JP2015044760A - Base proliferator and base-reactive resin composition containing the base proliferator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base proliferator usable for crosslinking reaction of base reactive compositions containing epoxy compounds and capable of generating, by the presence of a base, a new base, where the base proliferation reaction progresses efficiently without accompanying the generation of carbon dioxide gas when the base proliferation takes place, and also to provide a base-reactive resin composition containing the base proliferator.SOLUTION: A base proliferator according to the present invention is highly sensitive and decomposable by the action of a base in the presence of an epoxy compound to generate a base in a chain-reaction manner. In addition, the base proliferator proliferates the base by a cyclization reaction without accompanying the generation of carbon dioxide gas, when the base proliferation takes place. When thus incorporated with a base reactive compound for application as a base-reactive resin composition, the base proliferator causes no unevenness due to bubbles of carbon dioxide in a cured film, thereby being capable of providing cured films excellent in product characteristics and values.

Description

  The present invention relates to a base proliferating agent and a base-reactive resin composition containing the base proliferating agent. More specifically, the present invention relates to a base proliferating agent capable of decomposing by the action of a base and generating a new base, 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 or a photocuring material, and the acid generated from the acid generator is used as a catalyst or a polymerization initiator. Works. When forming a pattern using a photosensitive resin composition containing an acid generator or the like as a photoresist material, for example, the acid generator is irradiated with light to generate a strong acid that becomes a catalyst or the like, and the resin component is Chemically modify. A pattern is formed by a 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 material capable of forming a pattern having resistance to oxygen plasma etching is required. It has been demanded. 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, polymers, etc., and radical photopolymerization that polymerizes many vinyl monomers using radical species generated by the action of light as initiators. System 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. On the other hand, in the case of radical photopolymerization type materials, since the polymerization reaction is inhibited by the oxygen in the air and the curing reaction is suppressed, 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 means for solving the above problems, a method using a polymerization reaction or a 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 (base reactive resin composition) using a base generated by the above as a catalyst to a photoresist material, a photo-curing 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 or the like at a high temperature in order to further increase the curing rate. It was a fact.

  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, by adding a base proliferating agent that increases the base in a proliferative manner in this way, it is possible to improve the performance of the resin composition. For example, when the base grows in the surface layer of the membrane, In this case, it is possible to cure the deep part (shadow part) of the film and to cure the thick film. And the photosensitive resin composition containing the base proliferation agent which is a urethane type compound which raise | generates a base proliferation reaction is disclosed (for example, refer patent document 1 and patent document 2).

JP 2000-330270 A JP 2002-128750 A

However, the conventionally provided base proliferating agent has low sensitivity, and it has been difficult to efficiently advance the base proliferating reaction in the resin composition system. In addition, the conventional base proliferating agent was accompanied by the generation of carbon dioxide (CO ₂ ) as a decomposition product when proliferating the base. However, such carbon dioxide is used in the photosensitive resin composition (base reactive resin composition). ) Was formed as bubbles, causing unevenness in the cured film. Here, in the case where the photosensitive resin composition is formed, if bubbles remain in the cured film, the strength of the cured film is reduced, and when used as an adhesive, the adhesive strength is reduced. It was. Furthermore, when it is used for a sealing material or a coating material, there arises a problem that the barrier property against impurities in the air such as water is lowered, so that the use is limited, and the base is proliferated. At the same time, the development of a base proliferating agent that does not generate carbon dioxide has been desired.

  The present invention has been made in view of the above problems, and can be used for, for example, a crosslinking reaction of a base-reactive compound including an epoxy-based compound, can generate a new base by the presence of a base, and An object of the present invention is to provide a base proliferating agent that allows the base proliferating reaction to proceed efficiently and does not generate carbon dioxide during base proliferation, and a base-reactive resin composition containing the base proliferating agent.

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

（式（Ａ）中、Ｒ_１〜Ｒ_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は酸素原子または硫黄原子、Ｚは水素原子、Ｗはハメット置換基定数σが０以上の電子求引性の置換基またはフェニル基であり、ｉ及びｊはそれぞれ独立して１または２の整数で、ｉ＋ｊ＝３となる。）

(In formula (A), R _{1 to} R 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, an aryl group having 6 to 14 carbon atoms, or carbon. Q represents 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, and an alkyl group having 7 to 15 carbon atoms. An arylalkyl group, a group represented by the following formula (B ₁ ) or a group represented by the following formula (B ₂ ), wherein R ₃ and Q may be bonded to each other to form a ring structure. An oxygen atom or a sulfur atom, Z is a hydrogen atom, W is an electron-attracting substituent or phenyl group having a Hammett substituent constant σ of 0 or more, i and j are each independently an integer of 1 or 2, i + j = 3.)

（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_５〜Ｒ_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_１７及びＲ_１８、Ｄ_２が下記式（Ｖ_３）である場合のｍ_２個のＲ_１９、Ｒ_２０、並びにＲ_７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。Ｘ’は酸素原子または硫黄原子、Ｚ’は水素原子、Ｗ’はハメット置換基定数σが０以上の電子求引性の置換基またはフェニル基であり、ｇ及びｈはそれぞれ独立して１または２の整数で、ｇ＋ｈ＝３となり、ｎ_１は０〜２０の整数を示す。）

(In the 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 _{5 to} R ₈ each independently represents 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. When R ₃ and D ₁ of the formula (A) are the following formula (V ₂ ), m ₁ R ₁₇ and R ₁₈ and m ₂ when the D ₂ is the following formula (V ₃ ) ₁₉ , R ₂₀ , and R ₇ may form a ring structure by bonding at least two of these Rs together, X ′ is an oxygen atom or sulfur atom, Z ′ is a hydrogen atom, and W ′ is Hammett substituent constant σ is an electron-withdrawing substituent or phenyl group having 0 or more, and g and h are respectively In independently an integer of 1 or 2, g + h = 3 becomes, _{n 1} is an integer of 0 to 20.)

（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_５〜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_１７及びＲ_１８、Ｄ_２が下記式（Ｖ_３）である場合のｍ_２個のＲ_１９及びＲ_２０、Ｒ_７、Ｄ_３が下記式（Ｖ_４）である場合のｍ_３個のＲ_２１及びＲ_２２、並びにＲ_１１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。Ｘ’及びＸ”は酸素原子または硫黄原子、Ｚ’及びＺ”は水素原子、Ｗ’及びＷ”はハメット置換基定数σが０以上の電子求引性の置換基またはフェニル基であり、ｅ、ｆ、ｇ及びｈはそれぞれ独立して１または２の整数で、ｅ＋ｆ＝３、ｇ＋ｈ＝３となり、ｎ_１、ｎ_２、ｎ_３はそれぞれ独立して、０〜２０の整数を示す。）

(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 R _{5 to} R ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or the number of carbon atoms, each having the formula (V ₁ ) or the following formula (V ₄ ). 6 represents an aryl group having 6 to 14 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, m ₁ R ₁₇ and R ₁₈ when R ₃ and D _{1 in} the formula (A) are the following formula (V ₂ ). M ₂ R ₁₉ and R ₂₀ when D ₂ is the following formula (V ₃ ), R ₇ , m ₃ R ₂₁ and R ₂₂ when D ₃ is the following formula (V ₄ ), and R ₁₁ is good .X 'and be bonded to form a cyclic structure of at least two R are together of these R "Is an oxygen atom or sulfur atom, Z 'and Z" are hydrogen atoms, W' and W "are electron-withdrawing substituents or phenyl groups having a Hammett substituent constant σ of 0 or more, and e, f, g And h are each independently an integer of 1 or 2, and e + f = 3 and g + h = 3, and n ₁ , n ₂ , and n ₃ each independently represent an integer of 0 to 20.)

（式（Ｖ_２）中、ｍ_１個のＲ_１７及びＲ_１８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 ₁₇ and R ₁₈ 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_１９及びＲ_２０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 ₁₉ and R ₂₀ 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_２１及びＲ_２２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 ₂₁ and R ₂₂ 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 base proliferating agent according to the present invention is characterized in that, in the above-described present invention, the formula (A) is represented by the following formula (A ₁ ).

（式（Ａ_１）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｘ、Ｚ、Ｗ、ｉ及びｊ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 , R ₃ , R ₄ , X, Z, W, i and j are the same as those in the above formula (A), R ₃ ′ is a hydrogen atom, carbon number 1 Represents an alkyl group having 12 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, and R ₃ and R ₃ ′ are bonded to each other to form a ring structure May be formed.)

The base proliferating agent according to the present invention is characterized in that, in the above-described present invention, the formula (A) is represented by the following formula (A ₂ ).

（式（Ａ_２）中、Ｄ_１及びＤ_２、Ｒ_１〜Ｒ_８、ｎ_１、Ｘ及びＸ’、Ｚ及びＺ’、Ｗ及びＷ’、ｇ、ｈ、ｉ及びｊ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 to} R ₈ , n ₁ , X and X ′, Z and Z ′, W and W ′, g, h, i and j are the same as those in the formula (A ) And the same formula (B ₁ ).)

The base proliferating agent according to the present invention is characterized in that, in the above-described present invention, 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_１２、ｎ_１、ｎ_２及びｎ_３、Ｘ、Ｘ’及びＸ”、Ｚ、Ｚ’及びＺ”、Ｗ、Ｗ’及びＷ”、ｅ、ｆ、ｇ、ｈ、ｉ及びｊ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 to} R ₁₂ , n ₁ , n ₂ and n ₃ , X, X ′ and X ″, Z, Z ′ and Z ″, W, W ′ and W ″, e, f, g, h, i, and j are the same as those in the formula (A) and the formula (B ₂ ).

