JP5754166B2 - Method for producing base generator - Google Patents

Description

  The present invention relates to a method for producing a base generator that generates a base by irradiation with electromagnetic waves and heating.

  The photosensitive resin composition is used for, for example, an electronic component, an optical product, a molding material of an optical component, a layer forming material or an adhesive, and particularly preferably used for a product or a member formed through a patterning process using electromagnetic waves. Has been.

For example, polyimide, which is a polymer material, exhibits top-class performance among organic materials such as heat resistance, dimensional stability, and insulation characteristics, so it is widely applied to insulating materials for electronic components. It has been actively used as a coating film, a base material for flexible printed wiring boards, and the like.
However, in general, polyimide is poorly soluble in a solvent and difficult to process. Therefore, as a method of patterning polyimide into a desired shape, patterning is performed by exposure and development in the state of a polyimide precursor having excellent solvent solubility, and then There is a method of obtaining a polyimide pattern by imidization by heat treatment or the like.

  As one of the polyimide precursor patterning methods, the polyamic acid of the polyimide precursor is mixed with a photobase generator and heated after exposure to advance the cyclization by the action of the base generated by the exposure. A technique for obtaining a polyimide pattern by reducing the solubility, forming a pattern by increasing the contrast of the dissolution rate in the developing solution of the exposed part and the unexposed part, and then imidizing is reported ( Patent Document 1).

  As another example of the photosensitive resin composition using the photobase generator, there is an example using an epoxy compound (for example, Patent Document 2). By irradiating the photobase generator with light, amines are generated in the layer containing the epoxy compound, so that the amines act as an initiator or a catalyst, and the epoxy compound can be cured only in the exposed area. Pattern formation can be performed.

  A photosensitive resin composition using a photobase generator is a resin composition because a photosensitive polymer precursor can be obtained simply by mixing a photobase generator at a certain ratio with an existing polymer precursor. The process for manufacturing is simple. In particular, a polyimide precursor in which the structure of a precursor compound used in the past is restricted has an advantage of high versatility because it can be applied to polyimide precursors having various structures. However, since conventional photobase generators have low sensitivity, there has been a problem that the amount of electromagnetic wave irradiation increases. When the amount of electromagnetic wave irradiation increases, there is also a problem that the processing amount (throughput) per unit time decreases.

  As a photobase generator having high sensitivity, the present inventors have developed a photobase generator comprising a hydroxycinnamic amide derivative (Patent Document 3).

JP-A-8-227154 Japanese Patent Laid-Open No. 2003-212856 International Publication No. 2009/123122 Pamphlet

  Until now, a base generator composed of a hydroxycinnamic amide derivative described in Patent Document 3 has been used as a condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) or N, N′-. Dicyclohexylcarbodiimide (DCC) was used to produce a product by condensing a carboxylic acid and a basic compound. However, EDC has a problem that it is expensive for industrial use, and DCC produces a large amount of solid waste derived from a condensing agent, so that it is difficult to separate from the target product and has a large environmental load. There was a problem. In addition, when it is produced by the above method, there is a problem that the yield of the base generator obtained is not sufficient. Therefore, there has been a demand for a production method that has a low environmental load, can be produced at low cost, and has a higher yield.

  The present invention has been made in view of the above circumstances, and its main object is to provide a method for producing a base generator capable of producing a high-sensitivity base generator at a low cost and in a high yield with a small environmental load. There is to do.

As a result of intensive studies to achieve the above object, the present inventors can produce a base generator without using the condensing agent by using a benzaldehyde derivative and an acetamide derivative as starting materials. And gained knowledge.
Furthermore, the present inventors have found that a base generator can be obtained with a high reaction yield by reacting a benzaldehyde derivative and an acetamide derivative in the presence of a base.

In the method for producing a base generator represented by the following general formula (1) of the present invention, a benzaldehyde derivative represented by the following general formula (A) is added to the benzaldehyde derivative in the presence of a base in dimethylformamide. It has the process of reacting the acetamide derivative represented by these.

（一般式（Ａ）、一般式（Ｂ）及び一般式（１）において、Ｒ^１は、水素原子、或いは、加熱及び／又は電磁波の照射により脱保護可能な保護基である。Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、アジド基又は有機基であり、同一であっても異なっていても良い。Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それらの２つ以上が結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は有機基であり、同一であっても異なっていても良い。Ｒ^６及びＲ^７は、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ｒ^６及びＲ^７のうち少なくとも１つは有機基である。）

(In General Formula (A), General Formula (B), and General Formula (1), R ¹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves. R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group Phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, azide group or organic group, which may be the same or different, and R ² , R ³ , R ⁴ and R ⁵ are Two or more may combine to form a cyclic structure, and may include a heteroatom bond, and R ⁶ and R ⁷ are each independently a hydrogen atom or an organic group, and are the same. The May be different .R ⁶ and R ^7, which may be they are attached to form a cyclic structure, may contain a binding heteroatom. Provided that at least one of R ⁶ and R ⁷ Is an organic group.)

  In the method for producing a base generator produced in the present invention, the base is a metal alkoxide, because it is easily available industrially, has a strong basicity, and has a high yield of the base generator. Among them, potassium tert-butoxide having low nucleophilicity is more preferable from the viewpoint of high yield of the base generator.

In the production method of the base generator prepared in the present invention, since the organic solvent is dimethyl formamide, yield of base generator is not high.

  According to the production method of the present invention, it is possible to provide a production method of a base generator that can produce a highly sensitive base generator with a small environmental load at low cost and in high yield. Since the benzaldehyde derivative or acetamide derivative used as a raw material can be obtained as a chemical product or obtained with a small number of steps, the production method of the present invention is a production method with high industrial productivity.

The present invention will be described in detail below.
In the present invention, unless otherwise specified, the electromagnetic wave is not only an electromagnetic wave having a wavelength in the visible and invisible regions, but also a particle beam such as an electron beam, and radiation or a general term for the electromagnetic wave and the particle beam. Contains ionizing radiation. In this specification, irradiation with electromagnetic waves is also referred to as exposure. Note that electromagnetic waves with wavelengths of 365 nm, 405 nm, and 436 nm may be referred to as i-line, h-line, and g-line, respectively.

(Method for producing base generator)
In the method for producing a base generator represented by the following general formula (1) of the present invention, the benzaldehyde derivative represented by the following general formula (A) is added to the following general formula (B) in an organic solvent in the presence of a base. It has the process of reacting the acetamide derivative represented by these.

（一般式（Ａ）、一般式（Ｂ）及び一般式（１）において、Ｒ^１は、水素原子、或いは、加熱及び／又は電磁波の照射により脱保護可能な保護基である。Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、アジド基又は有機基であり、同一であっても異なっていても良い。Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それらの２つ以上が結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は有機基であり、同一であっても異なっていても良い。Ｒ^６及びＲ^７は、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ｒ^６及びＲ^７のうち少なくとも１つは有機基である。）

(In General Formula (A), General Formula (B), and General Formula (1), R ¹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves. R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group Phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, azide group or organic group, which may be the same or different, and R ² , R ³ , R ⁴ and R ⁵ are Two or more may combine to form a cyclic structure, and may include a heteroatom bond, and R ⁶ and R ⁷ are each independently a hydrogen atom or an organic group, and are the same. The May be different .R ⁶ and R ^7, which may be they are attached to form a cyclic structure, may contain a binding heteroatom. Provided that at least one of R ⁶ and R ⁷ Is an organic group.)

