaHCO ₃ aq, and NaClaq three times each, and finally the organic layer was dried over magnesium sulfate. I let you. Next, after the solvent was distilled off, the resulting residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1), whereby an intermediate yellow color represented by the following formula (H-6) was obtained. The solid was obtained in a yield of 2.4 g (79% yield).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.26 (t, 3H, J = 7.4 Hz, CH ₃ ), 1.39 (t, 3H, J = 7.4 Hz, CH ₃ ) _{, 2.70 (q, 2H, J} = 7.4Hz, CH 2), 3.2 (m, 2H, CH 2), 4.4-4.7 (m, 3H, CH, -O-CH 2 ), 7.1-7.5 (m, 7H, Ar-H), 7.5-8.1 (m, 16H, Ar-H)

[Example 1]
Production of base proliferating agent (1):
50mL egg plant flask was charged with Formula intermediates represented by (H-4) 0.22g (0.74 × 10 -3 mol) and pyridine ^{0.05g (0.74 × 10 -3 mol)} , anhydrous tetrahydrofuran 10ml Was added. While stirring, 0.15 g (0.74 × 10 ⁻³ mol) of chloroformate-4-nitrophenyl (NP-Cl) dissolved in 15 mL of dehydrated tetrahydrofuran was slowly added dropwise and stirred at room temperature for 4 hours. After completion of the reaction, a solution prepared by dissolving 0.06 g (0.70 × 10 ⁻³ mol) of piperidine in 1 mL of dehydrated tetrahydrofuran was added dropwise to this solution and stirred at room temperature for 3 hours. After completion of the reaction, dichloromethane was added to the reaction solution for extraction, and the organic layer was washed with HClaq, NaHSO ₃ aq and NaClaq three times each, and finally the organic layer was dried over magnesium sulfate. Subsequently, the solvent is distilled off by an evaporator, and the resulting residue is purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1), whereby a base represented by the following formula (Aa) is obtained. A white solid of the proliferating agent was obtained in a yield of 0.22 g (yield 72%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.24 (t, 3H, J = 7.5 Hz, CH ₃ ), 1.36 (t, 3H, J = 7.4 Hz, CH ₃ ) _{, 1.4-1.6 (m, 6H, CH} 2), 2.66 (q, 2H, J = 7.5Hz, CH 2), 3.0-3.5 (m, 6H, N-CH ₂ , CH ₂ ), 4.5-4.7 (m, 3H, CH, —O—CH ₂ ), 7.1-7.9 (m, 6H, Ar—H)

[Example 2]
Production of base proliferating agent (2):
In a 50 mL eggplant flask, 0.50 g (1.0 × 10 ⁻³ mol) of the intermediate represented by the formula (H-6) was dissolved in 20 mL of dehydrated tetrahydrofuran. To this solution, a solution prepared by dissolving 0.09 g (1.0 × 10 ⁻³ mol) of piperidine in 1 mL of dehydrated tetrahydrofuran was added dropwise and stirred at room temperature for 12 hours. After completion of the reaction, ethyl acetate was added to the reaction solution for extraction, the organic layer was washed with NaHSO ₃ aq and NaClaq three times each, and finally the organic layer was dried over magnesium sulfate. Next, the solvent was distilled off by an evaporator, and the resulting residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 4: 1), whereby a base represented by the following formula (Ab) A light yellow solid of the proliferating agent was obtained in a yield of 0.31 g (yield 70%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.25 (t, 3H, J = 7.5 Hz, CH ₃ ), 1.38 (t, 3H, J = 7.4 Hz, CH ₃ ) _{, 1.4-1.6 (m, 6H, CH} 2), 2.66 (q, 2H, J = 7.5, Hz, CH 2), 3.2-3.5 (m, 6H, N _{-CH 2, CH 2), 4.5-4.7} (m, 3H, CH, -O-CH 2), 7.1-8.1 (m, 6H, Ar-H)