The base proliferating agent according to the present invention is characterized in that, in the above-described present invention, at least one of the CZ _i W _j , CZ ′ _g W ′ _h, and CZ ″ _e W ″ _f is represented by the following formula (C): And

（式（Ｃ）中、Ｙ_１及びＹ_２はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、シクロアルキル基またはニトロ基を示す。）

(In Formula (C), Y ₁ and Y ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a nitro group.)

  The base-reactive resin composition according to the present invention is characterized by containing at least one of the above-described base proliferating agents according to the present invention and a base-reactive compound including an epoxy compound.

  The base-reactive resin composition according to the present invention is characterized by containing at least one of the above-described base proliferating agents according to the present invention and a base-reactive compound including a base generator and an epoxy 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 an epoxy compound.

  The base proliferating agent according to the present invention has high sensitivity and can be decomposed by the action of a base in the presence of an epoxy compound to generate bases in a chain. In addition, the base is proliferated by a cyclization reaction during the base growth, and becomes a base proliferating agent that does not generate carbon dioxide.

  Further, the base-reactive compound according to the present invention contains a base proliferating agent of the present invention, or a base generated from the base proliferating agent in the presence of an epoxy compound by containing the base proliferating agent of the present invention and a base generator. -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. In addition, since the added base proliferating agent does not accompany the generation of carbon dioxide during growth of the base, it provides a cured film with high product characteristics and product value without causing unevenness due to carbon dioxide bubbles in the cured film. can do. 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.

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 illustrates a reaction scheme for 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). 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). For formula _{(A 2),} a diagram showing a synthesis scheme in the case where a base portion of 1,3-bis (4-piperidyl) propane. For formula (A _2), a diagram showing a synthesis scheme in the case where the base unit and 2-methyl-1,5-diamine. It is a diagram illustrating a synthetic scheme for formula (A _3). A diagram showing the results of assignment by ¹ H-NMR and the like. 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 a heating time and the production rate of an olefin. It is the figure which showed the relationship between the heating time, the production | generation rate of an olefin, and the reduction | decrease rate of a base growth agent and an epoxy-type compound (BGE). It is the figure which showed the relationship between the heating time, the production | generation rate of an olefin, and the reduction | decrease rate of a base growth agent and an epoxy-type compound (BGE). 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 heating time, heating temperature, and pencil hardness. It is the figure which showed the relationship between heating time, heating temperature, and pencil hardness. It is the figure which showed the relationship between heating time, heating temperature, 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. It is the figure which showed the relationship between exposure amount and pencil hardness. It is the figure which showed the measurement result by TG-DTA (differential heat-thermogravimetry). It is the figure which showed the measurement result by TG-DTA (differential heat-thermogravimetry).

  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_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は酸素原子または硫黄原子、Ｚは水素原子、Ｗはハメット置換基定数σが０以上の電子求引性の置換基またはフェニル基であり、ｉ及びｊはそれぞれ独立して１または２の整数で、ｉ＋ｊ＝３となる。）

(In formula (A), R _{1 to} R 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, an aryl group having 6 to 14 carbon atoms, or carbon. Q represents 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, and an alkyl group having 7 to 15 carbon atoms. An arylalkyl group, a group represented by the following formula (B ₁ ) or a group represented by the following formula (B ₂ ), wherein R ₃ and Q may be bonded to each other to form a ring structure. An oxygen atom or a sulfur atom, Z is a hydrogen atom, W is an electron-attracting substituent or phenyl group having a Hammett substituent constant σ of 0 or more, i and j are each independently an integer of 1 or 2, i + j = 3.)

（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_５〜Ｒ_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_１７及びＲ_１８、Ｄ_２が下記式（Ｖ_３）である場合のｍ_２個のＲ_１９、Ｒ_２０、並びにＲ_７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。Ｘ’は酸素原子または硫黄原子、Ｚ’は水素原子、Ｗ’はハメット置換基定数σが０以上の電子求引性の置換基またはフェニル基であり、ｇ及びｈはそれぞれ独立して１または２の整数で、ｇ＋ｈ＝３となり、ｎ_１は０〜２０の整数を示す。）

(In the 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 _{5 to} R ₈ each independently represents 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. When R ₃ and D ₁ of the formula (A) are the following formula (V ₂ ), m ₁ R ₁₇ and R ₁₈ and m ₂ when the D ₂ is the following formula (V ₃ ) ₁₉ , R ₂₀ , and R ₇ may form a ring structure by bonding at least two of these Rs together, X ′ is an oxygen atom or sulfur atom, Z ′ is a hydrogen atom, and W ′ is Hammett substituent constant σ is an electron-withdrawing substituent or phenyl group having 0 or more, and g and h are respectively In independently an integer of 1 or 2, g + h = 3 becomes, _{n 1} is an integer of 0 to 20.)

（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_５〜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_１７及びＲ_１８、Ｄ_２が下記式（Ｖ_３）である場合のｍ_２個のＲ_１９及びＲ_２０、Ｒ_７、Ｄ_３が下記式（Ｖ_４）である場合のｍ_３個のＲ_２１及びＲ_２２、並びにＲ_１１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。Ｘ’及びＸ”は酸素原子または硫黄原子、Ｚ’及びＺ”は水素原子、Ｗ’及びＷ”はハメット置換基定数σが０以上の電子求引性の置換基またはフェニル基であり、ｅ、ｆ、ｇ及びｈはそれぞれ独立して１または２の整数で、ｅ＋ｆ＝３、ｇ＋ｈ＝３となり、ｎ_１、ｎ_２、ｎ_３はそれぞれ独立して、０〜２０の整数を示す。）

(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 R _{5 to} R ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or the number of carbon atoms, each having the formula (V ₁ ) or the following formula (V ₄ ). 6 represents an aryl group having 6 to 14 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, m ₁ R ₁₇ and R ₁₈ when R ₃ and D _{1 in} the formula (A) are the following formula (V ₂ ). M ₂ R ₁₉ and R ₂₀ when D ₂ is the following formula (V ₃ ), R ₇ , m ₃ R ₂₁ and R ₂₂ when D ₃ is the following formula (V ₄ ), and R ₁₁ is good .X 'and be bonded to form a cyclic structure of at least two R are together of these R "Is an oxygen atom or sulfur atom, Z 'and Z" are hydrogen atoms, W' and W "are electron-withdrawing substituents or phenyl groups having a Hammett substituent constant σ of 0 or more, and e, f, g And h are each independently an integer of 1 or 2, and e + f = 3 and g + h = 3, and n ₁ , n ₂ , and n ₃ each independently represent an integer of 0 to 20.)

（式（Ｖ_２）中、ｍ_１個のＲ_１７及びＲ_１８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 ₁₇ and R ₁₈ 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_１９及びＲ_２０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 ₁₉ and R ₂₀ 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_２１及びＲ_２２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 ₂₁ and R ₂₂ 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.)

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). Incidentally, in the formula _{(A 2),} where R 3, _{D 1} is the formula _{(V 2)} when it is _{m 1} pieces of _{R 17} and _R 18, _{D 2} is the formula _{(V 3)} m _Two of R ₁₉ and R ₂₀ , and R ₇ 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 ₁₇ and R ₁₈ and D ₂ are the formula (V ₃ ). m ₂ pieces of _{R 19} and _{R 20,} R 7, _{D 3} is the formula _{(V 4) m 3} pieces of the case where _{R 21} and _{R 22,} and _{R 11,} 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、Ｒ_３、Ｒ_４、Ｘ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。Ｚは水素原子、Ｗはハメット置換基定数σが０以上の電子求引性の置換基またはフェニル基であり、ｉ及びｊはそれぞれ独立して１または２の整数で、ｉ＋ｊ＝３となる。）

(In the formula (A ₁ ), R ₁ , R ₂ , R ₃ , R ₄ and X 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, and R ₃ and R ₃ ′ may be bonded to each other to form a ring structure. Is a hydrogen atom, W is an electron-withdrawing substituent or phenyl group having a Hammett substituent constant σ of 0 or more, i and j are each independently an integer of 1 or 2, and i + j = 3.

（式（Ａ_２）中、Ｄ_１及びＤ_２、Ｒ_１〜Ｒ_８、ｎ_１、Ｘ及びＸ’は前記式（Ａ）及び前記式（Ｂ_１）と同様である。Ｚ及びＺ’は水素原子、Ｗ及びＷ’はハメット置換基定数σが０以上の電子求引性の置換基またはフェニル基であり、ｇ及びｈはそれぞれ独立して１または２の整数で、ｇ＋ｈ＝３となる。）

(In the formula (A ₂ ), D ₁ and D ₂ , R _{1 to} R ₈ , n ₁ , X and X ′ are the same as those in the above formula (A) and the above formula (B ₁ ). A hydrogen atom, W and W ′ are an electron-attracting substituent or phenyl group having a Hammett substituent constant σ of 0 or more, and g and h are each independently an integer of 1 or 2, and g + h = 3 .)

（式（Ａ_３）中、Ｄ_１、Ｄ_２及びＤ_３、Ｒ_１〜Ｒ_１２、ｎ_１、ｎ_２及びｎ_３、Ｘ、Ｘ’及びＸ”は前記式（Ａ）及び前記式（Ｂ_２）と同様である。Ｚ、Ｚ’及びＺ”は水素原子、Ｗ、Ｗ’及びＷ”はハメット置換基定数σが０以上の電子求引性の置換基またはフェニル基であり、ｅ及びｆはそれぞれ独立して１または２の整数で、ｅ＋ｆ＝３となる。）

(In the formula (A ₃ ), D ₁ , D ₂ and D ₃ , R _{1 to} R ₁₂ , n ₁ , n ₂ and n ₃ , X, X ′ and X ″ represent the formula (A) and the formula (B ₂ ) Z, Z ′ and Z ″ are hydrogen atoms, W, W ′ and W ″ are electron-withdrawing substituents or phenyl groups having a Hammett substituent constant σ of 0 or more, and e and f is independently an integer of 1 or 2, and e + f = 3.)