  In the method for producing a base generator according to the present invention, the benzaldehyde derivative represented by the general formula (A) is reacted with the acetamide derivative represented by the general formula (B) in the presence of a base in an organic solvent. By having a process, it is possible to produce a base generator having excellent sensitivity at a low yield and high yield with a small environmental load.

  By having the step of reacting the benzaldehyde derivative represented by the general formula (A) with the acetamide derivative represented by the general formula (B) in an organic solvent in the presence of a base, the environmental load is low and inexpensive. In addition, it is not yet elucidated that a base generator having excellent sensitivity can be produced, but it is presumed as follows.

When the acetamide derivative represented by the general formula (B) is used, a basic compound generated without using a dehydration condensation reaction can be introduced in advance. For this reason, the conventional dehydration condensation reaction of carboxylic acid and basic compound is unnecessary, and expensive 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and a large amount of solids during the reaction Since a condensing agent such as N, N′-dicyclohexylcarbodiimide (DCC) is not required, it can be produced at low cost and at low cost.
Further, the acetamide derivative represented by the general formula (B) generates an enolate anion in the presence of a base, and the enolate anion is highly reactive with the benzaldehyde derivative represented by the general formula (A). It is estimated that the selectivity is high. For this reason, it is presumed that a trans isomer represented by the general formula (1) is preferentially produced, and a base generator having a high yield and excellent sensitivity can be produced. In addition, when an acetamide derivative represented by the general formula (B) is reacted with a benzaldehyde derivative represented by the general formula (A) in an organic solvent in the presence of an acid, a base represented by the general formula (1) is generated. The reaction yield of the agent was extremely low.

  The base generator represented by the above formula (1) produced in the present invention is a kind of photobase generator, and generates a base only by being irradiated with electromagnetic waves, but by appropriately heating, Generation of base is promoted. The base generator produced in the present invention can efficiently generate a base with a small amount of electromagnetic wave irradiation by combining electromagnetic wave irradiation and heating, and is higher than conventional photobase generators. Has sensitivity.

When the base generator represented by the above formula (1) produced by the production method of the present invention is irradiated with electromagnetic waves, as shown by the following formula, (—CH═CH in the formula (1) The —C (═O) —) moiety is isomerized from the trans isomer to the cis isomer, and the protecting group R ¹ is optionally deprotected by heating and / or irradiation with electromagnetic waves, and cyclized to give a base (NHR ⁶ R ⁷ ) is generated.

  A photosensitive resin composition can be easily prepared by combining the base generator with various polymer precursors. Due to the catalytic action of the base generated by the above reaction, the temperature at which the reaction when the polymer precursor becomes the final product is lowered, or the curing reaction where the polymer precursor becomes the final product is started. Can do.

[Benzaldehyde derivative represented by general formula (A), acetamide derivative represented by general formula (B), base generator represented by general formula (1)]
R ^{1 to} R ⁵ in the benzaldehyde derivative represented by the general formula (A) and the base generator represented by the general formula (1) are the same, and the acetamide derivative represented by the general formula (B) Since R ⁶ and R ⁷ in the base generator represented by the general formula (1) are the same, R ^{1 to} R ⁷ will be described below in order.

<R ¹ >
In the general formula (A) and the general formula (1), R ¹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves. Here, “deprotectable” means that there is a possibility of changing from —OR ¹ to —OH. When R ¹ is a hydrogen atom, the base generator according to the present invention loses the phenolic hydroxyl group by cyclization to change the solubility, and the solubility decreases in the case of a basic aqueous solution or the like. To do. When the base generator is used as a photosensitive resin composition, for example, when the polymer precursor contained in the photosensitive resin composition is a polyimide precursor or a polybenzoxazole precursor, the final product of the precursor It has a function of further assisting in lowering the solubility due to the reaction, and it is possible to increase the solubility contrast between the exposed portion and the unexposed portion.

In addition, when R ¹ is a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves, it is deprotected by heating and / or irradiation with electromagnetic waves to generate a hydroxyl group. R ¹ is heated and / or electromagnetic wave-free under conditions where decomposition other than deprotection does not occur in the base generator produced in the present invention, for example, under conditions where the amide group present in formula (1) does not decompose. Any protecting group of a phenolic hydroxyl group that can be deprotected by irradiation can be used without particular limitation. For example, amide groups can be heated under strong acidic conditions such as strong Lewis acids such as boron tribromide and aluminum trichloride, strong acids such as sulfuric acid, hydrochloric acid and nitric acid, and strong bases such as sodium hydroxide. Decomposes on heating under basic conditions. Accordingly, such a protecting group that can be deprotected only by heating under strongly acidic or strongly basic conditions is inappropriate as a protecting group used in the base generator of the present invention. R ¹ is appropriately selected depending on the type of compound used in combination with the base generator, the application method of the base generator, and the synthesis method for the purpose of improving solubility and compatibility or changing the reactivity during synthesis. It is what is done.

R ¹ as a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves can be selected from a silyl group, a silanol group, a phosphino group, a phosphinyl group, a phosphono group, or a monovalent organic group.

R ¹ is an amide present in the formula (1) that is at least one selected from the group consisting of organic groups represented by the following formulas (2-1) to (2-6) It is preferable from the viewpoint that it can be deprotected by heating and / or irradiation with electromagnetic waves under conditions where the group does not decompose.

（式（２−１）中、Ｒ^２０、Ｒ^２１、Ｒ^２２はそれぞれ独立に水素原子、ハロゲン原子、または１価の有機基であり、Ｒ^２３は１価の有機基であり、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３はそれぞれ互いに結合して環状構造を示していても良い。式（２−２）中、Ｒ^２４は、１価の有機基である。式（２−３）中、Ｒ^２５、Ｒ^２６、Ｒ^２７はそれぞれ独立に水素原子、ハロゲン原子、または１価の有機基である。式（２−４）中、Ｒ^２８は、１価の有機基である。式（２−５）中、Ｒ^２９は、置換基を有していても良い芳香環である。式（２−６）中、Ｒ^３０は、１価の有機基である。）

(In formula (2-1), R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom or a monovalent organic group, R ²³ is a monovalent organic group, R ²⁰ , R ²¹ , R ²² and R ²³ may be bonded to each other to show a cyclic structure, wherein R ²⁴ is a monovalent organic group in formula (2-3). , R ²⁵ , R ²⁶ and R ²⁷ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, wherein R ²⁸ is a monovalent organic group. In 2-5), R ²⁹ is an aromatic ring which may have a substituent, and in formula (2-6), R ³⁰ is a monovalent organic group.

  The organic group represented by the above formula (2-1) can be obtained, for example, by a reaction between a phenolic hydroxyl group and a vinyl ether compound as follows.

（式中、Ｒ^２０、Ｒ^２１、Ｒ^２２、及びＲ^２３はそれぞれ式（２−１）と同じである。）

(Wherein R ²⁰ , R ²¹ , R ²² , and R ²³ are the same as those in formula (2-1)).

When R ²⁰ , R ²¹ , R ²² and R ²³ of the organic group represented by the above formula (2-1) are obtained by the above reaction, they are determined by the structure of the vinyl ether compound used. When the base generator is used in a photosensitive resin composition, the organic group represented by the above formula (2-1) is a kind of compound such as a polymer precursor used in combination with the base generator. However, it may be appropriately selected depending on the application method, and is not particularly limited.
R ²⁰ , R ²¹ and R ²² are preferably a hydrogen atom or a substituted or unsubstituted alkyl group, allyl group or aryl group. In particular, a hydrogen atom is preferable from the viewpoint of easy availability of raw materials. Moreover, it is preferable that the substituent which has active hydrogen atoms, such as a primary, secondary, tertiary amino group, and a hydroxyl group, is not included from the point of stability of a compound.