[Example 3]
Production of base proliferating agent (3):
In a 200 mL eggplant flask, 0.50 g (1.7 × 10 ⁻³ mol) of the intermediate represented by the formula (H-4) and 0.12 g (0.2 × 10 ⁻³ mol) of dibutyltin dilaurate (IV) And 30 mL of benzene and 20 mL of acetonitrile were added and dissolved. While stirring, 0.14 g (0.83 × 10 ⁻³ mol) of hexamethylene diisocyanate dissolved in 1 mL of benzene was added dropwise and stirred for 13 hours. After completion of the reaction, the solvent of the reaction solution was distilled off, and the obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 3: 1), and represented by the following formula (Ac). A white solid of the base proliferating agent was obtained in a yield of 0.35 g (54% yield).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.2-1.4 (m, 20 H, CH ₂ , CH ₃ ), 2.67 (q, 4 H, J = 7.5 Hz, —CH _{2 -CH 3), 2.7-3.2 (m} , 8H, N-CH 2, -CH 2 -CH 3), 4.5-4.7 (m, 6H, CH, -O-CH 2 ), 5.04 (br, 2H, NH), 7.1-7.9 (m, 12H, Ar—H), ¹³ C-NMR (125 MHz, CDCl ₃ ): δ (ppm) 15.2, 16 7, 26.3, 28.7, 29.8, 128.0, 128.1, 128.2, 128.5, 13.9, 131.8, 140.0, 140.1, 156.4

[Example 4]
Production of base proliferating agent (4):
In a 300 mL eggplant flask, 1.0 g (3.2 × 10 ⁻³ mol) of an intermediate represented by the formula (H-5) and 0.18 g (0.3 × 10 ⁻³ mol) of dibutyltin dilaurate (IV) And 50 mL of benzene was added and dissolved. While stirring, 0.50 g (3.0 × 10 ⁻³ mol) of hexamethylene diisocyanate dissolved in 1 mL of benzene was added dropwise and stirred for 13 hours. After completion of the reaction, the solvent of the reaction solution was distilled off, and the obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1), and represented by the following formula (Ad). A white solid of the base proliferating agent was obtained in a yield of 0.50 g (yield 20%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.2-1.6 (m, 20H, CH ₂ , CH ₃ ), 2.66 (q, 4H, J = 7.8 Hz, CH ₂ ), 3.15 (dt, 2H, J = 6.0, 6.5 Hz, N—CH ₂ ), 3.26 (q, 4H, J = 7.3 Hz, CH ₂ ), 4.3-4. 5 (m, 6H, CH, —O—CH ₂ ), 4.93 (t, 2H, J = 6.0 Hz, NH), 7.1-8.1 (m, 12H, Ar—H), ¹³ C-NMR (125 MHz, CDCl ₃ ): δ (ppm) 15.0, 15.8 (CH ₃ ), 26.2, 26.6, 28.5, 29.7, 40.7, 46.0, 68.8 _(CH 2), 123.9,127.5,128.1,129.4,130.1,132.1,133.1,136.6,137. 8, 143.9, 148.6 (Ar), 156.1 (C = O)

[Example 5]
Production of base proliferating agent (5):
In a 300 mL eggplant flask, 2.5 g (7.9 × 10 ⁻³ mol) of the intermediate represented by the formula (H-5) and 0.42 g (0.7 × 10 ⁻³ mol) of dibutyltin dilaurate (IV) And 30 mL of benzene was added and dissolved. While stirring, 0.89 g (4.0 × 10 ⁻³ mol) of isophorone diisocyanate (isophorone diisocyanate) dissolved in 1 mL of benzene was added dropwise and stirred at 70 ° C. for 13 hours. After completion of the reaction, the solvent of the reaction solution was distilled off, and the resulting residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 3: 1), and represented by the following formula (Ae). A white solid of the obtained base proliferating agent was obtained in a yield of 1.40 g (yield 40%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 0.8-1.8 (m, 27H, CH ₂ , CH ₃ ), 2.6 (m, 4H, CH ₂ ), 2.9 ( _{m, 2H, N-CH 2} ), 3.2 (m, 4H, CH 2), 3.7-3.8 (m, 3H, N-CH, NH 2), 4.4-4.7 ( _{m, 6H, CH, -O-} CH 2), 5.0 (br, 1H, NH), 7.1-8.1 (m, 12H, Ar-H)

[Test Example 1]
Confirmation of degradation behavior of base proliferator in solution (1):
As shown in the above-described scheme, the base proliferating agent undergoes a decomposition reaction by adding a base, and an olefin is generated together with the base and carbon dioxide (CO ₂ ). Using the following method, the degradation behavior of the base proliferating agent was confirmed.