In R ₁ , R ₂ , R ₅ , R ₆ , R ₉ and R ₁₀ 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 ₅ , R ₆ , R ₉ and R ₁₀ 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.

R ₃ , R ₃ ′, R ₄ , R ₇ , R ₈ , R ₁₁ , R ₁₂ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ and Q in the above formula are alkyl groups. In such a case, the number of carbon atoms is preferably 2 to 6, 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.

  The above alkyl group, cycloalkyl group, aryl group, and arylalkyl 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, and an acyloxy group. Group, hydroxy group and the like. Further, the alkyl group, cycloalkyl group, aryl group, and arylalkyl group may have a branched structure.

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 "ring structure" may be any ring structure such as a saturated aliphatic ring, an unsaturated aliphatic ring, and an aromatic ring, and in addition, a hydrogen atom bonded to the carbon atoms constituting these rings Substituted with an alkyl group such as a methyl group, an ethyl group or a propyl group, a hydroxyl group, a mercapto group, a cyano group or a nitro group, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Also included in the concept of “ring structure” in the above formulas are ring structures and ring structures having hetero atoms other than nitrogen atoms (oxygen atoms, sulfur atoms, etc.) in the chain.

  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 hydroxyl 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 having a hetero atom other than nitrogen atom (oxygen atom, sulfur atom, etc.) in the chain, such as a 6-membered ring; for example, a 2,6-dimethylmorpholine ring (6-membered ring) Ring), 2,6-diethylmorpholine ring (6-membered ring), 2,6-dipropylmorpholine ring (6-membered ring), 2,6-dimethylthiomorpholine ring (6-membered ring), 2,6-diethylthio Saturated aliphatic rings having heteroatoms (oxygen atoms, sulfur atoms, etc.) other than nitrogen atoms such as morpholine rings (6-membered rings) and 2,6-dipropylthiomorpholine rings (6-membered rings) in the chain A hydrogen atom bonded to a carbon atom constituting, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a hydroxyl group, a mercapto group, a cyano group, a nitro group, such as a fluorine atom, a chlorine atom, a bromine atom, With halogen atoms such as iodine atoms Substituted nitrogen-containing saturated aliphatic ring having 3 to 10 carbon atoms; for example, 3 to 10 carbon atoms such as pyrrole ring (5-membered ring), imidazole ring (5-membered ring), pyrazole ring (5-membered ring), etc. Nitrogen-containing 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 ( Bonded to carbon atoms constituting unsaturated aliphatic rings or aromatic rings such as 5-membered rings), 3,5-diethylpyrazole rings (5-membered rings), 3,5-dipropylpyrazole rings (5-membered rings), etc. A hydrogen atom is, for example, an alkyl group such as a methyl group, ethyl group, propyl group A nitrogen-containing unsaturated aliphatic group 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. A ring, 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.

Further, W, Formula (B ₁ ), Formula (B ₂ ), Formula (A ₂ ), and Formula (A) in Formula (A), Formula (A ₁ ), Formula (A ₂ ), and Formula (A ₃ ) described above W ′ in ₃ ), W ″ in formula (B ₂ ) and formula (A ₃ ) is an electron-attracting substituent having a Hammett substituent constant σ of 0 or more, or a phenyl group. A), Z in Formula (A ₁ ), Formula (A ₂ ) and Formula (A ₃ ), Z ′ in Formula (B ₁ ), Formula (B ₂ ), Formula (A ₂ ) and Formula (A ₃ ), Z ″ in formula (B ₂ ) and formula (A ₃ ) is a hydrogen atom.

Further, the subscript i of Z in the above formula (A), formula (A ₁ ), formula (A ₂ ), and formula (A ₃ ) is the number of Z, the above formula (A), formula (A ₁ ), formula The subscript j of W in (A ₂ ) and the formula (A ₃ ) indicates the number of W, i and j are each independently an integer of 1 or 2, and i + j = 3.

Furthermore, the subscript g of Z ′ in the above formula (B ₁ ), formula (B ₂ ), formula (A ₂ ), and formula (A ₃ ) is the number of Z ′, the above formula (B ₁ ), formula In (B ₂ ), formula (A ₂ ), and formula (A ₃ ), the subscript h of W ′ represents the number of W ′, g and h are each independently an integer of 1 or 2, and g + h = 3 Become.

In the above formulas (B ₂ ) and (A ₃ ), the subscript e of Z ″ is the number of Z ″, and the subscript f of W ″ in the above formulas (B ₂ ) and (A ₃ ) is W ″. E and f are each independently an integer of 1 or 2, and e + f = 3.

For convenience, as shown below, -CZ _i W _j in formula (A), formula (A ₁ ), formula (A ₂ ), and formula (A ₃ ) is expressed by formula (T), formula (B ₁ ), In formula (B ₂ ), formula (A ₂ ), and formula (A ₃ ), —CZ ′ _g W ′ _h is converted to —CZ ″ _e W ″ in formula (T ′), formula (B ₂ ), and formula (A ₃ ). _f is shown as a formula (T ″).

  As W, W ′, and W ″ that are electron-withdrawing substituents having a Hammett substituent constant σ of 0 or more, conventional electron-withdrawing groups in organic electronic theory can be used. Carbonyl group, alkenylcarbonyl group, aralkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, alkenyloxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylsulfonyl group, alkenylsulfonyl group, aralkylsulfonyl group, arylsulfonyl group , Alkyl sulfoxide group, alkenyl sulfoxide group, aralkyl sulfoxide group, aryl sulfoxide group, halogen, nitro group, phenylsulfonyl group, acetyl group, cyano group or trifluoroalkyl group. But it is not limited.

In addition, a fluorenyl group can be applied to the above-described formula (T), formula (T ′), and formula (T ″). For example, a fluorenyl group represented by the following formula (C) and a derivative thereof may be used. In formula (C), Y ₁ and Y ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a nitro group, and the carbon number of the alkyl group is 2 The alkyl group and the cycloalkyl group may have a branched structure.

  As shown below, when the formula (T), formula (T ′), and formula (T ″) are fluorenyl groups, the number i of Z (Z ′, Z ″: hydrogen atoms) is 1 ( The same applies to g and e.), W (W ′, W ″) is a phenyl group, and the number j is 2 (the same applies to h and f).

  In addition, in the above formula (T), formula (T ′), and formula (T ″), an organic sulfoxide group may be applied. For example, the organic sulfoxide group represented by the following formula (D) includes: In the formula (D), Ar is an organic group, preferably an aryl group, and specific examples thereof include phenyl, tolyl, naphthyl, and the like. 6-18 are preferable, 6-12 are especially preferable, and the electron-withdrawing substituent may couple | bond with the aryl group.

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 ₇ are both hydrogen atoms, D ₁ is Formula (V ₂ ), and m ₁ in Formula (V ₂ ) is 1. R ₁₇ and R ₁₈ are both hydrogen atoms, D ₂ is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 1, and both R ₁₉ and R ₂₀ are hydrogen. A specific example in which n ₁ is 4 (or R ₃ and R ₇ are both hydrogen atoms, D ₁ is the formula (V ₂ ), and the formula (V ₂ ) m ₁ is 5, and all five R ₁₇ and R ₁₈ are hydrogen atoms, D ₂ is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 1, and Specific example in which R ₁₉ and R ₂₀ 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 ₁₇ and R ₁₈ are both hydrogen atoms, and D ₂ Is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 1, and R ₁₉ and R ₂₀ are both hydrogen atoms.

In Formula (A) and Formula (A ₁ ), R ₃ and R ₇ 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 ₁₉ and R ₂₀ 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 ) In the (V _2A ), R _17a , R _17b , R _18a , R _18b and R _18c are all hydrogen atoms, and R ₃ and R _17c 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 _19b , R _19c , R _20a , R _20b and R _{20c in the} formula (V _3A ) are all hydrogen atoms, and R _19a and R ₇ have 2 carbon atoms. Are bonded to each other through a dimethylene chain, and n ₁ is 3, Specific example in some cases (formula (G-8)). In the formula (A), Q is the formula (B ₁ ).

In the formula (A) and the formula (A ₂ ), D ₁ is the formula (V ₂ ), m ₁ in the (V ₂ ) is 3, and the formula in that case is represented by the following formula (V _2A ) In the formula (V _2A ), R _17a , R _17b , R _18a , R _18b and R _18c are all hydrogen atoms, and R ₃ and R _17c 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 _19b , R _19c , R _20a , R _20b and R _{20c in the} formula (V _3A ) are all hydrogen atoms, and R _19a and R ₇ have 2 carbon atoms. Specific examples (formula (G 8b)). 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 ₁₇ and R ₁₈ are hydrogen atoms. D ₂ is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 1, and R ₁₉ and R ₂₀ are both hydrogen atoms, n ₁ is 0, A specific example in which R ₃ and R ₇ 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 ₇ jump over (CH ₂ ) _n1 and bond to form a ring structure.

In the formulas (A) and (A ₃ ), R ₃ , R ₇ and R ₁₁ are all hydrogen atoms, D ₁ is the formula (V ₂ ), and m ₁ in the formula (V ₂ ) is 1 and R ₁₇ and R ₁₈ are both hydrogen atoms, D ₂ is the formula (V ₃ ), m ₂ in the formula (V ₃ ) is 1, and R ₁₉ and R ₂₀ Are hydrogen atoms, D ₃ is the formula (V ₄ ), m ₃ in the formula (V ₄ ) is 1, and R ₂₁ and R ₂₂ are both hydrogen atoms, and n ₁ , N ₂ and n ₃ are all specific examples (formula (G-10)). In the formula (A), Q is the formula (B ₂ ).