R ²³ of the organic group represented by the above formula (2-1) is a monovalent organic group having 1 or more carbon atoms. R ²³ is exemplified by a group having a hydrocarbon atomic skeleton. The group having a hydrocarbon atom skeleton may contain a bond other than a hydrocarbon atom such as a hetero atom or a substituent, and such a hetero atom part is incorporated into an aromatic ring to form a heterocyclic ring. Also good. Examples of the group having a hydrocarbon atom skeleton include a linear, branched, or cyclic saturated or unsaturated hydrocarbon atomic group, a linear, branched, or cyclic saturated or unsaturated halogenated alkyl group, or Aromatic groups such as phenyl and naphthyl, and further a group containing an ether bond in a linear or branched saturated or unsaturated hydrocarbon atom skeleton (for example, — (R—O) _n —R ′, wherein Wherein R and R ′ are substituted or unsubstituted saturated or unsaturated hydrocarbon atoms, n is an integer of 1 or more; —R ″ — (O—R ″ ′) _m , where R ″ and R ″ ′ are substituted or An unsubstituted saturated or unsaturated hydrocarbon atom, m is an integer of 1 or more,-(O—R ″ ′) _m is bonded to a carbon different from the terminal of R ″; A group containing a thioether bond in a saturated or unsaturated hydrocarbon atom skeleton of a chain or branched chain Various groups comprising hetero atoms or hetero atom-containing groups such as cyano group, silyl group, nitro group, acetyl group, acetoxy group, etc., bonded on a linear or branched saturated or unsaturated hydrocarbon atom skeleton. Groups. Further, ^{R 23} in the organic group represented by the above formula (2-1) ^may have a cyclic structure linked to ^{R 20} or ^{R 21.} R ²³ also preferably does not contain a substituent having an active hydrogen atom such as a primary, secondary, tertiary amino group, or a hydroxyl group from the viewpoint of stability of the compound.

The organic group represented by the following formula (2-1) is deprotected by irradiation of heat and / or electromagnetic waves, the temperature of the deprotection is generally in the R ²³ in the above formula, the ether bond vinyl ether compounds oxygen The carbon directly bonded to the atom is a tertiary carbon atom (hereinafter sometimes simply referred to as “tertiary carbon”) <secondary carbon atom (hereinafter sometimes simply referred to as “secondary carbon”) < It tends to increase in the order of the substituent of a primary carbon atom (hereinafter sometimes simply referred to as “primary carbon”). On the other hand, the reaction of the vinyl ether compound and a hydroxyl group to protect generally the R ²³ in the above formula, the order at a high reaction rate of the substituents of carbon bonded to the oxygen atom is primary carbon <secondary carbon <tertiary carbon There is a tendency to show. Therefore, it is preferable that the heating temperature for deprotection is selected depending on the compound combined with the base generator and the method of use, and the protecting group is appropriately selected from the heating temperature.
In the present invention, a vinyl ether compound for deriving a carbon atom bonded to ether oxygen (a carbon atom bonded to an oxygen atom in R ²³ of formula (2-1)) or an organic group of formula (2-1). As for the other carbon atom bonded to the ether oxygen bonded to the vinyl group, the primary carbon atom means the case where the other carbon atom bonded is 0 or 1, and the secondary carbon atom Means the case where there are two other carbon atoms bonded, and the tertiary carbon atom means the case where there are three other carbon atoms bonded.

R ²³ in the formula (2-1) preferably has 1 to 18 carbon atoms from the volatility of the decomposition product, and more preferably 3 to 10 carbon atoms.

R ^{23 in the} formula (2-1) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. Group, cyclohexylmethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, cyclohexyloxypropyl group, 2- Tetrahydropyranyl group etc. are mentioned. Moreover, in the formula (2-1), R ²³ is linked to R ²⁰ or R ²¹ to form a cyclic structure, and a cyclic ether such as a 2-tetrahydropyranyl group is exemplified.

  The organic group represented by the above formula (2-2) can be obtained, for example, by a reaction between a phenolic hydroxyl group and a so-called carbonate-based protecting group. Examples of carbonate-based protecting groups include tert-butoxycarbonyl group (Boc-), benzyloxycarbonyl group (Z-), 9-fluorenylmethoxycarbonyl group (Fmoc-), 1,1-dioxobenzo [b] thiophene. 2-ylmethoxycarbonyl group (Bsmoc-), 2- (4-nitrophenylsulfonyl) ethoxycarbonyl group (Nsc-), p-methoxybenzyloxycarbonyl group (Z (OMe-)), allyloxycarbonyl group (Alloc) -), 2,2,2-trichloroethoxycarbonyl group (Troc-) and the like.

R ^{24 in the} formula (2-2) is not particularly limited, and examples thereof include tert-butyl group, benzyl group, 9-fluorenylmethyl group, 2,2,2-trichloroethyl group, allyl group, p- Examples include a methoxybenzyl group, 1,1-dioxobenzo [b] thiophen-2-ylmethyl group, 2- (4-nitrophenylsulfonyl) ethyl group, o-nitrobenzyl group and the like. In the case of an o-nitrobenzyl group, deprotection is possible by irradiation with electromagnetic waves.

The organic group represented by the above formula (2-3) can be obtained, for example, by a reaction between a phenolic hydroxyl group and a silyl ether protecting group.
Examples of the silyl ether protecting group include trimethylsilyl group (TMS-), tert-butyldimethylsilyl group (TBDMS-), tert-butyldiphenylsilyl group (TBDPS-), triisopropylsilyl group (TIPS-) and the like. .

Although it does not specifically limit as R < ²⁵ >, R <^26> , R < ²⁷ > of said Formula (2-3), For example, alkyl groups, such as a methyl group, a tert- butyl group, an isopropyl group, and the aryl group of a phenyl group are used suitably. .

The organic group represented by the above formula (2-4) can be obtained, for example, from a phenolic hydroxyl group and an acid chloride or acid anhydride.
Examples of the ester protecting group represented by the formula (2-4) include an acetyl group (Ac-), a pivaloyl group, and a benzoyl group.

R ^{28 in the} formula (2-4) is not particularly limited. For example, an alkyl group such as a methyl group or a tert-butyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, or the like is preferably used. .

The organic group represented by the above formula (2-5) can be obtained, for example, from a phenolic hydroxyl group and a halogen atomized product using the Williamson reaction.
Examples of the ether protecting group represented by the formula (2-5) include a benzyl group which may have a substituent.

R ^{29 in the} formula (2-5) is an aromatic ring which may have a substituent, and is not particularly limited, and examples thereof include a phenyl group and a naphthyl group which may have a substituent. In particular, when the organic group represented by the formula (2-5) is an o-nitrobenzyl group, that is, when R ²⁹ is a 2-nitrophenyl group, deprotection is possible by electromagnetic wave irradiation.

The organic group represented by the above formula (2-6) can be obtained, for example, by a reaction between a phenolic hydroxyl group and an isocyanate. Examples of the carbamate protecting group include benzyl isocyanate.
Formula is not particularly limited as R ³⁰ in (2-6), for example, it is mentioned a benzyl group.

