JP6265374B2 - Base proliferating agent and base-reactive resin composition containing the base proliferating agent - Google Patents

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

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

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

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

  As one of the means for overcoming the above problems, a method using a polymerization reaction or chemical reaction by a base catalyst, for example, a method of generating a base by the action of light and chemically denaturing a resin using this as a catalyst, A means for applying a photosensitive resin composition using a base generated by the above as a catalyst to a photoresist material, a photocuring material or the like has been studied. The compound having an epoxy group is cured by causing a crosslinking reaction by the action of a base to generate amines as initiators or catalysts in the epoxy resin layer by the action of light or heat, and then heated. Methods of curing by processing are provided. However, even when amines are used as an initiator or a catalyst, the curing rate of the epoxy compound was slow. In order to fully cure the epoxy compound, it takes a long time, and further heat treatment or the like needs to be performed at a high temperature in order to increase the curing rate.

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

JP 2000-330270 A JP 2002-128750 A

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

  The present invention has been made in view of the above problems, and can be used for, for example, a crosslinking reaction of an epoxy compound, can generate a new base by the presence of a base, and has an efficient base growth reaction. An object of the present invention is to provide a base proliferating agent that progresses automatically 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 first invention of the present invention is represented by the following formula (A).

（式（Ａ）中、Ｒ_１ 及びＲ _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、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、Ｒ _３ は水素原子、Ｒ _４ は炭素数５〜１０のシクロアルキル基であり、ＸはＳＯまたはＳＯ_２、をそれぞれ示す。）

(In Formula (A), R ₁ and R ₂ 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 arylalkyl group of 7 to 15 carbon atoms, _{R 3} is a hydrogen atom, _{R 4} is a cycloalkyl group having 5 to 10 carbon atoms, X is respectively SO or SO _2, a.)

  The base proliferating agent according to the second aspect of the present invention is represented by the following formula (A ′).

（式（Ａ’）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示し、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７及びＲ_８は互いに結合して環構造を作ってもよい。ｎは０〜２０の整数、ＸはＳＯまたはＳＯ_２、をそれぞれ示す。）

(In formula (A ′), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, 12 alkyl group, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ And R ₈ may combine with each other to form a ring structure, n represents an integer of 0 to 20, and X represents SO or SO _2. )

The base proliferating agent according to the third aspect of the present invention is represented by the following formula (A ′ ₂ ).

（式（Ａ’_２）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０はそれぞれ独立して、水素原子、炭素数１〜１２のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜１５のアリールアルキル基を示す。ＸはＳＯまたはＳＯ_２、をそれぞれ示す。）

(In Formula (A ′ ₂ ), R ₁ , R ₂ , R ₃ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, X represents SO or SO ₂ )

  The base-reactive resin composition according to the present invention comprises the base proliferating agent according to at least one of the first to third inventions described above and a base-reactive compound.

  The base-reactive resin composition according to the present invention comprises the base proliferating agent according to at least one of the first to third inventions described above, a base generator and a base-reactive compound.

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

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

  The base proliferating agent according to the present invention has high sensitivity, can be decomposed by the action of a base to generate a base in a chain, and has a heterocycle, so that the oxidation number of a heteroatom is changed. Thus, the base growth reaction rate can be freely controlled, and a base proliferating agent capable of generating bases in a chain is obtained. In addition, since the solubility in organic solvents is good and the compatibility with the base-reactive compound is high, when the base proliferating agent of the present invention is coexisted with a base-reactive compound such as an epoxy compound that reacts with a base, The base-reactive compound can be efficiently cured by the base generated by proliferation.

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

It is 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, a conversion rate, and an olefin production | generation rate. It is the figure which showed the relationship between a heating time and an olefin production rate. It is the figure which showed the relationship between heating time and peak intensity ratio. It is the figure which showed the relationship between heating time and peak intensity ratio. It is the figure which showed the sensitivity evaluation result (relationship between exposure amount and remaining film rate). It is the figure which showed the sensitivity evaluation result (relationship between exposure amount and remaining film rate). It is the figure which showed the sensitivity evaluation result (relationship between exposure amount and remaining film rate). It is the figure which showed the relationship between exposure amount and pencil hardness. It is the figure which showed the relationship between exposure amount and pencil hardness.

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

In formula (A), R ₁ , R ₂ , R ₃ and 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, or 6 to 14 carbon atoms. Or an arylalkyl group having 7 to 15 carbon atoms, X represents SO or SO ₂ , respectively.

In R ₁ and R ₂ in Formula (A), the alkyl group is preferably 1 to 6 carbon atoms, the cycloalkyl group is preferably 6 to 8 carbon atoms, and the aryl group is aryl. Preferably has 6 to 10 carbon atoms, and preferably 7 to 11 carbon atoms in the case of an arylalkyl group. Specific examples of R ₁ and R ₂ include, for example, methyl, ethyl, propyl, butyl, cyclohexyl, phenyl, tolyl, naphthyl, benzyl, phenethyl, naphthylmethyl and the like.

In R ₃ and R ₄ in Formula (A), when an alkyl group is used, the number of carbon atoms is preferably 2 to 6, and examples thereof include ethyl, propyl, butyl, hexyl and the like. In the case of a cycloalkyl group, the carbon number is preferably 6 to 8, and examples thereof include cyclohexyl and cyclooctyl. In the case of an aryl group, the carbon number is preferably 6 to 10, and examples thereof include phenyl, tolyl, naphthyl and the like. In the case of an arylalkyl group, the carbon number is preferably 7 to 11, and examples thereof include benzyl, phenethyl, naphthylmethyl and the like.