In Formula (A) and Formula (A ₂ ), R ₃ and R ₇ are both hydrogen atoms, D ₁ is Formula (V ₂ ), and m ₁ in Formula (V ₂ ) is 2 and are those wherein the case is represented by the following formula _{(V 2A), R} 17a in the formula _{(V 2A),} R _17b, an _{R 18a} and _{R 18b} are all hydrogen atom, _{D 2} is a formula _{(V 3), m 2} and of the formula _{(V 3)} in two, and are those wherein the case is represented by the following formula _{(V 3A),} in the formula _{(V 3A)} A specific example in which R _19a , R _19b and R _20b are all hydrogen atoms, R _20a is a methyl group and n ₁ is 1 (formula (G-11)). In the formula (A), Q is the formula (B ₁ ).

  Moreover, an example of the compound contained in the base proliferating agent of this invention is shown below.

(BA1: W (W ′, W ″) = 2 (phenyl group, two fluorenyl groups such as W), Z (Z ′, Z ″) = 1)

(BA2: W (W ′, W ″) = 2 (phenyl group, two W and the like are fluorenyl groups), Z (Z ′, Z ″) = 1)

(BA3: W (W ′, W ″) = 1 (phenylsulfonyl group), Z (Z ′, Z ″) = 2)

(BA4: W (W ′, W ″) = 1 (phenylsulfonyl group), Z (Z ′, Z ″) = 2)

(BA5: W (W ′, W ″) = 1 (cyano group), Z (Z ′, Z ″) = 2)

(BA6: W (W ′, W ″) = 1 (cyano group), Z (Z ′, Z ″) = 2)

(BA7: W (W ′, W ″) = 1 (cyano group), Z (Z ′, Z ″) = 2)

(BA8: W (W ′, W ″) = 1 (nitro group), Z (Z ′, Z ″) = 2)

(BA9: W (W ′, W ″) = 1 (nitro group), Z (Z ′, Z ″) = 2)

(BA10: W (W ′, W ″) = 1 (acetyl group), Z (Z ′, Z ″) = 2)

(BA11: W (W ′, W ″) = 2 (acetyl group), Z (Z ′, Z ″) = 1)

(BA12: W (W ′, W ″) = 1 (acetyl group), Z (Z ′, Z ″) = 2)

(BA13: W (W ′, W ″) = 2 (acetyl group), Z (Z ′, Z ″) = 1)

The base proliferating agent according to the present invention has a property of generating a base (amine) by being decomposed by the action of a base in the presence of an epoxy compound. Regarding the reaction behavior, FIG. 1 shows the reaction scheme for the formula (A ₁ ), FIG. 2 shows the reaction scheme for the formula (A ₂ ), and FIG. 3 shows the reaction scheme for the formula (A ₃ ). In the schemes of FIGS. 1 to 3, for convenience, Z (Z ′, Z ″) may be represented by hydrogen atoms.

  As shown in the reaction scheme, the base proliferating agent of the present invention decomposes in a self-propagating manner by causing 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 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). R ″ ′ is an arbitrary alkyl group, and the compound containing the R ″ ′ is an arbitrary epoxy compound.

  As shown in the reaction scheme, the base proliferating agent of the present invention is a base proliferating agent that does not generate carbon dioxide gas by proliferating the base by a cyclization reaction in the presence of the epoxy compound. Therefore, even when the base-reactive agent is mixed with a base-reactive compound to form a base-reactive resin composition, even if such a base-reactive resin composition is formed into a film, unevenness due to carbon dioxide gas bubbles is not generated. In addition, a cured film having high product characteristics and product value can be provided.

  Since the base proliferating agent according to the present invention has good solubility in an organic solvent, when mixed with a base-reactive compound to form a base-reactive resin composition, it is easily compatible with the base-reactive compound. be able to. In addition, since the base proliferating agent according to the present invention has good heat resistance, when it is mixed with a base-reactive compound to form a base-reactive resin composition, a resin composition having high thermal stability and Become. Therefore, when forming a pattern using the said resin composition, a favorable pattern can be formed. The X, X ′, and X ″ groups are either S (sulfur atom) or O (oxygen atom). However, if the structure is the same, the decomposition rate is better when O is selected as the X (X ′, X ″) group. On the other hand, when S is selected, the thermal decomposition temperature becomes high. Therefore, the growth reaction rate and thermal stability can be easily adjusted by selecting the X (X ′, X ″) group.

  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 ₇ , R ₁₁ , D ₁ , D ₂ , D ₃ , n ₁ , n ₂ and n ₃ are the same as those in the formula (A), formula (A ₁ ), According to formula (A ₂ ) and formula (A ₃ ).

In order to synthesize a base proliferating agent represented by the formula (A ₁ ), formula (A ₂ ) and formula (A ₃ ), for example, (diphenyl phosphonic acid dichloride or thiophenyl phosphonic dichloride is used as a starting material. As shown in FIG. 4 to FIG. Figure A synthetic scheme for formula _{(A 1)} 4, wherein FIG synthetic scheme for _{(A 2)} 5, the formula _{(A 2),} a base portion of isophorone diamine (1-amino-3-amino-3, 5,5-trimethylcyclohexane) (corresponding to formula (G-7) when R ₁ , R ₂ , R ₅ and R ₆ are hydrogen atoms), the synthesis scheme is shown in FIG. For A ₂ ), the base portion is 1,3-bis (4-piperidyl) propane (corresponding to the case where R ₁ , R ₂ , R ₅ and R ₆ are hydrogen atoms in formula (G-8)). The synthesis scheme is as shown in FIG. 7, formula (A ₂ ), and the base moiety is 2-methylpentane-1,5-diamine (formula (G-11), R ₁ , R ₂ , R ₅ , R ₆ Is a hydrogen atom.) 8 respectively show synthesis schemes for formula (A ₃₎ in FIG. 9 scheme.

  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, orthonitrobenzyl urethane compounds and the like disclosed in JP 2000-330270 A are used. It may be.

  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 (E-1) thru | or Formula (E-6) 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 —.

  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 including an epoxy compound (a 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. Since the base proliferating agent according to the present invention releases a new base by reaction with an epoxy compound having at least one epoxy group, it is necessary to coexist with the epoxy compound. Accordingly, the base-reactive compound may be a main base-reactive compound that cures the epoxy-based compound, or a sufficient amount of the epoxy-based compound to cause decomposition of the base proliferating agent. (The same number of epoxy groups as the functional group of the base generator is preferably present), the base-reactive compound contributing to curing may be a base-reactive compound other than the epoxy compound. The base-reactive compound in that case is not particularly limited, and a conventionally known base-reactive compound can be used. For example, a silicon-based compound having at least one alkoxysilyl group, silanol group, etc. It is preferable to use a compound, an oxetane compound containing an oxetane ring, or the like. Base reactive compounds other than such epoxy compounds may be used singly 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 compound (silicon resin) added in addition to the epoxy compound, 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) added in addition to the epoxy compound, 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.

  All of the base-reactive compounds are preferably epoxy compounds. 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. In addition, the following No. 2-1. Among the polymerized compounds (base reactive compounds) of No. 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 2-8 base-reactive compound 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.

  Further, as the base reactive compound added in addition to the epoxy 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. By using a sensitizer described later, a higher wavelength region 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 generally about 100 parts by mass 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 0.1 to 350 parts by mass, and preferably 0.1 to 120 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 0.1-60 mol per monomer unit of a base reactive compound (epoxy type compound etc.). In addition, when the base-reactive compound is an epoxy compound, the base proliferating agent is 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. Alternatively, it is preferably 40 to 80 mol%. 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). Moreover, you may make it contain in 0.1-80 mol% with respect to an epoxy-type compound.

  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 (epoxy type compound etc.). In addition, when the base-reactive compound is an epoxy compound, the base generator is 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. Alternatively, it is preferably 10 to 80 mol%. Moreover, you may make it contain in 0.1-80 mol% with respect to an epoxy-type compound.

  The base-reactive resin composition of the present invention has the above-described No. 1 as a base-reactive compound. 4-1. As the epoxy compound (polymerizable epoxy compound) exhibiting polymerization reactivity, such as 4-14, and the base reactive compound added in addition to the epoxy compound, the above-mentioned No. 4 is used. 5-1 to No. It is good also as a silicon type compound (polymerizable silicon type compound) which shows 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, pentaerythritol tetrakis (3-mercaptobutyrate) 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 may be, for example, thiol equivalent (SH equivalent) / epoxy equivalent, etc. = 0.3 / 1.7 to 1.7 / 0.3 with respect to the epoxy compound or the like. Preferably, the ratio is 0.8 / 1.2 to 1.2 / 0.8. If this ratio is within the range of 0.3 / 1.7 to 1.7 / 0.3, it is possible to prevent a large amount of unreacted thiol groups, epoxy groups, etc. from remaining in the cured product. The tendency for the mechanical properties of objects to deteriorate 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 within the range of 150 ° C, and it is particularly preferable to be within the range of 60 ° C to 140 ° 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, a curing accelerator, a filler, and the like. 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 contains 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 in the presence of an epoxy compound. The reaction between the base generated from the base proliferating agent and a base-reactive compound such as an epoxy compound proceeds in a chain, resulting in excellent curing speed and reaction efficiency. Curing is carried out quickly and cured sufficiently. A base-reactive resin composition.

  In addition, the base-reactive resin composition of the present invention does not cause carbon dioxide gas generation when the added base proliferating agent grows the base, so that the cured film does not cause unevenness due to carbon dioxide gas bubbles. A cured film having high characteristics and product value can be provided.

  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.