<R ² , R ³ , R ⁴ and R ⁵ >
In the above general formula (A) and general formula (1), R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, or a silanol group. Nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group, azido group or organic group, which may be the same or different Also good. Two or more of R ² , R ³ , R ^4, and R ⁵ may be bonded to form a cyclic structure, or may include a hetero atom bond.
Examples of the halogen atom include fluorine, chlorine, bromine and the like.
The organic group is not particularly limited as long as the effect of the present invention is not impaired, and is saturated or unsaturated alkyl group, saturated or unsaturated cycloalkyl group, aryl group, aralkyl group, and saturated or unsaturated halogen atomized alkyl. Group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, hydroxyimino group , An epoxy group, an oxetane group, a thiirane group, a glycidyl ether group, a glycidyl ester group, a (meth) acryloyl group (—CO—CR═CH _2, where R is hydrogen or a methyl group), and the like. These organic groups may contain a bond or substituent other than a hydrocarbon atom group such as a hetero atom in the organic group, and these may be linear or branched.

The bond other than the hydrocarbon atom group in the organic group of R ^{2 to} R ⁵ is not particularly limited as long as the effect of the present invention is not impaired, and is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester. Examples include a bond, an amide bond, a urethane bond, a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond.
From the viewpoint of heat resistance, the bond other than the hydrocarbon atom group in the organic group includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C ( -R)-, -C (= NR)-: where R is a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

The substituent other than the hydrocarbon atom group in the organic group of R ^{2 to} R ⁵ is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group. , Isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl Group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group, And an aryl thioether group, Epoxy group, a glycidyl ether group, glycidyl ester group, an oxetane group, a thiirane group, (meth) acryloyl groups (-CO-CR = CH _2; where R is hydrogen or a methyl group), an amino group (--NH2, -NHR, —NRR ′: Here, R and R ′ are each independently a hydrocarbon atom group), an ammonio group, an azide group (—N—N≡N), or the like. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon atom group. Moreover, the hydrocarbon atom group contained in the substituent may be linear, branched, or cyclic.
Among them, examples of the substituent other than the hydrocarbon atom group in the organic group represented by R ^{2 to} R ⁵ include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, and an isothiocyanato group. Group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, Phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group, and aryl thioether group, epoxy group, glycidyl ether group, glycidyl Ester group, an oxetane group, a thiirane group, (meth) acryloyl groups (-CO-CR = CH _2; where R is hydrogen or a methyl group), is preferable.

Two or more of R ^{2 to} R ⁵ may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbon atoms, heterocyclic rings, and condensed rings, and the alicyclic hydrocarbon atoms, heterocyclic rings, and condensed rings. The structure formed may be sufficient. For example, R ² to R ⁵ are formed by combining two or more of them, naphthalene share atoms of the benzene ring of R ² to R ⁵ are attached, anthracene, phenanthrene, and fused ring indene You may do it.

In the present invention, it is preferable to introduce one or more substituents into the substituents R ^{2 to} R ⁵ . That is, at least one of R ² , R ³ , R ⁴ and R ⁵ is a halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, A phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, an azido group or a monovalent organic group is preferred. By introducing at least one substituent as described above into the substituents R ^{2 to} R ⁵ , the wavelength of light to be absorbed can be adjusted, and the desired wavelength is absorbed by introducing the substituent. It can also be made to do. The absorption wavelength can be shifted to a longer wavelength by introducing a substituent that extends the conjugated chain of the aromatic ring. Moreover, solubility can also be improved. When the base generator produced by the production method of the present invention is used in a photosensitive resin composition, the compatibility with the polymer precursor to be combined can be improved. Thereby, it is possible to improve the sensitivity of the photosensitive resin composition in consideration of the absorption wavelength of the polymer precursor to be combined.

  As a guideline of what substituents should be introduced to shift the absorption wavelength with respect to a desired wavelength, the Interspection of the Ultraviolet Products (AI Scott 1964) and the spectrum of organic compounds The table described in the identification method 5th edition (RM Silverstein 1993) can be referred to.

R ^{2 to} R ⁵ include, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a cycloalkyl group having 4 to 23 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a cyclopentenyl group and a cyclohexenyl group. A cycloalkenyl group having 4 to 23 carbon atoms such as a group; an aryloxyalkyl group having 7 to 26 carbon atoms (-ROAr group) such as a phenoxymethyl group, a 2-phenoxyethyl group and a 4-phenoxybutyl group; a benzyl group, 3 An aralkyl group having 7 to 20 carbon atoms such as phenylpropyl group; an alkyl group having 2 to 21 carbon atoms having a cyano group such as cyanomethyl group and β-cyanoethyl group; 1 to 20 carbon atoms having a hydroxyl group such as hydroxymethyl group Alkyl group, methoxy group, ethoxy group, etc., C1-C20 alkoxy group, acetamide group, benzenesulfonamide group _{C 6 H 5 SO 2 NH 2} -) amide group having a carbon number of 2 to 21, such as a methylthio group, an alkylthio group (-SR group having 1 to 20 carbon atoms such as an ethylthio group), an acetyl group, carbon atoms such as benzoyl group 6 to 20 carbon atoms such as an acyl group having 1 to 20 carbon atoms, a methoxycarbonyl group, an acetoxy group and the like, an ester group having 2 to 21 carbon atoms (—COOR group and —OCOR group), a phenyl group, a naphthyl group, a biphenyl group, a tolyl group, etc. ˜20 aryl group, electron donating group and / or electron withdrawing group substituted aryl group having 6 to 20 carbon atoms, electron donating group and / or electron withdrawing group substituted benzyl group, cyano group, and Methylthio group (—SCH ₃ ), epoxy group, glycidyl ether group, glycidyl ester group, oxetane group, thiirane group, (meth) acryloyl group (—CO—CR═CH ₂ ; R is preferably hydrogen or a methyl group. The alkyl moiety may be linear, branched or cyclic.
In addition, as R ^{2 to} R ⁵ , two or more of them are bonded to each other and a condensed ring such as naphthalene, anthracene, phenanthrene, or indene is shared by sharing the atoms of the benzene ring to which R ^{2 to} R ⁵ are bonded. Even if it forms, it is preferable from the point which absorption wavelength becomes long.

Further, the base generator prepared in the present ^invention, R ^2, R 3, if at least one of ^{R 4} and ^{R 5} is a hydroxyl ^group, R ^2, R 3, ^{R 4} and not containing a hydroxyl group at ^{R 5} Compound In view of the ability to improve the solubility in a basic aqueous solution and to increase the absorption wavelength. In particular, when R ⁵ is a phenolic hydroxyl group, a reaction site for cyclization of a compound isomerized to a cis isomer increases, which is preferable from the viewpoint of easy cyclization.

Of R ^{2 to} R ⁵ , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ² and R ^3, and R ⁴ and R ⁵ are represented by the following formula (3): It is also preferable to have the partial structure from the viewpoint of excellent sensitivity.

（式（３）において、Ｘは、２つの酸素原子と結合可能な連結基である。）

(In Formula (3), X is a linking group capable of binding to two oxygen atoms.)

  In the —O—X—O— moiety, a substituent similar to an alkoxy group having an effect of shifting the absorption wavelength to a long wavelength is introduced into adjacent positions among the 3rd to 6th positions of the benzene ring. It is a structure in which a substituent is bonded. Therefore, the base generator having such a substituent is bonded to —O—X—O— as compared to the case where an alkoxy group is introduced into each of adjacent positions among the 3rd to 6th positions of the benzene ring. Thus, it is presumed that oxygen atoms are fixed, the absorption wavelength is efficiently increased, a basic compound can be generated with a small amount of electromagnetic wave irradiation, and the sensitivity can be increased.