  The 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, an acyloxy group, and a hydroxy group. Etc.

  The base proliferating agent according to the second invention of the present invention is a compound represented by the following formula (A ′).

In formula (A ′), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, 1 to 12 carbon atoms. An alkyl group, 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 , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be bonded to each other to form a ring structure. n represents an integer of 0 to 20, and X represents SO or SO ₂ .

In R < ₁ >, R < ₂ >, R < ₉ > and R < ₁₀ > in formula (A '), the number of carbon atoms is preferably 1-6 when it is an alkyl group, and the number of carbon atoms is 6-8 when it is a cycloalkyl group. In the case of aryl, the carbon number is preferably 6 to 10, and in the case of an arylalkyl group, the carbon number is preferably 7 to 11. Specific examples of R ₁ and R ₂ include, for example, methyl, ethyl, propyl, butyl, cyclohexyl, phenyl, tolyl, naphthyl, benzyl, phenethyl, naphthylmethyl and the like.

In _{R 3, R 4, R 5} , R 6, R 7 and _{R 8} of formula (A '), the number of carbon atoms in the case of the alkyl group is 2-6 are preferable, for example, ethyl, propyl, butyl, hexyl Etc. In the case of a cycloalkyl group, the carbon number is preferably 6 to 8, and examples thereof include cyclohexyl and cyclooctyl. In the case of an aryl group, the carbon number is preferably 6 to 10, and examples thereof include phenyl, tolyl, naphthyl and the like. In the case of an arylalkyl group, the carbon number is preferably 7 to 11, and examples thereof include benzyl, phenethyl, naphthylmethyl and the like.

  The 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, an acyloxy group, and a hydroxy group. Etc.

  Further, n in the formula (A ′) is an integer of 0 to 20, but is preferably an integer of 0 to 8.

Furthermore, the base proliferating agent according to the third invention of the present invention, which is a type of the second invention described above, is a compound represented by the following formula (A ′ ₂ ).

In formula (A ′ ₂ ), R ₁ , R ₂ , R ₃ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, carbon 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 is shown. X represents SO or SO ₂ , respectively.

Similarly to formula (A ′), in R ₁ , R ₂ , R ₉ and R ₁₀ of formula (A ′ ₂ ), when an alkyl group is used, the number of carbon atoms is preferably 1 to 6, and a cycloalkyl group The number of carbon atoms is preferably 6-8, and in the case of aryl, the carbon number is preferably 6-10, and in the case of an arylalkyl group, the carbon number is preferably 7-11. Specific examples of R ₁ and R ₂ include, for example, methyl, ethyl, propyl, butyl, cyclohexyl, phenyl, tolyl, naphthyl, benzyl, phenethyl, naphthylmethyl and the like.

In R ₃ , R ₆ , R ₇ and R ₈ in the formula (A ′ ₂ ), the alkyl group is preferably 2 to 6 carbon atoms, and examples thereof include ethyl, propyl, butyl, and hexyl. In the case of a cycloalkyl group, the carbon number is preferably 6 to 8, and examples thereof include cyclohexyl and cyclooctyl. In the case of an aryl group, the carbon number is preferably 6 to 10, and examples thereof include phenyl, tolyl, naphthyl and the like. In the case of an arylalkyl group, the carbon number is preferably 7 to 11, and examples thereof include benzyl, phenethyl, naphthylmethyl and the like.

  The 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, an acyloxy group, and a hydroxy group. Etc.

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

Specific examples (formula (Q-1) and formula (Q-2)) when R ₃ is a hydrogen atom and R ₄ is a cycloalkyl group having 5 to 10 carbon atoms in the formula (A).

A specific example in which R ₄ , R ₅ , R ₆ and R ₇ are hydrogen atoms and n is 4 in Formula (A ′) ((Formula (Q-3)).

In formula (A ′), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are bonded to each other to produce a ring structure (formula (Q-4) and formula (Q-5) ).

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

(Reaction scheme: Formula (A))

(Reaction scheme: Formula (A ′))

(Reaction scheme: Formula (A ′ ₂ ))

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

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

  Since the base proliferating agent according to the present invention is highly soluble in an organic solvent, when mixed with a base-reactive compound to form a base-reactive resin composition, the base-reactive compound is easily mixed. The

  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.

As the base generated by decomposition of the base proliferating agent represented by the formula (A), formula (A ′) or formula (A ′ ₂ ), the following formula (Am-1), formula (Am-2) or formula A primary amine or a secondary amine represented by (Am-3) is generated. In the formula, R _{3 to} R ₈ conform to the formula (A), the formula (A ′), and the formula (A ′ ₂ ).

In order to synthesize the base proliferating agent represented by the formula (A), formula (A ′) or formula (A ′ ₂ ), for example, using thioxanthone or a derivative thereof as a starting material, the following synthesis scheme is used. Good. In addition, the following scheme is an example, and there is no problem in synthesizing the base proliferating agent of the present invention by a method other than the following scheme. In the scheme, for convenience, some R groups are shown as hydrogen atoms.

(Synthesis scheme)

(Synthesis scheme)

(Synthesis 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. A scheme when a photobase generator is used is shown.

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.