[Example 1]
Production of base proliferating agent (1):
In a 200 mL eggplant flask, 2.0 g (10 mmol) of phenylphosphonic dichloride (phenylphosphonic dichloride), 1.6 g (20 mmol) of pyridine, 0.02 g of tetrazole and 15 ml of THF were added and stirred in an ice bath. A solution prepared by dissolving 1.7 g (8 mmol) of 9-fluorenylmethanol in 5 mL of THF was added dropwise thereto and stirred at room temperature for 3 hours. Thereafter, 0.80 g (9.4 mmol) of cyclohexylamine added to 10 mL of THF was added dropwise in an ice bath, and the mixture was stirred at room temperature for 12 hours. After stirring, the solution was distilled off under reduced pressure, diluted with chloroform, and extracted with a 5% hydrochloric acid aqueous solution, a saturated aqueous sodium bicarbonate solution, and a saturated saline solution three times each. Thereafter, the solution was distilled off under reduced pressure, and a white solid of the base proliferating agent of Example 1 represented by the following formula (Aa) was obtained by column chromatography (developing solvent ratio: ethyl acetate / dichloromethane = 1/3). Obtained in 1.1 g (yield 30%).

[Example 2]
Production of base proliferating agent (2):
The four-necked flask is brought to an N ₂ atmosphere, and 2.0 g (10 mmol) of phenylphosphonic dichloride, 2.0 g (25 mmol) of pyridine and 20 mL of THF are added and stirred in an ice bath. A solution prepared by dissolving 1.8 g (9.2 mmol) of 9-fluorenylmethanol in 20 mL of THF was added dropwise thereto and stirred at room temperature for 7 hours. Thereafter, piperidine (0.80 g, 9.4 mmol) added to THF (10 mL) was added dropwise in an ice bath, and the mixture was stirred at room temperature for 12 hours. After stirring, the solution was distilled off under reduced pressure, diluted with chloroform, and extracted with a 5% hydrochloric acid aqueous solution, a saturated aqueous sodium bicarbonate solution, and a saturated saline solution three times each. Thereafter, the solution was distilled off under reduced pressure, and a white solid of the base proliferating agent of Example 2 represented by the following formula (A-b) was obtained by column chromatography (developing solvent ratio: ethyl acetate / dichloromethane = 1/2). Obtained in 71 g (19% yield).

[Example 3]
Production of base proliferating agent (3):
The four-necked flask was placed in an N ₂ atmosphere, and 2.0 g (10 mmol) of phenylphosphonic dichloride, 2.0 g (25 mmol) of pyridine and 20 mL of THF were added and stirred in an ice bath. A solution prepared by dissolving 1.8 g (9.2 mmol) of 9-fluorenylmethanol in 20 mL of THF was added dropwise thereto and stirred at room temperature for 7 hours. Thereafter, 1.0 g (4.8 mmol) of 1,3-bis (4-piperidyl) propane added to 10 mL of THF was dropped in an ice bath and stirred at room temperature for 12 hours. After stirring, the solution was distilled off under reduced pressure, diluted with chloroform, and extracted with a 5% hydrochloric acid aqueous solution, a saturated aqueous sodium bicarbonate solution, and a saturated saline solution three times each. Thereafter, the solution was distilled off under reduced pressure, and a white solid of the base proliferating agent of Example 3 represented by the following formula (Ac) was obtained by column chromatography (developing solvent ratio: ethyl acetate / hexane = 10/1). Obtained in 50 g (12% yield).

[Example 4]
Production of base proliferating agent (4):
The four-necked flask was placed in an N ₂ atmosphere, and 2.0 g (10 mmol) of phenylphosphonic dichloride, 2.0 g (25 mmol) of pyridine and 20 mL of THF were added and stirred in an ice bath. A solution prepared by dissolving 1.8 g (9.2 mmol) of 9-fluorenylmethanol in 20 mL of THF was added dropwise thereto and stirred at room temperature for 7 hours. Thereafter, 1.6 g (4.8 mmol) of 1.6-diaminohexane added to 10 mL of THF was added dropwise in an ice bath, and the mixture was stirred at room temperature for 12 hours. After stirring, the solution was distilled off under reduced pressure, diluted with chloroform, and extracted with a 5% hydrochloric acid aqueous solution, a saturated aqueous sodium bicarbonate solution, and a saturated saline solution three times each. Thereafter, the solution was distilled off under reduced pressure, and 0.91 g (yield 16%) of a white solid of the base proliferating agent of Example 4 represented by the following formula (Ad) was represented by column chromatography (developing solvent: ethyl acetate). ).

[Example 5]
Production of base proliferating agent (5):
A four-necked flask was placed in an N ₂ atmosphere, and a solution of 1.5 g (4.6 mmol) of phenylphosphonic dichloride dissolved in 10 mL of THF was added with 0.5 g (6.3 mmol) of pyridine and 2.7− in an ice bath. A solution prepared by dissolving 0.95 g (4.6 mmol) of t-butyl-9-fluorenylmethanol in 10 mL of THF was added dropwise and stirred at room temperature for 4 hours. Thereafter, 0.18 g (1.5 mmol) of 1,6-diaminohexane added to 10 mL of THF was added dropwise in an ice bath and stirred at room temperature for 12 hours. After stirring, the solution was distilled off under reduced pressure, diluted with chloroform, and extracted three times with 5% aqueous hydrochloric acid and saturated brine. Thereafter, the solution was distilled off under reduced pressure, and a white solid of the base proliferating agent of Example 5 represented by the following formula (Ae) was obtained by column chromatography (developing solvent: ethyl acetate) in a yield of 0.37 g (yield 14%). ).

[Example 6]
Production of base proliferating agent (6):
The four-necked flask was placed in an N ₂ atmosphere, and 2.0 g (10 mmol) of phenylphosphonic dichloride, 3.0 g (38 mmol) of pyridine and 15 mL of THF were added and stirred in an ice bath. A solution prepared by dissolving 9.95 g (10 mmol) of 9-fluorenylmethanol in 15 mL of THF was added dropwise thereto and stirred at room temperature for 5 hours. Thereafter, 0.79 g (4.8 mmol) of isophoronediamine added to 10 mL of THF was added dropwise in an ice bath, and the mixture was stirred at room temperature for 24 hours. After stirring, the solution was distilled off under reduced pressure, diluted with chloroform, and extracted three times with 5% aqueous hydrochloric acid and saturated brine. Thereafter, the solution was distilled off under reduced pressure, and 0.24 g (yield 6%) of a white solid of the base proliferating agent of Example 6 represented by the following formula (A-f) by column chromatography (developing solvent: ethyl acetate). Got in.

[Example 7]
Production of base proliferating agent (7):
A four-necked flask was placed in an N ₂ atmosphere, and 3.0 g (38 mmol) of pyridine and 9-fluorenyl in an ice bath were added to a solution of 3.0 g (14.3 mmol) of thiophenylphosphonic dichloride dissolved in 20 mL of THF. A solution prepared by dissolving 3.0 g (15.3 mmol) of methanol in 20 mL of THF was added dropwise and stirred at room temperature for 12 hours. Thereafter, piperidine 1.3 g (15.3 mmol) added to THF 10 mL was added dropwise in an ice bath and stirred at room temperature for 12 hours. After stirring, the solution was distilled off under reduced pressure, diluted with chloroform, and extracted with a 5% hydrochloric acid aqueous solution, a saturated aqueous sodium bicarbonate solution, and a saturated saline solution three times each. Thereafter, the solution was distilled off under reduced pressure, and it was represented by the following formula (Ag) by column chromatography (developing solvent ratio, (1) ethyl acetate / dichloromethane = 1/5, (2) ethyl acetate: dichloromethane = 1/7). A white solid of the base proliferating agent of Example 7 was obtained in a yield of 0.45 g (yield 7.7%).

[Example 8]
Production of base proliferating agent (8):
In a four-necked flask, 2.0 g (20 mmol) of pyridine and 2.0 g of 9-fluorenylmethanol in an ice bath were added to a solution of 2.0 g (10 mmol) of thiophenylphosphonic dichloride dissolved in 10 mL of THF. 10 mmol) dissolved in 20 mL of THF was added dropwise and stirred at room temperature for 6 hours. Thereafter, 0.8 g (4.0 mmol) of 1,3-bis (4-piperidyl) propane added to 10 mL of THF was added dropwise in an ice bath, and the mixture was stirred at room temperature for 36 hours. After stirring, the solution was distilled off under reduced pressure, diluted with chloroform, and extracted with a 5% hydrochloric acid aqueous solution, a saturated aqueous sodium bicarbonate solution, and a saturated saline solution three times each. Thereafter, the solution was distilled off under reduced pressure, and a white solid of the base proliferating agent of Example 8 represented by the following formula (Ah) was obtained by column chromatography (developing solvent ratio: ethyl acetate / hexane = 1/20). Obtained in 50 g (yield 11%).

[Example 9]
Production of base proliferating agent (9):
A four-necked flask was placed in an N ₂ atmosphere, and 3.0 g (38 mmol) of pyridine and 9-fluorenylmethanol in an ice bath were added to a solution of 2.0 g (10 mmol) of thiophenylphosphonic dichloride dissolved in 10 mL of THF. A solution of 2.0 g (10 mmol) dissolved in 20 mL of THF was added dropwise, and the mixture was stirred at room temperature for 8 hours. Thereafter, 0.5 g (4.3 mmol) of 2-methylpentane-1,5-diamine and 2.0 g (25 mmol) of pyridine in 20 mL of THF were added dropwise in an ice bath and stirred at room temperature for 2 days. After stirring, the solution was distilled off under reduced pressure, diluted with chloroform, and extracted with a 5% hydrochloric acid aqueous solution, a saturated aqueous sodium bicarbonate solution, and a saturated saline solution three times each. Thereafter, the solution was distilled off under reduced pressure, and a white solid of the base proliferating agent of Example 9 represented by the following formula (A-i) by column chromatography (developing solvent ratio, (1) ethyl acetate / hexane = 1/15). Was obtained in a yield of 0.67 g (yield 20%).

FIG. 10 shows the result of assignment by ¹ H-NMR or the like for the synthesis of Examples 1 to 9 described above.