X in the partial structure of the chemical formula (3) is not particularly limited as long as it is a linking group capable of binding to two oxygen atoms.
In the present invention, from the viewpoint of increasing the sensitivity of the base generator to be obtained, the above X may contain a hetero atom and may have a substituent, a straight chain having 1 to 20 carbon atoms, branched or Linear, branched or cyclic silicon having 1 to 20 silicon atoms, which may contain a cyclic saturated or unsaturated aliphatic or aromatic hydrocarbon atom group or hetero atom, and may have a substituent From a hydrogen silicide atom group that may contain a silicon double bond, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, and a sulfonyl bond, and combinations thereof A linking group selected from the group consisting of

The linear, branched, or cyclic saturated aliphatic hydrocarbon atom group in X above may contain a hetero atom, and may have a substituent. Examples of the saturated aliphatic hydrocarbon atom group include alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexylene group, a decylene group, a dodecylene group, a hexadecylene group, and an octadecylene group; Group, propylidene group; cycloalkylene group such as cyclohexylene group, norbonalene group, adamantalene group and the like.
The linear, branched, or cyclic unsaturated aliphatic hydrocarbon atom group in X above may contain a hetero atom, and may have a substituent. Examples of the unsaturated aliphatic hydrocarbon atom group include a vinylene group.
In addition, the substituent that the saturated aliphatic hydrocarbon atom group and the unsaturated aliphatic hydrocarbon atom group may have is a substituent other than the hydrocarbon atom group in the organic group of R ^{2 to} R ^5. It may be the same as the group.
In the case where the saturated aliphatic hydrocarbon atom group and the unsaturated aliphatic hydrocarbon atom group include a hetero atom, an ether bond is formed on the saturated aliphatic hydrocarbon atom group or the unsaturated aliphatic hydrocarbon atom group. Thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, carbonate bond, sulfonyl bond and the like.
The aromatic hydrocarbon atom group in X may contain a hetero atom, and may have a substituent. Examples of the aromatic hydrocarbon atom group include a phenylene group and a naphthylene group.
Moreover, as a substituent which the said aromatic hydrocarbon atom group may have, the same thing as the substituent which the said saturated aliphatic hydrocarbon atom group may have is mentioned.
When the aromatic hydrocarbon atom group includes a hetero atom (heterocycle), specific examples thereof include furan and thiophene.

The linear, branched, or cyclic hydrogen silicide atom group in X may contain a hetero atom, and may have a substituent. Moreover, the silicon-silicon double bond may be included.
Here, in the present invention, the silicide hydrogen atom group, for divalent is _{- (SiH 2) n -,} 1 -valent when the - _{(SiH 2)} n -H in silicon and consisting only group hydrogen atom And n is a natural number of 1 or more.

Examples of the substituent that the hydrogen silicide atom group may have include a halogen atom, a hydroxyl group, and a monovalent organic group. These substituents may be the same as those described for R ^{2 to} R ⁵ above.
Moreover, when the said hydrogen silicide atom group contains a hetero atom, what was illustrated in the said saturated aliphatic hydrocarbon atom group as a bond which X contains can be mentioned.

  Among these, the partial structure represented by the chemical formula (3) is preferably a partial structure represented by the following chemical formula (3 ′).

(In the chemical formula (3 '), Z is a carbon atom, a silicon atom, a carbon - carbon double bond (-C = C-), or silicon - is a silicon double bond (-Si = Si-) .R ^a And R ^b each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a mercapto group, a silanol group, a monovalent hydrogen silicide atom group optionally having a substituent, a phosphino group, A phosphinyl group, a phosphono group or a monovalent organic group, which may be the same or different, and R ^a and R ^b may be bonded to form a cyclic structure; (It may contain a bond. N represents an integer of 1 to 10.)

Examples of the cyclic structure formed by combining R ^a and R ^b include saturated or unsaturated alicyclic hydrocarbon atoms, heterocyclic rings, and aromatic hydrocarbon atoms, and the alicyclic hydrocarbon atoms, heterocyclic rings, And a structure in which two or more selected from the group consisting of aromatic hydrocarbon atoms are combined.
For example, when Z is a carbon atom, any two of n R ^a and R ^b may be bonded to form an alicyclic hydrocarbon atom or a heterocyclic ring. In addition, when Z is a carbon-carbon double bond, R ^a and R ^b may form a cyclic structure together with the carbon-carbon double bond of Z to form an aromatic ring.

When Z is a silicon atom, n R ^a and R ^b may each be an organic group, and carbon atoms may be bonded to each other to form a cyclic structure. Each of n R ^a and R ^b may be a hydrogen silicide atomic group which may have a substituent, and silicon atoms may be bonded to each other to form a cyclic structure. In addition, the cyclic structure may include a bond of a hetero atom such as oxygen.
When Z is a silicon-silicon double bond, R ^a and R ^b may form a cyclic structure with carbon atoms and / or silicon atoms together with the silicon-silicon double bond of Z, The structure may further include a silicon-silicon double bond.
Moreover, the halogen atom and monovalent organic group of R ^a and R ^b may be the same as those described in the above R ^{2 to} R ⁵ .
n represents an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably 1 to 3.

  Examples having a partial structure represented by the above formula (3 ′) are shown below, but are not limited thereto.

In addition, any of R ² , R ³ , R ^4, and R ⁵ has a partial structure represented by the following formula (4), which is highly sensitive and has high solubility in organic solvents and a polymer precursor to be combined. It is preferable from the viewpoint of excellent affinity with the body. Since the partial structure represented by the formula (4) is a substituent similar to an alkoxy group, it has an effect of shifting the absorption wavelength to a long wavelength, can generate a basic compound with a small amount of electromagnetic wave irradiation, and increases sensitivity. Is estimated to be possible. The partial structure represented by formula (4) has a R ^{c O} site a repeating structure, solubility and affinity can be estimated to be good.

（式（４）において、Ｒ^ｃは、２つの酸素原子と結合可能な連結基である。Ｒ^ｄは、水素原子、シリル基、シラノール基、ホスフィノ基、ホスフィニル基、ホスホノ基、又は１価の有機基である。ｎは１以上の整数である。）

(In Formula (4), R ^c is a linking group capable of binding to two oxygen atoms. R ^d is a hydrogen atom, a silyl group, a silanol group, a phosphino group, a phosphinyl group, a phosphono group, or a monovalent group. (It is an organic group. N is an integer of 1 or more.)

The partial structure of the above formula (4) may be included in at least one of R ² , R ³ , R ⁴ and R ⁵ . Typically, a structure in which the partial structure of the above formula (4) is directly bonded to the benzene ring as a substituent at any position of R ² , R ³ , R ⁴ and R ⁵ is exemplified. Any of R ² , R ³ , R ⁴ and R ⁵ is an organic group, and may have a partial structure of the above chemical formula (4) as a part of the organic group. When two or more of R ^{2 to} R ⁵ are bonded to form an alicyclic hydrocarbon atom structure such as a cyclohexyl group, or two or more of R ^{2 to} R ⁵ are bonded to bond them. When the condensed benzene ring atom is shared to form a condensed ring such as naphthalene, anthracene, phenanthrene, indene, fluorene, etc., the cyclic structure has a partial structure of the above formula (4) as a substituent. May be.