Examples of the photobase generator include JP2009-280785A and JP2010-8.
The base generator etc. which are indicated by 4144 gazette and JP, 2011-236416, A can be used. These are carboxylates composed of carboxylic acids and bases that are decarboxylated by light irradiation.

Moreover, the photobase generator represented by the following formula | equation can also be used. Formula (B-3)
In the formula, —R— represents — (CH ₂ ) ₆ — or —CH ₂ CH ₂ CH ₂ CH (CH ₃ ).
CH ₂ - shows the.

  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 generating agent are used in combination as a base proliferating agent composition, the mixing ratio of the base proliferating agent and the base generating agent is in mass ratio (even molar ratio), and base proliferating agent / base generating agent = 40. / 1 to 5/20 is preferable. 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 5/5 in mass ratio (even molar ratio).

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 base proliferating agents represented by the above formula (A), formula (A ′) and formula (A ′ ₂ ), or Such a base proliferating agent and base generating agent (base proliferating agent composition) and a base reactive compound that undergoes a curing reaction in the presence of a base are contained as essential components.

  The base-reactive compound constituting the base-reactive resin composition of the present invention reacts with the action of a base generated by a base proliferating agent or a base proliferating agent and a base generator (base proliferating agent composition), and crosslinks. For example, the following No. 2-1. The compound of 5-6 etc. can be used. In particular, it is preferable to use, for example, an epoxy compound having at least one epoxy group, a silicon compound having at least one alkoxysilyl group or silanol group, an oxetane compound containing an oxetane ring, and the like. Such base-reactive compounds may be used alone or in combination of two or more.

  Moreover, a base growth agent may be used individually by 1 type, and may be used in combination of 2 or more type. When a base proliferating agent and a base generator are used in combination as a base proliferating agent composition, one type of base generator may be used alone, or two or more types may be combined. It may be used.

  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. And these epoxy compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the silicon-based compound (silicon-based resin), for example, an alkoxysilane compound or a silane coupling agent can be used. Examples of alkoxysilane compounds include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, phenyl Examples include trimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. These alkoxysilane compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  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 individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

(scheme)

  Hereinafter, specific examples of the base-reactive compound will be given. The following No. 2-1. Among the 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 a desorption reaction by the action of a base and whose polarity is changed, and as a material (resist material) that performs patterning using the fact that solubility changes before and after decomposition. Can be applied.

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 substance (mixture) No. 3-1 undergoes dehydration condensation and crosslinking reactions by the action of the base. No. The substance (mixture) 3-2 causes dehydration condensation and crosslinking reaction by the action of the base. No. 3-3 substance (polymer) causes a decarboxylation reaction by the action of a base. The No. 3-4 substance causes an imide formation reaction by the action of a base. No
. 3-1. In 3-2, x represents a number exceeding 0 and 1 or less.

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

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

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

A base-reactive resin composition containing a base proliferating agent and a photobase generator (as a base proliferating agent composition) in combination with the above-mentioned photobase generator or the base proliferating agent of the present invention and a photobase generator ( In the photosensitive resin composition), the range of the wavelength of the irradiation light and the exposure amount include the type and amount of the photobase generator, and the base reactive compound constituting the base reactive resin composition (photosensitive resin composition). What is necessary is just to determine suitably according to a kind etc., For example, what is necessary is just to select and apply within the range of 190-400 nm as a wavelength, and 100-10000 mJ / cm < ² > as an exposure amount, By using the sensitizer mentioned later. It is also possible to use a higher wavelength region. 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 the thermal base generator include the type and amount of the thermal base generator used, the type of the base reactive compound constituting the base reactive resin composition (photosensitive resin composition), and the like. 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. What is necessary is just to select from the range of 0.1-300 mass parts, and it is preferable to set it as 0.1-60 mass parts. 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. Is more preferable, and 2 to 15 parts by mass is particularly preferable. Moreover, you may make it contain from the range of 0.1-50 mol per monomer unit of a base reactive compound (an epoxy-type compound or a silicon-type compound). The base proliferating agent may be selected from the range of 10 to 90 mol% in terms of the amine functional group ratio of the base proliferating agent to 100 mol of the epoxy group in the base-reactive compound, and should be 40 to 80 mol%. Is preferred. The amine functional group ratio is expressed as mol% of the number of amino groups in the base proliferating agent with respect to the number of epoxy groups in the epoxy compound when the target base reactive compound is an epoxy compound, for example. Yes, for example, an amine functional group ratio of 10 mol% (with respect to epoxy group) means that 10 amino groups (10 mol) are generated from the base proliferating agent with respect to 100 epoxy groups (100 mol) in the base-reactive compound. It refers to a base proliferating agent (the same applies to the amine functional group ratio for the base generator described later). In the above description, an epoxy compound having an epoxy group is taken as an example of the base-reactive compound, but the same applies to other base-reactive compounds such as silicon compounds.

  In the case where a base proliferating agent and a base generating agent are used in combination and the base reactive compound is contained as a base proliferating agent composition, the content of the base generating agent is the amount of the base proliferating agent and the base generating agent described above. It is preferable to contain a base generator so as to correspond to the blending ratio. Moreover, it is preferable to set it as 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 30 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the base-reactive compound, and 5 to 20 parts by mass. It is particularly preferable to do this. Moreover, you may make it contain from the range of 0.1-50 mol per monomer unit of a base reactive compound (an epoxy-type compound or a silicon-type compound). The base generator may be selected from the range of 5 to 90 mol% in terms of the amine functional group ratio of the base generator to 100 mol of the epoxy group in the base-reactive compound, and it should be 10 to 80 mol%. Is preferred.