In the NMR sample tube, the base proliferating agent 70 × 10 ⁻³ mol / L obtained in Example 2, piperidine 13 × 10 ⁻³ mol / L as a base, dioxane-d ₈ as a solvent, and mesitylene 13 as an internal standard solution. After putting * 10 < ^-3 > mol / L and sealing, it heated at 100 degreeC for the predetermined time. Then, by analyzing the olefin peak to be generated by ¹ H-NMR, the decomposition behavior (generation of olefin) of the base proliferating agent was confirmed, and compared with the case where no base was added. FIG. 11 shows the relationship between the heating time, the conversion rate of the base proliferating agent, and the olefin production rate. The olefin production rate was calculated from a ¹ H-NMR spectrum. In FIG. 11, the solid line represents the conversion rate of the base proliferating agent, and the broken line represents the olefin production rate.

  The same operation was also performed for the base proliferating agent obtained in Example 1 (only the production rate of olefin was confirmed). FIG. 12 shows the relationship between the heating time and the olefin production rate.

  As shown in FIG. 11, for the base proliferating agent of Example 2, a nonlinear reaction curve peculiar to the proliferative reaction is obtained including a system to which a base (piperidine) common to the base constituting the base proliferating agent is added. It was confirmed that a base growth reaction was produced and olefin was produced. In the system to which the base was added, the base proliferating agent decomposed faster and the olefin was also generated faster.

On the other hand, as shown in FIG. 12, with respect to the base proliferating agent of Example 1, the decomposition behavior of the base proliferating agent in the solution was not confirmed, including those to which a base was added. Therefore, the solvent as methanol-dioxane -d ₈ (methanol -d _4), the test was carried out again.

[Test Example 2]
Confirmation of degradation behavior of base proliferator in solution (2)
In the NMR sample tube, the base proliferating agent 70 × 10 ⁻³ mol / L obtained in Example 1, piperidine 13 × 10 ⁻³ mol / L as a base, deuterated methanol (methanol-d ₄ ) as a solvent, internal standard Mesitylene 13 × 10 ⁻³ mol / L was added as a liquid, sealed, and heated at 100 ° C. for a predetermined time. Then, by analyzing the olefin peak to be generated by ¹ H-NMR, the decomposition behavior (generation of olefin) of the base proliferating agent was confirmed, and compared with the case where no base was added. FIG. 13 shows the relationship between the heating time, the conversion rate of the base proliferating agent, and the olefin production rate. The olefin production rate was calculated from a ¹ H-NMR spectrum. In FIG. 13, the solid line represents the conversion rate of the base proliferating agent, and the broken line represents the olefin production rate.

As shown in FIG. 13, when the solvent is deuterated methanol (methanol-d ₄ ), the system to which the base (piperidine) common to the base constituting the base proliferating agent is added is a nonlinear reaction peculiar to the growth reaction. The above curve was obtained, and it was confirmed that the olefin was decomposed more efficiently than the system in which no base was added.

[Test Example 3]
Confirmation of solubility in organic solvents:
The solubility of the base proliferating agent obtained in Example 3 and Example 4 in an organic solvent was confirmed. The results are shown in FIG. The solubility of the base proliferating agent was confirmed by calculating the amount of solvent dissolved in 0.01 g of the base proliferating agent. In FIG. 14, the result of the dissolution amount is “++” when the solvent amount is less than 1 mL (when the solvent is dissolved without requiring 1 mL), “+” when 2 to 5 mL, and “−” when 6 to 9 mL. "When exceeding 10 mL, indicated as"-". For comparison, the compounds represented by the following formulas (S-1) and (S-2) (in order, Comparative Example 1 and Comparative Example 2) were also evaluated.

Furthermore, Example 3, Example 4, Comparative Example 1 and Comparative Example 2, the thermal decomposition temperature (T d ^₅₎ were measured and compared. Note that the thermal decomposition temperature ^{_{(T d 5), TG-}} DTA - was determined by (differential thermal Thermogravimetry).