R ^c in the partial structure of the chemical formula (4) is not particularly limited as long as it is a linking group capable of binding to two oxygen atoms. Further, the n R ^c included in the repeating unit may be the same or different.
In the present invention, from the viewpoint of increasing sensitivity, the above R ^c may contain a hetero atom, and may have a substituent, a linear, branched or cyclic saturated or unsaturated group having 1 to 20 carbon atoms. A saturated aliphatic or aromatic hydrocarbon atom group, a hetero atom, a linear, branched or cyclic silicon-silicon double bond having 1 to 20 silicon atoms which may have a substituent. A linking group selected from the group consisting of a hydrogen silicide atom group, a carbonyl bond, a thiocarbonyl bond, a sulfonyl bond, a sulfinyl bond, and an azo bond that may be contained is preferable.
From the viewpoint of heat resistance, the above R ^c may contain a hetero atom, and may have a substituent, a linear, branched or cyclic saturated or unsaturated aliphatic group having 1 to 20 carbon atoms, or aromatic. A hydrocarbon group, a hetero atom, a silicon group having 1 to 20 silicon atoms which may have a substituent, and a silicon atom which may contain a silicon-silicon double bond having a linear, branched or cyclic structure. A linking group selected from the group consisting of a hydrogen halide atom group, a carbonyl bond, a thiocarbonyl bond, a sulfonyl bond, and a sulfinyl bond is preferable. As these, those similar to Z in the above formula (3 ′) can be used.

Among them, as R ^c , a C1-C20 linear, branched or cyclic saturated or unsaturated aliphatic or aromatic hydrocarbon which may contain a hetero atom and may have a substituent It is preferably an atomic group, and is preferably a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon atomic group having 1 to 10 carbon atoms which may have a substituent. Especially, it is preferable that it is a C1-C6 linear, branched or cyclic saturated aliphatic hydrocarbon atom group which may have a substituent, and also the carbon number 1 which may have a substituent. It is preferable that it is a -3 linear, branched or cyclic saturated aliphatic hydrocarbon atom group.

N which is the number of repetitions of OR ^c is an integer of 1 or more. n is preferably adjusted as appropriate depending on the structure and molecular weight of R ^c , but 1 to 20 is preferable and 1 to 10 is more preferable.

R ^d is a hydrogen atom, a silyl group, a silanol group, a phosphino group, a phosphinyl group, a phosphono group, or a monovalent organic group, and examples of the monovalent organic group include those described in R ^{2 to} R ⁵ above. A thing similar to a valent organic group can be used.
Among these, from the viewpoints of sensitivity and solvent solubility, R ^d is preferably a monovalent organic group.

As R ² , R ³ , R ⁴ and R ⁵ , for example, a substituent in which a part of the structure is changed by heating and / or irradiation with an electromagnetic wave to become a hydroxyl group, a carboxyl group, or an amino group, or heating and / or It has a substituent that becomes part of an isocyanato group or thioisocyanato group by irradiation with electromagnetic waves and becomes a alkynyl group that changes part of its structure by irradiation with heat and / or electromagnetic waves. Also good.

As a substituent that is partially hydroxylated by heating and / or irradiation with an electromagnetic wave, the terminal hydrogen atom of the hydroxyl group is an organic group represented by the above formula (2-1) to the above formula (2-6). From the viewpoint of easy synthesis, it is preferable to have a structure substituted with one or more selected from the group consisting of:
Each substituent in the above formula (2-1) to the above formula (2-6) can be the same as that described in the above R ¹ .

Moreover, as a substituent which a part of structure changes by heating and / or electromagnetic wave irradiation and becomes a carboxyl group, the hydrogen of the terminal of a carboxyl group is an organic group represented by the said Formula (2-1), said Formula ( From the viewpoint of easy synthesis, it is preferable to have a structure substituted with one or more selected from the group consisting of the organic group represented by 2-3) and the organic group. The structure in which the hydrogen at the terminal of the carboxyl group is substituted with an organic group is an ester group (—COOR ⁴¹ ; where R ⁴¹ is an organic group). Especially, it is preferable from the point with an easy synthesis | combination that the hydrogen of the terminal of a carboxyl group has the structure substituted by the organic group represented by the said Formula (2-1) or the said Formula (2-3).

A structure in which the hydrogen at the terminal of the carboxyl group is substituted with an organic group, an ester group (—COOR ⁴¹ ) can be obtained by a reaction between a carboxyl group and a hydroxyl group using the Williamson reaction.
No particular limitation is imposed on the R ⁴¹ of the above ester groups, for example, a methyl group, an alkyl group such as a tert- butyl group, an aryl group such as a phenyl group, aralkyl groups such as benzyl group is preferably used.

In addition, as a substituent in which a part of the structure is changed to be an amino group (—NH ² ) by heating and / or electromagnetic wave irradiation, one hydrogen at the terminal of the amino group (—NH ² ) is represented by the above formula (2 It is preferable from the viewpoint of easy synthesis that it has a structure substituted with an organic group represented by -2).

In addition, as a substituent that is partially converted into an isocyanato group or a thioisocyanato group by heating and / or irradiation with electromagnetic waves, a reaction for blocking a known isocyanato group or a reaction for forming an isocyanato group by transfer. It can be obtained using it.
Substituents whose structure is partially changed by heating and / or irradiation with electromagnetic waves to become isocyanato groups or thioisocyanato groups are composed of substituents represented by the following formulas (5-1) to (5-6). One or more structures selected from the group are preferably included from the viewpoint of easy synthesis. Substituents represented by the following formulas (5-1) to (5-6) are dissociated or transferred by heating and / or irradiation with electromagnetic waves to become isocyanato groups or thioisocyanato groups.

（式（５−１）中、Ｑは酸素原子又は硫黄原子であり、Ｒ^４２は有機基である。式（５−２）中、Ｅｗはそれぞれ独立に電子吸引性基であり、Ｑは酸素原子又は硫黄原子である。式（５−３）中、Ｑは酸素原子又は硫黄原子であり、Ｒ^４３及びＲ^４４はそれぞれ独立に水素原子又は有機基である。式（５−４）中、Ｑは酸素原子又は硫黄原子であり、ｎは３〜７である。）

(In Formula (5-1), Q is an oxygen atom or a sulfur atom, R ⁴² is an organic group. In Formula (5-2), Ew is each independently an electron-withdrawing group, and Q is oxygen. In formula (5-3), Q is an oxygen atom or sulfur atom, and R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an organic group, in formula (5-4), Q is an oxygen atom or a sulfur atom, and n is 3-7.)

The substituent represented by the above formula (5-1) can be obtained by reacting an isocyanato group or a thioisocyanato group with a hydroxyl group-containing compound such as alcohol or phenol.
No particular limitation is imposed on the R ⁴² of formula (5-1), for example, a methyl group, an alkyl group such as a tert- butyl group, an aryl group such as a phenyl group, aralkyl groups such as benzyl group is preferably used.

The substituent represented by the above formula (5-2) can be obtained by reacting an isocyanato group or a thioisocyanato group with a compound having an active methylene group. Here, the active methylene group means a methylene group (—CH ₂ —) having reaction activity, and means a methylene group sandwiched between two electron-withdrawing groups. Examples of the electron withdrawing group include a carbonyl group, a cyano group, a nitro group, a sulfonyl group, a sulfinyl group, and a phosphono group.
Examples of the compound having an active methylene group include malonic acid esters such as dimethyl malonate and diethyl malonate, acetoacetate esters such as methyl acetoacetate and ethyl acetoacetate, acetylacetone, malononitrile, ethyl cyanoacetate, ethyl nitroacetate, p -Ethyl trissulfonyl acetate, ethyl phenylsulfinyl acetate, trimethyl phosphonoacetate and the like can be used. Of these, malonic acid ester and acetoacetic acid ester are preferable from the viewpoint of reactivity.

Ew in the formula (5-2) is a residue in the compound having an active methylene group, and is not particularly limited. For example, an ester group (—COOR), an acyl group (—COR), a cyano group (—CN), a nitro group (—NO ₂ ), a sulfonyl group (—S (═O) ₂ R), a sulfinyl group (—S ( ═O) R), a phospho group (—P (═O) (OR) ₂ )) and the like (where R is an organic group).