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

  The base-reactive resin composition of the present invention preferably further contains a thiol compound. The thiol compound acts as a curing functional group such as epoxy when used in combination with an epoxy compound or the like. As the thiol compound, a polythiol compound having two or more thiol groups is preferably used. For example, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), dipentaerythritol hexakis. (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3 -Mercaptoisobutyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), tris [(3-mercaptopropionyloxy) Ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), diethylene glycol bis (3-mercaptopro) 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 individually by 1 type, and may be used in combination of 2 or more type.

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

  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.

  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 130 ° C. The heating time is preferably 10 seconds to 60 minutes, particularly preferably 60 seconds to 30 minutes. 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.

  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. These sensitizers may be used alone or in combination of two or more.

  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, cyclohexene, dipentene, n-pentane, isopentane, n-hexane, Saturated or unsaturated hydrocarbon compounds such as isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; diethyl ether, di-n-propyl ether, Di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibuty 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 monoethyl ether acetate, ethylcyclohexane, methylcyclohexane, p-menthane, o- Ethers such as dipropyl ether and dibutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone and cycloheptanone; Examples thereof include esters such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl acetate cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, and butyl stearate. One type of these solvents may be used alone, or two or more types may be used in combination.

  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, and a filler. One of these may be used alone, or two or more may be used in combination.

  The base-reactive resin composition of the present invention described above is a base generated from a base proliferating agent by containing the base proliferating agent of the present invention or the base proliferating agent of the present invention, a base generator and a base-reactive compound. The reaction between the epoxy compound and the epoxy compound proceeds in a chain, resulting in an excellent curing rate and reaction efficiency. The base reactive resin composition is cured quickly and sufficiently cured. 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, this invention is not limited to this Example at all.

[Production Example 1]
Intermediate production (1)
50 mL of dehydrated diethyl ether was placed in a 300 mL four-necked flask, and 1.6 g (44 × 10 ⁻³ mol) of lithium aluminum hydride was slowly added thereto while stirring. While stirring the inside of the flask in an ice bath, a solution prepared by dissolving 5.6 g (84 × 10 ⁻³ mol) of aluminum chloride in 50 mL of dehydrated diethyl ether was slowly added dropwise. Thereafter, 5.0 g (24 × 10 ⁻³ mol) of thioxanthone represented by the following formula (H-1) was added little by little to the reaction system, and when all was added, the mixture was stirred at reflux for 30 minutes. After completion of the reaction, ice was gradually added to the reaction system, HClaq was slowly added to dissolve the residue, and extraction was performed with diethyl ether. The organic layer was extracted three times each with NaHCO ₃ aq and NaClaq, and finally the organic layer was dried over magnesium sulfate. Then, the solvent was distilled away with an evaporator and dried under reduced pressure, thereby obtaining 4.5 g (yield 95%) of a pale yellow solid of an intermediate (compound) represented by the following formula (H-2).

[Production Example 2]
Intermediate production (2)
A 200 mL two-necked eggplant flask is charged with 1.0 g (5.0 × 10 ⁻³ mol) of an intermediate represented by the formula (H-2) and 0.3 g (10 × 10 ⁻³ mol) of p-formaldehyde and nitrogen. Under atmosphere, 40 mL of dehydrated diethyl ether was added and placed in an ice bath. To this, 3.2 mL (5.0 × 10 ⁻³ mol) of n-butyllithium in hexane was slowly added dropwise, and the mixture was refluxed and stirred for 15 minutes after the completion of the addition. After completion of the reaction, ice was gradually added to the reaction system, 25% H ₂ SO ₄ aq was slowly added to dissolve the residue, and extraction was performed with diethyl ether. The organic layer was extracted three times each with NaHSO ₃ aq and NaClaq, and finally the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off with an evaporator, and column chromatography (developing solvent hexane: ethyl acetate = 3: 1) was performed, followed by drying under reduced pressure, whereby an intermediate (compound) represented by the following formula (H-3) was a white solid. Was obtained in a yield of 0.7 g (57% yield).

[Production Example 3]
Production of intermediate (3):
In a 100 mL eggplant flask, 0.20 g (0.8 × 10 ⁻³ mol) of the intermediate represented by the formula (H-3) was added and dissolved in 10 mL of dichloromethane. M-Chloroperbenzoic acid 0.2g (1.2 * 10 < ^-3 > mol) was added here, and it stirred at room temperature for 1 day. After completion of the reaction, water was added to the reaction system little by little and extracted with dichloromethane. The organic layer was extracted three times each with NaHCO ₃ aq and NaClaq, and finally the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off by an evaporator, and column chromatography (developing solvent hexane: ethyl acetate = 1: 3) was performed, followed by drying under reduced pressure. Thus, an intermediate white solid represented by the following formula (H-5) was obtained in a yield of 0. .14 g (69% yield) and an intermediate (compound) represented by the following formula (H-6) were obtained in a yield of 0.01 g (yield 4%).

In this reaction, 1.0 g (4.4 × 10 ⁻³ mol) of the intermediate represented by the formula (H-3), 40 mL of dichloromethane, and 2.5 g (14.0) of m-chloroperbenzoic acid are used. × give ¹⁰ -3 intermediate represented by the following formula (H-6) by the mol) of white solid (compound) in a yield of 0.9 g (86% yield).