  FIG. 14 is a diagram showing the solubility in an organic solvent such as a base proliferating agent. As shown in FIG. 14, the base proliferating agents of Example 3 and Example 4 showed better solubility in organic solvents, and the base proliferating agent of Example 3 was better than the base proliferating agent of Comparative Example 1 and It was confirmed that the base proliferating agent of Example 4 exhibited superior solubility than the base proliferating agent of Comparative Example 2, respectively.

Further, as shown in FIG. 14, the thermal decomposition temperature (T _d ⁵ ) is higher than the thermal decomposition temperature of the base proliferating agent of Comparative Example 1, and the excellent thermal resistance. Indicated. Similarly, the thermal decomposition temperature of the base proliferating agent of Example 4 was higher than that of Comparative Example 2 and showed excellent heat resistance.

[Examples 6 to 8]
Production of base-reactive resin composition (photosensitive resin composition) (1):
The sorbitol polyglycidyl ether (Denacol (registered trademark) EX-622 / manufactured by Nagase ChemteX Corp.) 0.1 g which is an epoxy compound represented by the formula (No. 4-13) is represented by the formula (E- 2) The photobase generator represented by 2) was obtained in Example 5, 0.031 g (31 parts by mass with respect to 100 parts by mass of the epoxy compound) (amine functional group ratio: 10 mol% (vs. epoxy group)). The base reactive resin composition (photosensitive resin composition) of the present invention was obtained by containing the base proliferating agent in the following content.

(Content of base proliferating agent)
Content (g) Mass parts Amine functional group ratio (Note)
Example 6 0.15 150 40 mol%
Example 7 0.23 230 60 mol%
Example 8 0.31 310 80 mol%
(Note) Epoxy group (mol%)

[Reference Example 1]
Production of resin composition (1)
In Example 6, a resin composition was obtained using the same method as in Example 6 except that the base proliferating agent obtained in Example 5 was not added.

[Test Example 4]
Curing confirmation (1) (confirmation of addition amount dependency):
The base-reactive resin composition obtained in Example 6 was dissolved in 0.1 g of chloroform (CHCl ₃ ) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 1 minute and prebaked to prepare a coating film having a thickness of 5.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 1000, 5000 and 10000 mJ / cm ² , and the hardness of the coating film after heating at 80 ° C. for 40 minutes as baked to JIS K5600-5-4. In accordance with the pencil hardness measurement. And the same operation was implemented with respect to the base reactive resin composition etc. of Example 7, Example 8, and Reference Example 1, etc., and compared and evaluated. FIG. 15 shows the relationship between the exposure amount and the pencil hardness.

As shown in FIG. 15, the curing progressed as the content of the base proliferating agent was increased, and when the exposure amount was 10000 mJ / cm ² , a hardness of 3H in Example 7 and 4H in Example 8 was obtained. .

[Test Example 5]
Curing confirmation (2) (confirmation of heating time dependency):
The base-reactive resin composition obtained in Example 7 was dissolved in 0.1 g of chloroform (CHCl ₃ ) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 1 minute and prebaked to prepare a coating film having a thickness of 5.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 1000, 5000 and 10000 mJ / cm ² , and the hardness of the coating film after heating at 80 ° C. for 10 minutes as a post bake was JIS K5600-5-4. In accordance with the pencil hardness measurement. The same operation was performed with post-baking heating times of 20 minutes, 40 minutes, and 60 minutes, and compared and evaluated. FIG. 16 shows the relationship between the exposure amount and the pencil hardness.

As shown in FIG. 16, the curing progresses as the heating time is increased. When the exposure amount is 10,000 mJ / cm ² , the heating time is 20 minutes, 40 minutes, 3H, 60 minutes. A hardness of 4H was obtained.