The substituent represented by the above formula (5-3) includes an isocyanato group or a thioisocyanato group, and formal oxime, acetal oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, 2-butanone oxime, or diethylglyoxime It can obtain by reaction with oximes.
R ⁴³ and R ^{44 in} the formula (5-3) are not particularly limited. For example, an alkyl group such as a methyl group and a tert-butyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group are preferable. Used.

  The substituent represented by the above formula (5-4) can be obtained by reacting an isocyanato group or a thioisocyanato group with a lactam such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam.

  The substituent represented by the above formula (5-5) can be obtained by dimerizing an isocyanato group using a catalyst and carbodiimidizing as shown in the following formula. The substituent represented by the above formula (5-5) is dissociated by heating to generate an isocyanato group. In the present invention, a base generator having an isocyanato group at the terminal is prepared, and the base generator can be obtained by dimerization using a catalyst. Here, as the catalyst, for example, any known phosphorus catalyst is preferably used. For example, 1-phenyl-2-phosphorin-1-oxide, 3-methyl-2-phosphorin-1-oxide, 1-ethyl- Examples include 2-phosphorin-1-oxide, 3-methyl-1-phenyl-2-phosphorin-1-oxide, and phospholine oxides such as these 3-phosphorin isomers.

（式中、Ｒは有機基である。）

(In the formula, R is an organic group.)

  The substituent represented by the above formula (5-6) can be obtained by reacting the carboxyl group with an acid azide such as diphenyl phosphate azide. The substituent represented by the above formula (5-6) undergoes a Curtius transition by heating to generate an isocyanato group. In this invention, it can obtain by preparing the base generator which has a carboxyl group at the terminal, and reacting acid azides, such as diphenylphosphoric acid azide, with the carboxyl group of the said base generator.

Moreover, as a substituent which a part of structure changes by heating and / or electromagnetic wave irradiation, and becomes an alkynyl group, it can obtain using the reaction which blocks a well-known alkynyl group.
Examples of the reaction for blocking an alkynyl group include a reaction for blocking with a silyl group represented by the above formula (2-3).

The functional group whose structure is partially changed by heating and / or irradiation with electromagnetic waves may be directly bonded to the benzene ring as a substituent at any position of R ² , R ³ , R ⁴ and R ^5. In addition, it may be bonded to a benzene ring through a linking group as appropriate.

When two or more of R ^{2 to} R ⁵ are bonded to form an alicyclic hydrocarbon structure such as a cyclohexyl group, or two or more of R ^{2 to} R ⁵ are bonded to bond them When a condensed ring such as naphthalene, anthracene, phenanthrene, indene, and fluorene is formed by sharing the atoms of the benzene ring, a part of the structure is changed to the cyclic structure by heating and / or irradiation with electromagnetic waves. It may have a functional group.

^{<R 6} and ^R 7>
In the general formula (B) and the general formula (1), R ⁶ and R ⁷ are each independently a hydrogen atom or an organic group, but at least one of R ⁶ and R ⁷ is an organic group.
Examples of the organic group include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogen atomized alkyl group. These organic groups may contain a bond or substituent other than a hydrocarbon atom group such as a hetero atom in the organic group, and these may be linear or branched.
The organic group in R ⁶ and R ⁷ is usually a monovalent organic group. However, in the case of forming a cyclic structure to be described later, the generated NHR ⁶ R ⁷ is an NH group capable of forming an amide bond such as diamine. In the case of a basic substance having two or more, it can be a divalent or higher organic group.

R ⁶ and R ⁷ may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbon atoms, heterocyclic rings, and condensed rings, and the alicyclic hydrocarbon atoms, heterocyclic rings, and condensed rings. The structure formed may be sufficient.

The bond other than the hydrocarbon atom group in the organic group of R ⁶ and R ⁷ is not particularly limited as long as the effect of the present invention is not impaired. An ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester Bond, amide bond, urethane bond, imino bond (-N = C (-R)-, -C (= NR)-, where R is a hydrogen atom or a monovalent organic group), carbonate bond, sulfonyl bond, sulfinyl Examples include a bond and an azo bond. From the viewpoint of heat resistance, the bond other than the hydrocarbon atom group in the organic group includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C ( -R)-, -C (= NR)-: where R is a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

The substituent other than the hydrocarbon atom group in the organic group of R ⁶ and R ⁷ is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group. , Isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl Group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group, And arylthioether groups Amino group (-NH2, -NHR, -NRR ': wherein, R and R' are each independently a hydrocarbon atom group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon atom group. Moreover, the hydrocarbon atom group contained in the substituent may be linear, branched, or cyclic.
Examples of the substituent other than the hydrocarbon atom group in the organic group of R ⁶ and R ⁷ include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, and an isothiocyanato group. , Silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino A group, a phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group are preferred.

Since the base produced from the base generator represented by the general formula (1) produced by the production method of the present invention is NHR ⁶ R ⁷ , primary amines, secondary amines, or heterocyclic compounds can be mentioned. The bases include aliphatic amines and aromatic amines, respectively. In addition, the heterocyclic compound here means that NHR ⁶ R ⁷ has a cyclic structure and has aromaticity. Non-aromatic heterocyclic compounds that are not aromatic heterocyclic compounds are included here in aliphatic amines as alicyclic amines.

Furthermore, the base generated from the base generator represented by the general formula (1) is not only a basic compound such as monoamine having only one NH group capable of forming an amide bond, but also an amide such as diamine, triamine and tetraamine. It may be a basic compound having two or more NH groups capable of forming a bond. The base generator for generating such a basic compound is further provided with an N (C═O) CH ₃ structure at one or more terminals of R ⁶ and / or R ^{7 having} the structure represented by the general formula (B). It can manufacture using the acetamide derivative which has this. Furthermore, when the acetamide derivative having such a structure is synthesized by reacting a basic compound represented by NHR ⁶ R ⁷ with acetic anhydride, for example, diamine, triamine, tetraamine can be used as the basic compound. It can be synthesized by using a basic compound having two or more NH groups capable of forming an amide bond.

  Aliphatic primary amines include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, pentylamine, isoamylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine , Heptylamine, cycloheptaneamine, octylamine, 2-octaneamine, 2,4,4-trimethylpentan-2-amine, cyclooctylamine and the like.

  Examples of the aromatic primary amine include aniline, 2-aminophenol, 3-aminophenol, and 4-aminophenol.

  Aliphatic secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, ethylmethylamine, aziridine, azetidine, pyrrolidine, piperidine, azepan, azocan, methylaziridine, dimethylaziridine, methylazetidine, dimethyl Examples thereof include azetidine, trimethylazetidine, methylpyrrolidine, dimethylpyrrolidine, trimethylpyrrolidine, tetramethylpyrrolidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, pentamethylpiperidine and the like, among which alicyclic amine is preferable.

  Aromatic secondary amines include methylaniline, diphenylamine, and N-phenyl-1-naphthylamine. In addition, as an aromatic heterocyclic compound having an NH group capable of forming an amide bond, an imino bond (—N═C (—R) —, —C (═NR) —, Here, R preferably has a hydrogen atom or a monovalent organic group), and examples thereof include imidazole, purine, triazole, and derivatives thereof.