[Example 1]
Production of base proliferating agent (1):
In a 50 mL eggplant flask, 0.20 g (0.8 × 10 ⁻³ mol) of the intermediate represented by the formula (H-6) and 0.06 g (0.1 × 10 ⁻³ mol) of dibutyltin dilaurate (IV) Was dissolved in a mixed solvent of 10 mL of dehydrated benzene and 15 mL of dehydrated acetonitrile. A solution prepared by dissolving 0.2 g (1.2 × 10 ⁻³ mol) of cyclohexyl isocyanate in 1 mL of dehydrated benzene was added dropwise thereto and stirred at room temperature for 6 hours. After completion of the reaction, the solvent was distilled off with an evaporator, and column chromatography (developing solvent hexane: ethyl acetate = 4: 1) was performed and dried under reduced pressure, whereby a white solid of a base proliferating agent represented by the following formula (A-1) Was obtained in a yield of 0.2 g (yield 74%).

[Example 2]
Production of base proliferating agent (2):
0.75 g (2.9 × 10 ⁻³ mol) of the intermediate represented by the formula (H-6) and 0.18 g (0.3 × 10 ⁻³ mol) of dibutyltin dilaurate (IV) in a 50 mL eggplant flask Was dissolved in a mixed solvent of 30 mL of dehydrated benzene and 30 mL of dehydrated acetonitrile. A solution prepared by dissolving 0.2 g (1.2 × 10 ⁻³ mol) of hexamethylene diisocyanate in 1 mL of dehydrated benzene was added dropwise thereto and stirred at room temperature for 10 hours. After completion of the reaction, the solvent was distilled off by an evaporator, and column chromatography (developing solvent hexane: ethyl acetate = 4: 1) was performed and dried under reduced pressure, whereby a white base proliferating agent represented by the following formula (A′-1) was obtained. A solid was obtained in a yield of 0.69 g (69% yield).

[Example 3]
Production of base proliferating agent (3):
In a 50 mL eggplant flask, 0.50 g (1.9 × 10 ⁻³ mol) of the intermediate represented by the formula (H-6) and 0.12 g (0.2 × 10 ⁻³ mol) of dibutyltin dilaurate (IV) Was dissolved in a mixed solvent of 30 mL of dehydrated benzene and 30 mL of dehydrated acetonitrile. A solution prepared by dissolving 0.21 g (0.96 × 10 ⁻³ mol) of isophorone diisocyanate in 1 mL of dehydrated benzene was added dropwise thereto and stirred at room temperature for 12 hours. After completion of the reaction, the solvent was distilled off with an evaporator, and column chromatography (developing solvent hexane: ethyl acetate = 4: 1) was performed and dried under reduced pressure, whereby the white of the base proliferating agent represented by the following formula (A′-2) A solid was obtained in a yield of 0.50 g (70% yield).

[Example 4]
Production of base proliferating agent (4):
In a 100 mL eggplant flask, 0.2 g (0.8 × 10 ⁻³ mol) of the intermediate represented by the formula (H-5) and 0.06 g (0.1 × 10 ⁻³ mol) of dibutyltin dilaurate (IV) Was dissolved in 20 mL of dehydrated acetonitrile. A solution prepared by dissolving 0.1 g (0.8 × 10 ⁻³ mol) of cyclohexyl isocyanate in 1 mL of dehydrated acetonitrile was added dropwise thereto and stirred at room temperature for 1 day. After completion of the reaction, the solvent was distilled off by an evaporator, and column chromatography (developing solvent hexane: ethyl acetate = 1: 1) was performed and dried under reduced pressure, whereby a white solid of a base proliferating agent represented by the following formula (A-2) Was obtained in a yield of 0.3 g (yield 89%).

[Production Example 4]
Production of photobase generator (1):
In a 100 mL eggplant flask, 0.3 g (1.4 × 10 ⁻³ mol) of 4,5-dimethoxy-2-nitrobenzyl alcohol and 0.06 g (0.1 × 10 ⁻³ mol) of dibutyltin dilaurate (IV) were added. And dissolved in 18 mL of dehydrated benzene. A solution prepared by dissolving 0.2 g (1.4 × 10 ⁻³ mol) of cyclohexyl isocyanate in 2 mL of dehydrated benzene was added dropwise thereto and stirred at reflux for 3 hours. After completion of the reaction, the cooled crystals are suction filtered and dried under reduced pressure, yielding 0.3 g (95% yield) of a pale yellow solid of the photobase generator represented by the formula (B-1). Got in.

[Production Example 5]
Production of photobase generator (2):
A photobase generator represented by the formula (B-2) was obtained according to the method described in Production Example 4.

[Production Example 6]
Production of photobase generator (3):
A photobase generator (R: — (CH ₂ ) ₆ —) represented by the formula (B-3) was obtained according to the method described in Production Example 4 described above.

[Test Example 1]
Confirmation of solubility in organic solvents:
The solubility of the base proliferating agent obtained in Examples 1 to 4 in an organic solvent was confirmed. The results are shown in FIG. The solubility of the base proliferating agent was confirmed by the amount of solvent dissolved in 0.01 g of the base proliferating agent. In FIG. 1, 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 9 mL. "When exceeding 10 mL, indicated as"-". For comparison, a compound represented by the following formula (C) was also evaluated.

  FIG. 1 is a diagram showing the solubility in an organic solvent such as a base proliferating agent. As shown in FIG. 1, the base proliferating agents of Examples 1 to 4 showed good solubility in organic solvents.