[Test Example 6]
Curing confirmation (3) (confirmation of heating temperature dependence):
The base-reactive resin composition obtained in Example 7 was dissolved in 0.1 g of chloroform (CHCl ₃ ) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 1 minute and prebaked to prepare a coating film having a thickness of 5.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was set to 0 (blank), 1000, 5000 and 10000 mJ / cm ² , and the hardness of the coating film after heating at 60 ° C. for 40 minutes as post-baking was JIS K5600-5-4 In accordance with the pencil hardness measurement. And the same operation was implemented by making the post-baking heating temperature 80 degreeC and 100 degreeC, and compared and evaluated. The relationship between the exposure amount and the pencil hardness is shown in FIG.

As shown in FIG. 17, curing progresses as the heating temperature is increased. When the exposure amount is 10,000 mJ / cm ² , the hardness is 3H when the heating temperature is 80 ° C., and the hardness is 4H when the heating temperature is 100 ° C. was gotten.

[Production Example 6]
Production of intermediate (6):
Placed in 200mL4 neck flask equation (H-5) 10.0g (31.6 × 10 -3 mmol) and sodium carbonate ^{3.35g (31.6 × 10 -3 mmol)} , was added dehydrated tetrahydrofuran 60 mL. While stirring, 6.19 g (20.8 × 10 ⁻³ mmol) of triphosgene dissolved in 60 mL of dehydrated tetrahydrofuran was slowly added dropwise and stirred at room temperature for 48 hours. After completion of the reaction, the resulting salt was removed by filtration and the solvent was distilled off. Diisopropyl ether was added to the resulting crude product for washing, followed by drying under reduced pressure to obtain an intermediate white solid represented by the following formula (H-7) in a yield of 5.9 g (yield 49%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 1.27 (t, 3H, J = 7.5 Hz), 1.38 (t, 3H, J = 7.5 Hz), 2.70 (q , 2H, J = 7.5 Hz), 3.25 (q, 2H, J = 7.5 Hz), 4.46 (t, 1H, J = 8.3 Hz), 4.72 (d, 2H, J = 8.3 Hz), 7.12 (s, 1H), 7.17 (s, 1H), 7.46 (d, 1H, J = 9.0 Hz), 7.54-7.59 (m, 2H) , 8.15 (d, 1H, J = 9.0 Hz)

[Example 9]
Production of base proliferating agent (6):
In a 200 mL four-necked flask, put 5.90 g (15.57 × 10 ⁻³ mol) of an intermediate represented by the formula (H-7) and 4.32 g (51.38 × 10 ⁻³ mol) of sodium hydrogen carbonate, 5 ml of water and 10 ml of dimethoxyethane were added. While stirring, 0.54 g (5.19 × 10 ⁻³ mol) of diethylenetriamine was added dropwise, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 10 mL of ethyl acetate was added, the organic layer was washed with HClaq, then washed with water three times, and the organic layer was dried over magnesium sulfate. Next, the solvent was distilled off by an evaporator, 20 mL of isopropyl alcohol and 20 mL of diisopropyl ether were added to the obtained residue, washed, drained, and dried under reduced pressure, whereby base growth represented by the following formula (Af) was performed. A white powder of the agent was obtained in a yield of 4.18 g (71% yield).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 1.12 to 1.26 (brm, 9H), 1.34 to 1.38 (brm, 9H), 2.62 (brm, 6H), 3.08-3.31 (brm, 14H), 4.41-4.47 (brm, 9H), 5.09 (brs, 1H), 5.40 (brs, 1H), 7.06-7. 14 (brm, 6H), 7.37-7.56 (brm, 9H), 8.05-8.15 (brm, 3H)

[Example 10]
Production of base-reactive resin composition (photosensitive resin composition) (2):
The bisphenol diglycidyl ether oligomer (jER828 (registered trademark) / manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), which is an epoxy compound represented by the formula (No. 4-11), is used with respect to 0.1 g. -4) 0.017 g (17 parts by mass with respect to 100 parts by mass of the epoxy compound) of the photobase generator, and 0.16 g (amine functional group ratio) of the base proliferating agent obtained in Example 9 The base-reactive resin composition of the present invention was obtained by containing 80 mol% (vs. epoxy group).

[Reference Example 2]
Production of resin composition (2)
In Example 10, a resin composition was obtained using the same method as in Example 10 except that the base proliferating agent obtained in Example 9 was not added.