[Test Example 1]
Confirmation of solubility in organic solvents:
The solubility of the base proliferating agent obtained in Examples 1 to 8 in an organic solvent was confirmed. 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. The results are shown in FIG. In FIG. 11, the result of the dissolution amount is shown as “++” 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 10 mL. "When exceeding 10 mL, indicated as"-". In addition, the thermal decomposition temperature (T _d ⁵ ) of the base proliferating agent obtained in Examples 1 to 9 was measured and compared. Note that the thermal decomposition temperature ^{_{(T d 5), TG-}} DTA - was determined by (differential thermal Thermogravimetry).

  FIG. 11 is a diagram showing the solubility of the base proliferating agent in an organic solvent. As shown in FIG. 11, it was confirmed that the base proliferating agents of Examples 1 to 8 showed good solubility in organic solvents.

[Test Example 2]
Confirmation of degradation behavior of base proliferator in solution (1):
In the base proliferating agent according to the present invention, the phosphoric acid amide (when X is O (oxygen atom)) generated by elimination of a fluorenyl group or the like by addition of a base and an epoxy system are obtained in the above-described examples. The compound reacts and releases the amine by further cyclization reaction. Thus, a decomposition reaction occurs by the addition of a base, and an olefin is generated together with the base. Therefore, it was confirmed whether or not the present invention functions as a base proliferating agent by tracing the peaks derived from the base proliferating agent and the epoxy compound using ¹ H-NMR and performing thermal decomposition behavior.

In the NMR sample tube, the base proliferating agent 70 × 10 ⁻³ mol / L obtained in Example 2 and the base piperidine 1 × 10 ⁻³ mol / L or 10 × 10 ⁻³ mol / L, epoxy compound A certain butyl glycidyl ether 70 × 10 ⁻³ mol / L, dioxane-d ₈ as a solvent, and mesitylene 14 × 10 ⁻³ mol / L as an internal standard solution are put into a sealed tube, and then sealed at 100 ° C. for a predetermined time using an oven. Heated. Then, by analyzing the generated olefin peak 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 (piperidine) was added. FIG. 12 shows the relationship between the heating time and the olefin production rate. The production rate of olefin (dibenzofulvene (hereinafter sometimes referred to as “DF”)) was calculated from a ¹ H-NMR spectrum.

  As shown in FIG. 12, with respect to the base proliferating agent of Example 2, it was confirmed that the base proliferating reaction and the production of olefin were confirmed with respect to the production rate of olefin. In addition, a correlation with the amount of piperidine added as a base was observed, and in the system to which a base was added, the base proliferating agent decomposed faster and the olefin was also produced faster.

[Test Example 3]
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 7, piperidine 10 × 10 ⁻³ mol / L as a base, and butyl glycidyl ether (BGE) 70 × as an epoxy compound. 10 ⁻³ mol / L, dioxane-d ₈ as a solvent, and mesitylene 14 × 10 ⁻³ mol / L as an internal standard solution were placed, sealed, and then heated at 100 ° C. for a predetermined time using an oven. Then, by analyzing the generated olefin peak by ¹ H-NMR, the decomposition behavior (generation of olefin) of the base proliferating agent was confirmed and compared with the base (when piperidine was not added). FIG. 13 and FIG. 14 show the relationship between the heating time, the olefin production rate, the base growth agent, and the reduction rate of the epoxy compound (BGE). The production rate of olefin (DF) was calculated from ¹ H-NMR spectrum.

  As shown in FIG. 13, the system to which the base (piperidine) common with the base constituting the base proliferating agent of Example 7 was added had a nonlinear reaction curve peculiar to the growth reaction. It was confirmed that it decomposed efficiently and produced olefins. Moreover, as shown in FIG. 14, the system which does not add a base (piperidine) did not produce an olefin, and the base proliferating agent did not decompose.

[Test Example 4]
Confirmation of carbon dioxide generation (1) (comparison with decarboxylated base proliferator):
The sorbitol polyglycidyl ether (Denacol (registered trademark) EX-622 / manufactured by Nagase ChemteX Corp.) 0.05 g which is an epoxy compound represented by the formula (No. 4-13) is represented by the formula (E- 4) 0.003 g of the photobase generator shown in 4) (6 parts by mass with respect to 100 parts by mass of the epoxy compound, 10 mol% with respect to the epoxy compound), 0.05 g of the base proliferating agent of Example 3 (epoxy) A chloroform solution (1) to which 100 parts by mass with respect to 100 parts by mass of the system compound and 25 mol% with respect to the epoxy compound was added was prepared. For comparison, with respect to 0.03 g of the epoxy compound, 0.003 g of the photobase generator shown in Formula (E-4) (10 parts by mass with respect to 100 parts by mass of the epoxy compound, 10 mol%) and 0.038 g of decarboxylation type base proliferating agent represented by the following formula (F-1) (127 parts by mass with respect to 100 parts by mass of the epoxy compound and 25 mol% with respect to the epoxy compound) were added. A chloroform solution (2) was prepared. The chloroform solution corresponds to a solution of the base-reactive resin composition comprising the base proliferating agent, photobase generator and base-reactive compound according to the present invention dissolved in chloroform as a solvent.

The obtained chloroform solution (1) and chloroform solution (2) are dropped onto a glass substrate placed on a hot plate at 100 ° C., and after removing the solvent sufficiently, the glass substrate is covered from above and sandwiched between clips to form a film. Produced. The film was irradiated with light having a wavelength of 365 nm of 5000 mJ / cm ² and heated in an oven at 120 ° C. for 2 hours to observe the state of the film.

  The film taken out of the oven was adhered to both the chloroform solution (1) and the chloroform solution (2) so that they could not be removed by hand. In the system using the base proliferating agent of Example 3, bubbles due to the generation of carbon dioxide were not recognized, and the membrane was adhered on the entire surface. On the other hand, bubbles due to carbon dioxide were observed in the film using the decarboxylated base proliferating agent, and the adhesion area was about half of the whole. From the above, the superiority of the base proliferating agent of Example 3 over the decarboxylated base proliferating agent was confirmed.

[Test Example 5]
Confirmation of carbon dioxide generation (2) (Comparison with epoxy compounds):
With respect to 0.03 g of sorbitol polyglycidyl ether which is an epoxy compound represented by the formula (No. 4-13) used in Test Example 4, the photobase generator represented by the formula (E-4) is 0. 0.003 g (10 parts by mass with respect to 100 parts by mass of the epoxy compound), 0.03 g of the base proliferating agent of Example 4 (100 parts by mass with respect to 100 parts by mass of the epoxy compound, 60 mol% with respect to the epoxy compound) ) An added chloroform solution (1 ') was prepared.

  Further, the epoxy compound was converted from the sorbitol polyglycidyl ether to 4,4′-methylenebis (N, N-diglycidylaniline) (NN / Aldrich) 0.1 g represented by the formula (No. 4-6). In contrast, 0.014 g (14 parts by mass with respect to 100 parts by mass of the epoxy compound) of the photobase generator represented by the formula (E-4), and 0.12 g of the content of the base proliferating agent of Example 4 A chloroform solution (3) was prepared (120 parts by mass with respect to 100 parts by mass of the epoxy compound and 60 mol% with respect to the epoxy compound).

  Further, the epoxy compound is converted from the sorbitol polyglycidyl ether to 0.1 g of the epoxy compound (JER-828 / Mitsubishi Chemical Corporation) represented by the formula (No. 4-14). 4) 0.006 g (6 parts by mass with respect to 100 parts by mass of epoxy compound) of the photobase generator shown in 4), and 0.06 g (100 parts by mass of epoxy compound) of the base proliferating agent of Example 4 Chloroform solution (4) with 60 parts by mass) was prepared.

  Then, the epoxy compound is converted from the sorbitol polyglycidyl ether to pentaerythritol polyglycidyl ether represented by the formula (No. 4-15) (Denacol (registered trademark) EX-411 / manufactured by Nagase ChemteX Corporation). 0.014 g (14 parts by mass with respect to 100 parts by mass of the epoxy compound) of the photobase generator represented by the formula (E-4) with respect to 1 g, and 0.1 g of the base proliferating agent of Example 4 A chloroform solution (5) was prepared (100 parts by mass with respect to 100 parts by mass of the epoxy compound and 60 mol% with respect to the epoxy compound).

  And about the obtained chloroform solution (1 '), chloroform solution (3), chloroform solution (4), and chloroform solution (5), the method similar to the method shown in Test Example 4 was used, and the state of the film was changed. Observed.

  As in Test Example 4, the film taken out of the oven was adhered to the chloroform solution (1 ′), chloroform solution (3), chloroform solution (4) and chloroform solution (5) so that they could not be peeled off by hand. Was. Moreover, in any system, bubbles due to the generation of carbon dioxide were not observed, and the film was adhered on the entire surface. In the system using the epoxy compound represented by the formula (No. 4-14) which is the chloroform solution (4), a transparent cured film was obtained, but in other systems, a cloudy cured film was obtained. . The cause of white turbidity is considered to be the cause of white turbidity because the olefin generated during the reaction is not covered by the film in the state where it is sandwiched by covering the glass substrate. In addition, when used as a photo-curing material, a resist material (pattern forming material), etc., the generated olefin is volatilized, so there is no problem.

[Test Example 6]
Confirmation of carbon dioxide generation (3) (Relationship with the content of base proliferating agent):
Using sorbitol polyglycidyl ether, which is an epoxy compound represented by the formula (No. 4-13) as an epoxy compound, studying how to make a highly transparent film by changing the content of the base proliferating agent did.

  With respect to 0.03 g of sorbitol polyglycidyl ether which is an epoxy compound represented by the formula (No. 4-13) used in Test Example 4, the photobase generator represented by the formula (E-4) is 0. 0.003 g (10 parts by mass with respect to 100 parts by mass of the epoxy compound) and the chloroform solution (6), chloroform solution (7) and chloroform solution (8) prepared by adding the base proliferating agent of Example 4 as follows were prepared. did.