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

In the NMR sample tube, the base proliferating agent 70 × 10 ⁻³ mol / L obtained in Example 1, the base cyclohexylamine 13 × 10 ⁻³ mol / L, dioxane-d ₈ as a solvent, and mesitylene as an internal standard solution. 13 × 10 ⁻³ mol / L was added, sealed, and heated at 100 ° C. for a predetermined time. 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 was added. FIG. 2 shows the relationship between the heating time, the conversion rate, and the olefin production rate. The olefin production rate was calculated from a ¹ H-NMR spectrum.

  As shown in FIG. 2, the system to which the base (cyclohexylamine) common to the base composing the base proliferating agent is added can obtain a nonlinear reaction curve peculiar to the growth reaction and decomposes more efficiently than the system to which no base is added. It was confirmed that olefin was produced.

  Table 1 shows the results of the slope of the straight line after the acceleration of the half-life and nonlinear response curves.

(Half life and slope)

[Test Example 3]
Confirmation of degradation behavior of base proliferator in solution (2)
In an NMR sample tube, the base proliferating agent 70 × 10 ⁻³ mol / L obtained in Example 4, diazabicycloundecene (DBU) 13 × 10 ⁻³ mol / L as a base, and methanol-d ₄ as a solvent. Then, mesitylene 13 × 10 ⁻³ mol / L was added as an internal standard solution, sealed, and heated at 100 ° C. for a predetermined time. Then, by analyzing the generated olefin peak by ¹ H-NMR, the decomposition behavior of the base proliferating agent (generation of olefin) was confirmed, and when cyclohexylamine was added instead of DBU as the base, and the base was added. Compared to not doing. The relationship between the heating time and the olefin production rate is shown in FIG. The olefin production rate was calculated in the same manner as in Test Example 1.

  As shown in FIG. 3, the system to which the base (DBU) common to the base constituting the base proliferating agent is added has a nonlinear reaction curve peculiar to the growth reaction and decomposes more efficiently than the system to which no base is added. It was confirmed that olefin was produced.

  Table 2 shows the results of the slope of the straight line after the acceleration of the half-life and non-linear response curves.

(Half life and slope)

[Test Example 4]
Confirmation of decomposition behavior of base proliferating agent in polymer solid (polystyrene) (1):
0.023 g (0.060 × 10 ⁻³ mol%) of the base proliferating agent obtained in Example 1 against 0.058 g of polystyrene (manufactured by Sigma-Aldrich, Mw = 280000) (based on 100 parts by mass of polystyrene) 40 parts by mass) and 0.0023 g (4 parts by mass with respect to 100 parts by mass of polystyrene) of the photobase generator represented by the formula (B-1) were added to obtain a resin composition. Such a resin composition is dissolved in 1 g of tetrahydrofuran (THF) as a cast solvent to form a sample solution. This sample solution is spin-coated on a silicon wafer at 3000 rpm for 30 seconds, and prebaked at 100 ° C. for 30 seconds on a hot plate. To form a film. The film was irradiated with light of 100, 1000, 10000 J / cm ² at a wavelength of 365 nm, heated at 60 ° C. for a predetermined time, and converted to a peak of carbonyl group (C═O) (1757 cm ⁻¹ ) by IR spectrum. ) Was traced to confirm the degradation behavior of the base proliferating agent (the system without exposure (0 mJ / cm ² ) was also implemented as a blank). The relationship between the heating time and the peak intensity ratio is shown in FIG. The conversion rate of the carbonyl group is
Calculation was performed based on the peak intensity before the start of heating.

As shown in FIG. 4, the exposed system showed nonlinear decomposition behavior in which decomposition proceeds immediately after heating. This means that the base was present in the system due to exposure, and the concentration of the base increased with the subsequent heating, and the decomposition progressed explosively when a certain threshold was exceeded, that is, the base growth reaction proceeded. Means that. On the other hand, the non-exposure system (shown as 0 mJ / cm ² ) was slower decomposed than the base-added system. From the above, it was confirmed that the base proliferating agent was autocatalytically decomposed in the polymer solid using a small amount of base generated by light irradiation of the photobase generator as a trigger.

[Test Example 5]
Confirmation of decomposition behavior of base proliferating agent in polymer solid (polystyrene) (2):
0.023 g (0.062 × 10 ⁻³ mol%) of the base proliferating agent obtained in Example 4 against 0.058 g of polystyrene (manufactured by Sigma-Aldrich, Mw = 280000) (based on 100 parts by mass of polystyrene) 40 parts by mass), and 1.0 × 10 ⁻³ g (about 1.7 parts by mass with respect to 100 parts by mass of polystyrene) of cyclohexylamine as a base was contained to obtain a resin composition. This resin composition is dissolved in 1 g of chloroform as a casting solvent to prepare a sample solution. This sample solution is spin-coated on a silicon wafer at 3000 rpm for 30 seconds and prebaked at 100 ° C. for 30 seconds on a hot plate. Filmed. This membrane was heated at 120 ° C. for a predetermined time, and the decomposition behavior of the base proliferating agent was confirmed by following the peak (1757 cm ⁻¹ ) of the carbonyl group (C═O) to be converted by IR spectrum. It compared with the case where no is added. FIG. 5 shows the relationship between the heating time and the peak intensity ratio. The conversion rate of the carbonyl group was calculated based on the peak intensity before the start of heating.