[Test Example 7]
Curing confirmation (4):
The base-reactive resin composition obtained in Example 10 was dissolved in 0.1 g of chloroform (CHCl ₃ ) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 1 minute and prebaked to prepare a coating film having a thickness of 5.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 1000, 5000 and 10000 mJ / cm ² , and the hardness of the coating film after heating at 100 ° C. for 40 minutes as post-baking was JIS K5600-5-4. In accordance with the pencil hardness measurement. And the same operation was implemented with respect to the resin composition of the reference example 2, and it compared and evaluated. FIG. 18 shows the relationship between the exposure amount and the pencil hardness.

As shown in FIG. 18, curing does not proceed in a system that does not contain any base proliferating agent (the resin composition of Reference Example 2), whereas the base-reactive resin composition of Example 10 increases the exposure amount. as the curing proceeds, in case of the exposure amount 1000 mJ / cm ² 1B, in case of a 5000 mJ / cm ² HB, the hardness of 2H was obtained in case of the 10000 mJ / cm ^2.

  The present invention can be advantageously used as a material for providing a highly sensitive photocuring material, resist material (pattern forming material), and the like.

Claims (8)

A base proliferating agent comprising a compound represented by the following formula (A).

(In the formula _{(A), R 1, R} 2 and _{R 3} are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, aryl having 6 to 14 carbon atoms Or an arylalkyl group having 7 to 15 carbon atoms, Q is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 7 carbon atoms. To 15 arylalkyl groups, groups represented by the following formula (B ₁ ) or groups represented by the following formula (B ₂ ), wherein R ₃ and Q are bonded to each other to contain 2 to 10 carbon atoms. Nitrogen saturated aliphatic ring; the number of carbon atoms in which the hydrogen atom bonded to the carbon atom constituting the saturated aliphatic ring is substituted with at least one of an alkyl group, a hydroxy group, a mercapto group, a cyano group, a nitro group or a halogen atom 2-10 nitrogen-containing saturated fat A ring; a nitrogen-containing saturated aliphatic ring having 3 to 10 carbon atoms having a heteroatom other than a nitrogen atom in the chain; a heteroatom other than a nitrogen atom in the chain, and bonded to a carbon atom constituting the saturated aliphatic ring A nitrogen-containing saturated aliphatic ring having 3 to 10 carbon atoms in which a hydrogen atom to be substituted is substituted with at least one of an alkyl group, a hydroxy group, a mercapto group, a cyano group, a nitro group or a halogen atom; A nitrogen-containing unsaturated aliphatic ring or aromatic ring; or a hydrogen atom bonded to a carbon atom constituting the unsaturated aliphatic ring or aromatic ring is an alkyl group, a hydroxy group, a mercapto group, a cyano group, a nitro group or a halogen atom. A nitrogen-containing unsaturated aliphatic ring or aromatic ring having 3 to 10 carbon atoms substituted with at least one may be formed, X ₁ represents SO or SO ₂ , and Y ₁ , Y ₂ , Y ₃ , Y ₄ , Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl having 6 to 14 carbon atoms. Group, an arylalkyl group having 7 to 15 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, a halogen atom or a nitro group, provided that Y ₁ , Y ₂ , Y ₃ , Y ₄ , Z ₁ , Z ₂ , Z ₍ Except when ₃ and Z ₄ are all hydrogen atoms)

(In formula (B ₁ ), D ₁ represents the following formula (V ₁ ) or the following formula (V ₂ ), and D ₂ represents the following formula (V ₁ ) or the following formula (V ₃ ): R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. N ₁ represents an integer of 0 to 20, X ₂ represents SO or SO ₂ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Z ₅ , Z ₆ , Z ₇ and Z ₈ are each independent. And a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, and an alkyl group having 1 to 12 carbon atoms. A haloalkyl group, a halogen atom or a nitro group.)