(Content of base proliferating agent)
Content (g) Mass part mol% (Note)
(6) 0.01 33 20 mol%
(7) 0.02 67 40 mol%
(8) 0.03 100 60 mol%
(Note) For epoxy compounds

  And about the obtained chloroform solution (6), chloroform solution (7), and chloroform solution (8), the method similar to the method shown in Test Example 4 was used, and the state of the film | membrane was observed.

  As in Test Example 4 and the like, the film taken out from the oven was adhered to the chloroform solution (6), the chloroform solution (7), and the chloroform solution (8) so that they could not be removed by hand. Moreover, in any system, bubbles due to the generation of carbon dioxide were not observed, and the film was adhered on the entire surface. As the content decreased, the white turbidity in the cured film disappeared, and in the chloroform solution (6) (20 mol%) system, a beautiful and highly cured film (transmittance: 89%) was obtained. From the above, it was confirmed that a cured film having high transparency can be obtained even in a system using sorbitol polyglycidyl ether as an epoxy compound.

[Example 10 and Example 11]
Production of base-reactive resin composition (1):
The sorbitol polyglycidyl ether (Denacol (registered trademark) EX-622 / manufactured by Nagase ChemteX Corp.) 0.03 g which is an epoxy compound represented by the formula (No. 4-13) is represented by the formula (E- 4) 0.001 g of the photobase generator represented by 4) (3.3 parts by mass with respect to 100 parts by mass of the epoxy compound and 18 mol% with respect to the epoxy compound), the base proliferating agent obtained in Example 4 Was added at the following content to obtain a base-reactive resin composition of the present invention.

(Content of base proliferating agent)
Content (g) Mass part mol% (Note)
Example 10 0.01 33 20 mol%
Example 11 0.02 67 40 mol%
(Note) For epoxy compounds

[Reference Example 1]
Production of resin composition (1)
In Example 10, a resin composition was obtained using the same method as in Example 6 except that the base proliferating agent obtained in Example 4 was not added.

[Test Example 7]
Curing confirmation (1) (confirmation of heating temperature dependence):
The base-reactive resin composition obtained in Example 11 was dissolved in 0.3 g of chloroform (CHCl ₃ ) to obtain a sample solution. The sample solution was bar-coated on a glass substrate to form a film, heated at 100 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 1.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 100, 1000 and 5000 mJ / cm ² , and the hardness of the coating film after heating at 100 ° C. for 60 minutes as post-baking was JIS K5600-5-4. In accordance with the pencil hardness measurement. Then, similar operations were carried out at post-baking heating temperatures of 120 ° C. and 140 ° C. for comparison and evaluation. FIG. 15 shows the relationship between the exposure amount and the pencil hardness.

  As shown in FIG. 15, the curing progressed as the heating temperature was increased, and the maximum hardness was obtained.

[Test Example 8]
Curing confirmation (2) (confirmation of content dependency):
The base-reactive resin composition obtained in Example 10 was dissolved in 0.3 g of chloroform (CHCl ₃ ) to obtain a sample solution. The sample solution was bar-coated on a glass substrate to form a film, heated at 100 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 1.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 100, 1000 and 5000 mJ / cm ² , and the hardness of the coating film after heating at 120 ° C. for 60 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 base reactive resin composition etc. of Example 11 and Reference Example 1, etc., and compared and evaluated. FIG. 16 shows the relationship between the exposure amount and the pencil hardness.

As shown in FIG. 16, curing progressed as the content of the base proliferating agent was increased, and when the exposure amount was 5000 mJ / cm ² , a hardness of 3B was obtained in Example 10 and a hardness of H was obtained in Example 11. .

[Example 12]
Production of base-reactive resin composition (2):
The sorbitol polyglycidyl ether (Denacol (registered trademark) EX-622 / manufactured by Nagase ChemteX Corp.) 0.03 g which is an epoxy compound represented by the formula (No. 4-13) is represented by the formula (E- 2) 0.003 g (10 parts by mass with respect to 100 parts by mass of the epoxy compound) of the photobase generator represented by 2), and 0.02 g (100 parts by mass of the epoxy compound) of the base proliferating agent obtained in Example 4 The base-reactive resin composition of this invention was obtained by making it contain by 67 mass parts).

[Test Example 9]
Curing confirmation (3) (confirmation of heating temperature and heating time dependence):
The base-reactive resin composition obtained in Example 12 was dissolved in 0.3 g of chloroform (CHCl ₃ ) to prepare a sample solution. The sample solution was bar-coated on a glass substrate to form a film, heated at 100 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 1.0 μm. 365 nm monochromatic light is applied to this coating film, the exposure amount is 5000 mJ / cm ² , post baking, four baking baking temperatures of 80, 100, 120 and 140 ° C., and heating time of 0 (blank), 30, The hardness of the coating film after heating was measured according to JIS K5600-5-4 as 4 types for 60 and 120 minutes (16 types in total). FIG. 17 shows the relationship between the heating temperature, heating time, and pencil hardness.

As shown in FIG. 17, when the exposure dose is 5000 mJ / cm ² , the curing proceeds as the heating temperature increases and the heating time increases, and the heating temperature is 140 ° C. and the heating time is 120 minutes. The hardness of F was obtained.

[Example 13]
Production of base-reactive resin composition (3):
The sorbitol polyglycidyl ether (Denacol (registered trademark) EX-622 / manufactured by Nagase ChemteX Corp.) 0.03 g which is an epoxy compound represented by the formula (No. 4-13) is represented by the formula (E- 2) 0.003 g (10 parts by mass with respect to 100 parts by mass of the epoxy compound) of the photobase generator represented by 2), and 0.02 g (100 parts by mass of the epoxy compound) of the base proliferating agent obtained in Example 6 The base-reactive resin composition of this invention was obtained by making it contain by 67 mass parts).

[Test Example 10]
Curing confirmation (4) (confirmation of heating temperature and heating time dependence):
The base-reactive resin composition obtained in Example 13 was dissolved in 0.3 g of chloroform (CHCl ₃ ) to prepare a sample solution. The sample solution was bar-coated on a glass substrate to form a film, heated at 100 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 1.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 5000 mJ / cm ² , post baking, heating temperatures of post baking were 80, 100 and 120 ° C., heating time was 0 (blank), 30, 60 and The hardness of the coating film after heating was measured according to JIS K5600-5-4 as four types for 120 minutes (total of 12 types). FIG. 18 shows the relationship between the heating temperature, heating time, and pencil hardness.

As shown in FIG. 18, when the exposure dose is 5000 mJ / cm ² , curing proceeds as the heating temperature increases and the heating time increases, and the heating temperature is 120 ° C. and the heating time is 120 minutes. The hardness of F was obtained.

[Example 14]
Production of base-reactive resin composition (4):
The photobase generator represented by the formula (E-2) is changed to 0 with respect to 0.03 g of the epoxy compound (JER-828 / Mitsubishi Chemical Corporation) represented by the formula (No. 4-14). 0.003 g (10 parts by mass with respect to 100 parts by mass of the epoxy compound) and 0.02 g (67 parts by mass with respect to 100 parts by mass of the epoxy compound) of the base proliferating agent obtained in Example 4 A base-reactive resin composition of the present invention was obtained.

[Test Example 11]
Curing confirmation (5) (confirmation of heating temperature and heating time dependence):
The base-reactive resin composition obtained in Example 14 was dissolved in 0.3 g of chloroform (CHCl ₃ ) to obtain a sample solution. The sample solution was bar-coated on a glass substrate to form a film, heated at 100 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 1.0 μm. 365 nm monochromatic light is applied to this coating film, the exposure amount is 5000 mJ / cm ² , post baking, four baking baking temperatures of 80, 100, 120 and 140 ° C., and heating time of 0 (blank), 30, The hardness of the coating film after heating was measured according to JIS K5600-5-4 as 4 types for 60 and 120 minutes (16 types in total). FIG. 19 shows the relationship between the heating temperature, heating time, and pencil hardness.

As shown in FIG. 19, when the exposure dose is 5000 mJ / cm ² , curing proceeds as the heating temperature increases and the heating time increases, and the heating temperature is 140 ° C. and the heating time is 60 minutes. And 120 minutes, a hardness of 3B was obtained.

[Examples 15 to 17]
Production of base-reactive resin composition (5):
The sorbitol polyglycidyl ether (Denacol (registered trademark) EX-622 / manufactured by Nagase ChemteX Corp.) 0.03 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) is 0.0045 g (15 parts by mass with respect to 100 parts by mass of the epoxy compound, 10 mol% with respect to the epoxy compound), and the base proliferating agent obtained in Example 8 is as follows. The base-reactive resin composition of this invention was obtained by making it contain by content of.

(Content of base proliferating agent)
Content (g) Mass part mol% (Note)
Example 15 0.010 33 13 mol%
Example 16 0.020 67 33 mol%
Example 17 0.030 100 50 mol%
(Note) For epoxy compounds

[Reference Example 2]
Production of resin composition (2)
In Example 15, a resin composition was obtained in the same manner as in Example 15 except that the base proliferating agent obtained in Example 8 was not added.

[Test Example 12]
Curing confirmation (6) (confirmation of heating time dependency):
The base-reactive resin composition obtained in Example 17 was dissolved in 0.3 g of chloroform (CHCl ₃ ) to obtain a sample solution. The sample solution was bar-coated on a glass substrate to form a film, heated at 100 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 1.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 100, 1000, and 5000 mJ / cm ² , and the hardness of the coating film after heating at 140 ° C. for 20 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 0 minutes (no heating: blank), 40 minutes, and 60 minutes, and compared and evaluated. FIG. 20 shows the relationship between the exposure amount and the pencil hardness.