  As shown in FIG. 5, the system to which the base (cyclohexylamine) was added showed a nonlinear decomposition behavior in which the decomposition proceeds immediately after heating. This means that the decomposition of the base progressed explosively when the concentration of the base increased in the system and exceeded a certain threshold value, that is, the base growth reaction proceeded. On the other hand, in the system in which no base was added, decomposition was slower than in the system in which the base was added. From the above, it was confirmed that the base proliferating agent autocatalytically decomposes in the polymer solid using a small amount of base as a trigger.

[Test Example 6]
Confirmation of photoinsolubilization behavior in PGMA (1):
Formula polyglycidyl methacrylate is an epoxy compound represented by the _{(No.4-12) (PGMA: M W} = 13000) 0.1g respect, monomer units of PGMA the base multiplying agent obtained in Example 1 The resin composition was prepared by containing 2.2 mol% of the photobase generator represented by the formula (B-1) with respect to PGMA monomer units. By dissolving the obtained resin composition in 1.0 g of chloroform to obtain a sample solution, spin-coating the sample solution on a silicon wafer at 3000 rpm for 30 seconds, and prebaking on a hot plate at 60 ° C. for 1 minute, A film having a thickness of 0.5 μm was produced. This film was irradiated with a monochromatic light of 365 nm with a predetermined exposure amount, the post-baking temperature was set to 100 ° C., the heating time was carried out for 20 minutes, developed with chloroform for 1 minute, the thickness of the remaining film was measured, and the exposure was performed. A relationship (sensitivity curve) between the amount and the remaining film rate was created. And the sensitivity curve was created by making heating time into 40 minutes and 60 minutes. The results are shown in FIG. As shown in FIG. 6, the light insolubilization behavior of PGMA was confirmed with an exposure dose exceeding 1000 mJ / cm ² .

[Test Example 7]
Confirmation of photoinsolubilization behavior in PGMA (2):
Equation (No.4-12) polyglycidyl methacrylate is an epoxy compound represented by the _{(PGMA: M W = 13000)} 0.1g respect, monomer units of PGMA The resulting base amplifier in Example 2 The resin composition was obtained by adding 3.7 mol% of the photobase generator represented by the formula (B-1) to 2.2 mol% of the monomer unit of PGMA. By dissolving the obtained resin composition in 1.0 g of chloroform to obtain a sample solution, spin-coating the sample solution on a silicon wafer at 3000 rpm for 30 seconds, and prebaking on a hot plate at 60 ° C. for 1 minute, A film having a thickness of 0.5 μm was produced. This film was irradiated with a monochromatic light of 365 nm with a predetermined exposure amount, the post-baking temperature was set to 60 ° C., the heating time was performed for 10 minutes, the film was developed with chloroform for 1 minute, the thickness of the remaining film was measured, and the exposure was performed. A relationship (sensitivity curve) between the amount and the remaining film rate was created. And the sensitivity curve was created by heating time as 20 minutes and 40 minutes. The results are shown in FIG. As shown in FIG. 7, the light insolubilization behavior of PGMA was confirmed with an exposure dose exceeding 100 mJ / cm ² .

  FIG. 8 shows the results of Test Example 6 and Test Example 7 together with a sensitivity curve when the heating time is 40 minutes (for Test Example 6, a photobase without containing a base proliferating agent). The result (heating temperature: 100 ° C.) carried out by containing only the generator is also shown. As shown in FIG. 8, the sensitivity was increased by containing a base proliferating agent, and the sensitivity was higher in the system containing the base proliferating agent of Example 2.

[Example 5 and Example 6]
Production of base-reactive resin composition (1):
Polymethacrylic acid 3- (trimethoxysilyl) propyl is an epoxy compound represented by the formula _{(No.5-6) (PMAS, M W} = 20000) against 0.1 g, in the formula (B-3) The base-reactive resin composition of the present invention is contained by adding the photobase generator represented by 2.5 mol% with respect to the monomer unit of PMAS and the base proliferating agent obtained in Example 2 in the following content. Obtained.

(Content of base proliferating agent)
For epoxy compounds (mol% to monomer units)
Example 5 7.2 mol%
Example 6 14.0 mol%

[Reference Example 1]
Production of resin composition (1)
In Example 5, a resin composition was obtained using the same method as in Example 4 except that the base proliferating agent obtained in Example 2 was not added.

[Test Example 8]
Curing confirmation (1) (confirmation of heating temperature dependence):
The base-reactive resin composition obtained in Example 6 was dissolved in 1.0 g of chloroform (CHCl ₃ ) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 1 minute and prebaked to prepare a coating film having a thickness of 5.0 μm. The coating film after heating at 60 ° C. for 40 minutes as a post-baking with a monochromatic light of 365 nm on this coating film with an exposure amount of 0 (blank), 100, 1000, 5000 and 10000 mJ / cm ² and JIS K5600-5 The pencil hardness was measured according to 4. Then, similar operations were carried out at post-baking heating temperatures of 80 ° C. and 100 ° C. for comparison and evaluation. A result is shown to Fig.9 (a).

[Test Example 9]
Curing confirmation (2) (confirmation of heating time dependency):
The base-reactive resin composition obtained in Example 6 was dissolved in 1.0 g of chloroform (CHCl ₃ ) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 1 minute, prebaked, heated and prebaked to prepare a coating film having a thickness of 5.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 100, 1000, 5000 and 10000 mJ / cm ² , and the hardness of the coating film after heating at 80 ° C. for 20 minutes as post-baking was JIS K5600-5 The pencil hardness was measured according to 4. The same operation was performed with post-baking heating time of 40 minutes and 60 minutes, and compared and evaluated. The result is shown in FIG.