(In the formula (B ₂ ), D ₁ represents the following formula (V ₁ ) or the following formula (V ₂ ), D ₂ represents the following formula (V ₁ ) or the following formula (V ₃ ), and D ₃ represents Formula (V ₁ ) or the following formula (V ₄ ) is shown: R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, .n _{1, n 2} and _{n 3} showing the arylalkyl group aryl or 7 to 15 carbon atoms having 6 to 14 carbon atoms are each independently 0 to 20 integer W represents 0 or 1, X ₂ and X ₃ each independently represent SO or SO ₂ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ and Z ₁₂ are respectively Independently, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, and 1 to 1 carbon atom 12 haloalkyl groups, halogen atoms or nitro groups are shown.)

(In the formula (V ₂ ), m ₁ R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. And an arylalkyl group having 7 to 15 carbon atoms, and m ₁ represents an integer of ₁ to 7.)

(In the formula (V ₃ ), m ₂ R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. Or an arylalkyl group having 7 to 15 carbon atoms, and m ₂ represents an integer of 1 to 7.)

(In the formula (V ₄ ), m ₃ R ₁₁ and R ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 14 carbon atoms. Or an arylalkyl group having 7 to 15 carbon atoms, and m ₃ represents an integer of 1 to 7.) 2. The base proliferating agent according to claim 1, wherein the compound represented by the formula (A) is represented by the following formula (A ₁ ).

(In the formula (A ₁ ), R ₁ , R ₂ and R ₃ , X ₁ , Y ₁ , Y ₂ , Y ₃ and Y ₄ , and Z ₁ , Z ₂ , Z ₃ and Z ₄ are the same as those in the formula (A). R ₃ ′ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. R ₃ and R ₃ ′ are bonded to each other to form a nitrogen-containing saturated aliphatic ring having 2 to 10 carbon atoms; a hydrogen atom bonded to a carbon atom constituting the saturated aliphatic ring is an alkyl group, a hydroxy group, a mercapto A nitrogen-containing saturated aliphatic ring having 2 to 10 carbon atoms substituted with at least one of a group, a cyano group, a nitro group or a halogen atom; containing 3 to 10 carbon atoms having a hetero atom other than a nitrogen atom in the chain Nitrogen-saturated aliphatic ring; heteroatoms other than nitrogen atoms in the chain And a hydrogen atom bonded to a carbon atom constituting the saturated aliphatic ring is substituted with at least one of an alkyl group, a hydroxy group, a mercapto group, a cyano group, a nitro group or a halogen atom, and has 3 to 10 carbon atoms A nitrogen-containing saturated aliphatic ring; a nitrogen-containing unsaturated aliphatic ring or aromatic ring having 3 to 10 carbon atoms; or a hydrogen atom bonded to a carbon atom constituting the unsaturated aliphatic ring or aromatic ring is an alkyl group, hydroxy A nitrogen-containing unsaturated aliphatic ring having 3 to 10 carbon atoms or an aromatic ring substituted with at least one of a group, a mercapto group, a cyano group, a nitro group or a halogen atom may be formed.) The base growth agent according to claim 1, wherein the compound represented by the formula (A) is represented by the following formula (A ₂ ).

(In the formula (A ₂ ), D ₁ and D ₂ , R ₁ , R ₂ , R ₃ , R ₈ , R ₉ and R ₁₀ , n ₁ , X ₁ and X ₂ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ and Y ₈ , and Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ and Z ₈ are defined by the above formula (A) and the above formula ( Same as B ₁ ). 2. The base proliferating agent according to claim 1, wherein the compound represented by the formula (A) is represented by the following formula (A ₃ ).

(In the formula (A ₃ ), D ₁ , D ₂ and D ₃ , R ₁ , R ₂ , R ₃ , R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ and R ₁₅ , n ₁ , n ₂ and n ₃ , w, X ₁ , X ₂ and X ₃ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ , Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ and Z ₁₂ are the same as those in the above formula (A) and the above formula (B ₂ ). Is the same.)   A base-reactive resin composition comprising the base proliferating agent according to any one of claims 1 to 4 and a base-reactive compound.   A base-reactive resin composition comprising the base proliferating agent according to any one of claims 1 to 4, a base generator, and a base-reactive compound.   The base-reactive resin composition according to claim 6, wherein the base generator is a photobase generator.   8. The base reactive compound according to claim 5, wherein the base-reactive compound is at least one selected from the group consisting of an epoxy compound, a silicon compound, and an oxetane compound. Base-reactive resin composition.

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