As shown in FIG. 20, the cured higher the heating temperature at the exposure amount 1000 mJ / cm ² or more advanced, the heating time as 60 minutes, when the exposure amount was 1000 and 5000 mJ / cm ^2, hardness of 2H was gotten.

[Test Example 13]
Curing confirmation (7) (confirmation of content dependency):
The base-reactive resin composition obtained in Example 15 was dissolved in 0.3 g of chloroform (CHCl ₃ ) to obtain a sample solution. The sample solution was bar-coated on a glass substrate to form a film, heated at 100 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 1.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 100, 1000 and 5000 mJ / cm ² , and the hardness of the coating film after heating at 140 ° C. for 60 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 16, Example 17, and Reference Example 2, and compared and evaluated. FIG. 21 shows the relationship between the exposure amount and the pencil hardness.

As shown in FIG. 21, when the exposure amount 1000 mJ / cm ² or more as the content of the base multiplying agent increases the cure proceeds, the exposure amount was 5000 mJ / cm ^2, Example 16 H, Example In No. 17, a hardness of 2H was obtained.

[Example 18]
Production of base-reactive resin composition (6):
The sorbitol polyglycidyl ether (Denacol (registered trademark) EX-622 / manufactured by Nagase ChemteX Corp.) 0.02 g which is an epoxy compound represented by the formula (No. 4-13) is represented by the formula (E- 5) 0.003 g of the photobase generator represented by 5) (15 parts by mass with respect to 100 parts by mass of the epoxy compound, 18 mol% with respect to the epoxy compound), and 0% of the base proliferating agent obtained in Example 8 The base-reactive resin composition of this invention was obtained by making it contain by 0.02g (100 mass parts with respect to 100 mass parts of epoxy-type compounds, 50 mol% with respect to an epoxy-type compound).

[Reference Example 3]
Production of resin composition (3)
In Example 18, a resin composition was obtained in the same manner as in Example 18 except that the base proliferating agent obtained in Example 8 was not added.

[Test Example 14]
Curing confirmation (8) (presence or absence of base proliferator)
The base-reactive resin composition obtained in Example 18 was dissolved in 0.3 g of chloroform (CHCl ₃ ) to obtain a sample solution. The sample solution was bar-coated on a glass substrate to form a film, heated at 100 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 1.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 100, 1000 and 5000 mJ / cm ² , and the hardness of the coating film after heating at 120 ° C. for 60 minutes as post-baking was JIS K5600-5-4. In accordance with the pencil hardness measurement. Then, the same operation was performed on the base-reactive resin composition of Reference Example 3 and compared and evaluated. FIG. 22 shows the relationship between the exposure amount and the pencil hardness.

As shown in FIG. 22, in the system containing the base proliferating agent, the curing progressed as the exposure amount increased. When the exposure amount was 5000 mJ / cm ² , the hardness of F was obtained.

[Example 19 to Example 21]
Production of base-reactive resin composition (7):
The sorbitol polyglycidyl ether (Denacol (registered trademark) EX-622 / manufactured by Nagase ChemteX Corp.) 0.02 g which is an epoxy compound represented by the formula (No. 4-13) is represented by the formula (E- 6) The photobase generator represented by 6) is 0.002 g (10 parts by mass with respect to 100 parts by mass of the epoxy compound and 10 mol% with respect to the epoxy compound), and the base proliferating agent obtained in Example 9 is as follows. The base-reactive resin composition of this invention was obtained by making it contain by content of.

(Content of base proliferating agent)
Content (g) Mass part mol% (Note)
Example 19 0.008 40 20 mol%
Example 20 0.015 75 40 mol%
Example 21 0.023 115 60 mol%
(Note) For epoxy compounds

[Reference Example 4]
Production of resin composition (4)
In Example 19, a resin composition was obtained in the same manner as in Example 19 except that the base proliferating agent obtained in Example 9 was not added.

[Test Example 15]
Curing confirmation (9) (confirmation of content dependency):
The base-reactive resin composition obtained in Example 19 was dissolved in 0.2 g of chloroform (CHCl ₃ ) to prepare a sample solution. The sample solution was bar-coated on a glass substrate to form a film, heated at 100 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 1.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 100, 1000 and 5000 mJ / cm ² , and the hardness of the coating film after heating at 140 ° C. for 10 minutes as a post bake was 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 20, Example 21, and Reference Example 4, and compared and evaluated. FIG. 23 shows the relationship between the exposure amount and the pencil hardness.

As shown in FIG. 23, the curing progressed as the content of the base proliferating agent increased, and in Example 21, when the exposure amount was 5000 mJ / cm ² , the hardness of H was obtained.

[Test Example 16]
Comparison of thermal decomposition temperature using TG-DTA:
It was confirmed by TG-DTA (differential thermo-thermogravimetry) whether the base proliferating agent according to the present invention shifts the thermal decomposition temperature to the low temperature side in the presence of epoxy. The base proliferating agent of Example 9 (T _d ⁵ = 186.0 ° C.) and PGMA (T _d ⁵ = 242 ° C.), which is an epoxy compound represented by the formula (No. 4-12), are mixed in a mass ratio. A resin composition having a proliferation agent / epoxy compound = 1/2 was prepared, and the thermal decomposition temperature was measured by TG-DTA (differential heat-thermogravimetry). The results are shown in FIG. 24 (base proliferation agent only) and FIG. 25 (resin composition), respectively.

  As shown in FIG. 24 and FIG. 25, by using a resin composition in which a base proliferating agent and an epoxy compound are mixed, the thermal decomposition temperature is lower than that of the base proliferating agent alone (186.0 ° C.). To 150 ° C.).

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 (9)

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

(In formula (A), R _{1 to} R 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, an aryl group having 6 to 14 carbon atoms, or carbon. Q represents 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, and an alkyl group having 7 to 15 carbon atoms. An arylalkyl group, a group represented by the following formula (B ₁ ) or a group represented by the following formula (B ₂ ), wherein R ₃ and Q may be bonded to each other to form a ring structure. An oxygen atom or a sulfur atom, Z is a hydrogen atom, W is an electron-attracting substituent or phenyl group having a Hammett substituent constant σ of 0 or more, i and j are each independently an integer of 1 or 2, i + j = 3.)

(In the 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 _{5 to} R ₈ each independently represents 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. When R ₃ and D ₁ of the formula (A) are the following formula (V ₂ ), m ₁ R ₁₇ and R ₁₈ and m ₂ when the D ₂ is the following formula (V ₃ ) ₁₉ , R ₂₀ , and R ₇ may form a ring structure by bonding at least two of these Rs together, X ′ is an oxygen atom or sulfur atom, Z ′ is a hydrogen atom, and W ′ is Hammett substituent constant σ is an electron-withdrawing substituent or phenyl group having 0 or more, and g and h are respectively In independently an integer of 1 or 2, g + h = 3 becomes, _{n 1} is an integer of 0 to 20.)

(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 R _{5 to} R ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or the number of carbon atoms, each having the formula (V ₁ ) or the following formula (V ₄ ). 6 represents an aryl group having 6 to 14 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, m ₁ R ₁₇ and R ₁₈ when R ₃ and D _{1 in} the formula (A) are the following formula (V ₂ ). M ₂ R ₁₉ and R ₂₀ when D ₂ is the following formula (V ₃ ), R ₇ , m ₃ R ₂₁ and R ₂₂ when D ₃ is the following formula (V ₄ ), and R ₁₁ is good .X 'and be bonded to form a cyclic structure of at least two R are together of these R "Is an oxygen atom or sulfur atom, Z 'and Z" are hydrogen atoms, W' and W "are electron-withdrawing substituents or phenyl groups having a Hammett substituent constant σ of 0 or more, and e, f, g And h are each independently an integer of 1 or 2, and e + f = 3 and g + h = 3, and n ₁ , n ₂ , and n ₃ each independently represent an integer of 0 to 20.)

(In the formula (V ₂ ), m ₁ R ₁₇ and R ₁₈ 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 ₁₉ and R ₂₀ 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 ₂₁ and R ₂₂ 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 base proliferating agent according to claim 1, wherein the formula (A) is represented by the following formula (A ₁ ).

(In the formula (A ₁ ), R ₁ , R ₂ , R ₃ , R ₄ , X, Z, W, i and j are the same as those in the above formula (A), R ₃ ′ is a hydrogen atom, carbon number 1 Represents an alkyl group having 12 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, and R ₃ and R ₃ ′ are bonded to each other to form a ring structure May be formed.) The base proliferating agent according to claim 1, wherein the formula (A) is represented by the following formula (A ₂ ).

(In the formula (A ₂ ), D ₁ and D ₂ , R _{1 to} R ₈ , n ₁ , X and X ′, Z and Z ′, W and W ′, g, h, i and j are the same as those in the formula (A ) And the same formula (B ₁ ).) The base proliferating agent according to claim 1, wherein 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 to} R ₁₂ , n ₁ , n ₂ and n ₃ , X, X ′ and X ″, Z, Z ′ and Z ″, W, W ′ and W ″, e, f, g, h, i, and j are the same as those in the formula (A) and the formula (B ₂ ). 2. The base proliferating agent according to claim 1, wherein at least one of the CZ _i W _j , CZ ′ _g W ′ _h, and CZ ″ _e W ″ _f is represented by the following formula (C).

(In Formula (C), Y ₁ and Y ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a nitro group.)   6. A base-reactive resin composition comprising the base proliferating agent according to claim 1 and a base-reactive compound including an epoxy compound.   A base-reactive resin composition comprising the base proliferating agent according to claim 1, a base generator, and a base-reactive compound including an epoxy compound.   The base-reactive resin composition according to claim 7, wherein the base generator is a photobase generator.   The base-reactive resin composition according to claim 6, wherein the base-reactive compound is an epoxy compound.

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