[Test Example 10]
Curing confirmation (3) (confirmation of addition amount dependency):
The base-reactive resin composition obtained in Example 5 was dissolved in 1.0 g of chloroform (CHCl ₃ ) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 1 minute, prebaked, heated and prebaked to prepare a coating film having a thickness of 5.0 μm. The coating film after heating at 80 ° C. for 40 minutes as a post-baking with a monochromatic light of 365 nm, exposure doses of 0 (blank), 100, 1000, 5000 and 10000 mJ / cm ² as JIS K5600-5 The pencil hardness was measured according to 4. And the same operation was implemented with respect to the base reactive resin composition etc. of Example 6 and Reference Example 1, and compared and evaluated. The result is shown in FIG.

  As shown in FIG. 9, it was confirmed that curing progressed as the heating temperature was increased, the heating time was increased, and the content of the base proliferating agent was increased.

[Examples 7 to 9]
Production of photosensitive resin composition (2):
The sorbitol polyglycidyl ether (Denacol (registered trademark) EX-622 / manufactured by Nagase ChemteX Corp.) 0.1 g which is an epoxy compound represented by the formula (No. 4-13) is represented by the formula (B- 2) 0.031 g of photobase generator represented by (31 parts by mass with respect to 100 parts by mass of the epoxy compound) (amine functional group ratio: 10 mol% (vs. epoxy group)), the base obtained in Example 3 The photosensitive resin composition of this invention was obtained by containing a proliferation agent with the following content.

(Content of base proliferating agent)
Content (g) Mass parts Amine functional group ratio (Note)
Example 7 0.14 140 40 mol%
Example 8 0.21 210 60 mol%
Example 9 0.27 270 80 mol%
(Note) Epoxy group (mol%)

[Reference Example 2]
Production of resin composition (2)
In Example 7, a resin composition was obtained using the same method as in Example 6 except that the base proliferating agent obtained in Example 3 was not added.

[Test Example 11]
Curing confirmation (4) (confirmation of heating temperature dependence):
The base-reactive resin composition obtained in Example 8 was dissolved in 1.0 g of chloroform (CHCl ₃ ) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 5.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was set to 0 (blank), 1000, 5000, and 10000 mJ / cm ² , and the hardness of the coating film after heating at 50 ° C. for 20 minutes as post-baking was JIS K5600-5-4. In accordance with the pencil hardness measurement. Then, the same operation was carried out at post-baking heating temperatures of 60 ° C., 70 ° C., and 80 ° C. for comparison and evaluation. The results are shown in FIG.

[Test Example 12]
Curing confirmation (5) (confirmation of heating time dependency):
The base-reactive resin composition obtained in Example 8 was dissolved in 1.0 g of chloroform (CHCl ₃ ) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 30 seconds, prebaked, heated and prebaked to prepare a coating film having a thickness of 5.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 1000, 5000 and 10000 mJ / cm ² , and the hardness of the coating film after heating at 60 ° C. for 10 minutes as post-baking was JIS K5600-5-4. In accordance with the pencil hardness measurement. The same operation was performed with post-baking heating times of 20 minutes, 40 minutes, and 60 minutes, and compared and evaluated. The results are shown in FIG.

[Test Example 13]
Curing confirmation (6) (confirmation of addition amount dependency):
The base-reactive resin composition obtained in Example 7 was dissolved in 1.0 g of chloroform (CHCl ₃ ) to prepare a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 5.0 μm. 365 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 1000, 5000 and 10000 mJ / cm ² , and the hardness of the coating film after heating at 60 ° C. for 20 minutes as post bake was JIS K5600-5-4. In accordance with the pencil hardness measurement. The same operation was performed on the base-reactive resin compositions of Example 8, Example 9, and Reference Example 2 and compared and evaluated. The results are shown in FIG.

  As shown in FIG. 10, it was confirmed that curing progressed as the heating temperature was increased, the heating time was increased, and the content of the base proliferating agent was increased.

  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 (7)

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

(In Formula (A), R ₁ and R ₂ 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 arylalkyl group of 7 to 15 carbon atoms, _{R 3} is a hydrogen atom, _{R 4} is a cycloalkyl group having 5 to 10 carbon atoms, X is respectively SO or SO _2, a.) A base proliferating agent represented by the following formula (A ′).

(In formula (A ′), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, 12 alkyl group, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ And R ₈ may combine with each other to form a ring structure, n represents an integer of 0 to 20, and X represents SO or SO _2. ) A base proliferating agent represented by the following formula (A ′ ₂ ):

(In Formula (A ′ ₂ ), R ₁ , R ₂ , R ₃ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, X represents SO or SO ₂ )   A base-reactive resin composition comprising the base proliferating agent according to claim 1 and a base-reactive compound.   A base-reactive resin composition comprising the base proliferating agent according to claim 1, a base generator and a base-reactive compound.   The base-reactive resin composition according to claim 5, wherein the base generator is a photobase generator.   The base-reactive resin according to any one of claims 4 to 6, wherein the base-reactive compound is at least one selected from the group consisting of an epoxy-based compound, a silicon-based compound, and an oxetane-based compound. Composition.

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