As amines higher than diamine, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, Linear aliphatic alkylenediamines such as 1,9-nonanediamine and 1,10-decanediamine; 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl- 1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3- Branched aliphatic alkylenediamines such as dimethyl-1,4-butanediamine; diethylenetriamine, triethylenetetramine, tetraethylenepenta Formula _{NH 2 (CH 2 CH 2 NH} ) polyethylene amines represented by n _H such emissions; cyclohexane diamine, methylcyclohexane diamine, isophorone diamine, norbornane dimethylamine, tricyclodecane dimethylamine, alicyclic such as menthenediamine Formula diamines; aromatic diamines such as p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, diaminodiphenylsulfone; benzenetriamine, melamine, 2,4 And triamines such as 2,6-triaminopyrimidine; and tetraamines such as 2,4,5,6-tetraaminopyrimidine.

The thermal properties and basicity of the base produced from the base generator represented by the general formula (1) differ depending on the substituent introduced at the positions of R ⁶ and R ⁷ .
When the base generator is used as a photosensitive resin composition, the catalytic action, such as lowering the reaction start temperature for the reaction from the polymer precursor to the final product, is more effective as a base having a higher basicity. The smaller the addition, the lower the temperature enables the reaction to the final product. In general, secondary amines have higher basicity than primary amines, and their catalytic effect is greater.
In addition, aliphatic amines are preferred over aromatic amines because they are more basic.

  Moreover, when the base produced | generated from the base generator represented by General formula (1) is a secondary amine and / or a heterocyclic compound, it is preferable from the point that the sensitivity of the said base generator becomes high. It is presumed that the use of a secondary amine or a heterocyclic compound eliminates the active hydrogen atom at the amide bond site, which changes the electron density and improves the isomerization sensitivity. .

Further, from the viewpoint of the thermophysical properties of the base to be eliminated and the basicity, the organic groups of R ⁶ and R ⁷ are each independently preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably carbon atoms. It is preferable that it is number 1-8.

  The base generator represented by the general formula (1) has a geometric isomer, but it is preferable to use only the trans isomer. However, there is a possibility that the cis isomer, which is a geometric isomer, may be mixed during the synthesis and purification steps, storage, etc. In this case, a mixture of the trans isomer and the cis isomer may be used, but the solubility contrast can be increased. Therefore, it is preferable that the ratio of cis-isomer is less than 10%.

  Moreover, it is preferable from the point of the ease of the refinement | purification after a synthesis | combination that the base produced from the base generator represented by General formula (1) has one NH group which can form an amide bond. In particular, when the photosensitive resin composition is combined with a polyimide precursor or a polybenzoxazole precursor, it preferably has one NH group capable of forming an amide bond.

  On the other hand, when combined with an epoxy compound as a photosensitive resin composition, the base generated from the base generator represented by the general formula (1) has two or more NH groups capable of forming an amide bond. A thing can also be used suitably from the point which can function not only as a hardening accelerator but as a hardening | curing agent.

In the production method according to the present invention, when both R ⁶ and R ⁷ in the general formula (B) are organic groups, the reaction yield of the base generator represented by the general formula (1) becomes higher. Since there exists a tendency, the manufacturing method of the base generator which concerns on this invention is suitable for manufacture of the base generator which generates a secondary amine.

As the benzaldehyde derivative represented by the general formula (A), a commercially available product can be used if a derivative having a desired structure is commercially available. The benzaldehyde derivative may be obtained by appropriately synthesizing. When R ¹ is a protecting group, it can be obtained as described above. The aldehyde having each substituent in R ^{2 to} R ⁵ is, for example, a general ether synthesis method such as a Duff reaction or a Vilsmeier-Haack reaction with a phenol having a corresponding substituent, or a Williamson reaction with dihydroxybenzaldehyde. Can be synthesized. The introduction of other substituents can be appropriately performed using a known method.

As the acetamide derivative represented by the general formula (B), a commercially available product can be used if a derivative having a desired structure is commercially available. The acetamide derivative may be obtained by appropriately synthesizing using a known method. For example, it can be synthesized by reacting a basic compound represented by NHR ⁶ R ⁷ with acetic anhydride, acetyl halide, acetyl azide or the like.

  The use amount of the acetamide derivative represented by the general formula (B) used in the method for producing a base generator according to the present invention is 1.0 to 2 with respect to the benzaldehyde derivative represented by the general formula (A). It is preferably 0 molar equivalent, and further 1.0 to 1.3 molar equivalent suppresses the formation of by-products, and increases the reaction yield of the base generator represented by the general formula (1). It is preferable from the point of improving.

[Organic solvent]
The step of reacting the benzaldehyde derivative represented by the general formula (A) with the acetamide derivative represented by the general formula (B) is performed in an organic solvent.
As the organic solvent, a solvent in which a benzaldehyde derivative represented by the general formula (A), a base described later, and an acetamide derivative represented by the general formula (B) are dissolved and does not react with these compounds may be used. From the viewpoint of improving the reaction yield of the base generator. Among these, one or more solvents selected from the group consisting of toluene, dimethylformamide, and tetrahydrofuran are more preferable from the viewpoint of improving the reaction yield of the base generator, and further, dimethylformamide is preferable. This is more preferable from the viewpoint of improving the reaction yield of the generator.
The amount of the organic solvent to be used is not particularly limited, but usually an amount of about 5 to 30 times the mass of the benzaldehyde derivative represented by the general formula (A) is used.

[base]
In the method for producing a base generator according to the present invention, the reaction of the benzaldehyde derivative represented by the general formula (A) and the acetamide derivative represented by the general formula (B) is performed in the presence of a base. The base is presumed to extract the hydrogen at the α-position of the acetamide derivative and to proceed with the reaction with the benzaldehyde derivative.
Examples of the base used in the present invention include sodium hydroxide, potassium hydroxide, potassium carbonate, metal alkoxide, metal amide and the like. Among them, it is preferable to use a strong base having low nucleophilicity from the viewpoint of suppressing side reactions and improving the reaction yield of the base generator. For example, potassium-t-butoxide, sodium-t-butoxide, lithium-t -Butoxide, lithium diisopropylamide, potassium hexamethyldisilazide, lithium tetramethylpiperidide and the like are preferably used. Among strong bases having low nucleophilicity, it is more preferable to use potassium t-butoxide from the viewpoint of improving the reaction yield of the base generator.

  The addition amount of the base is not particularly limited, but is preferably 2.0 to 6.0 molar equivalents, more preferably 2.1 to 4.0 moles with respect to the acetamide derivative represented by the general formula (B). It is preferable that it is equivalent from the point which improves the reaction yield of a base generator.

[Other reaction conditions]
The procedure is not particularly limited as long as the benzaldehyde derivative represented by the general formula (A) can be reacted with the acetamide derivative represented by the general formula (B) in an organic solvent in the presence of a base. For example, in this step, first, a benzaldehyde derivative represented by the above general formula (A) and an acetamide derivative represented by the above general formula (B) are added and stirred in a solvent, and then a base is added. Can be mentioned.

Although the reaction temperature in the said reaction process does not have a restriction | limiting in particular, It is desirable that it is about 10 degreeC-110 degreeC. At such a temperature range, the reaction is not slow and the product can be obtained in good yield.
Moreover, there is no restriction | limiting in particular in the reaction pressure of these reaction, but normal pressure-0.1 MPa are desirable, and normal pressure is further more desirable.
In addition, the reaction time in this step cannot be generally stated because it may vary depending on the phosphonate derivative represented by the above general formula (B) and the amount of base used, reaction temperature, etc., but usually 1 to 48 hours, preferably Is set in the range of 3-24 hours.

The base generator represented by the general formula (1) produced by the production method of the present invention may be further subjected to a reaction for introducing a substituent thereafter. For example, a reactive functional group such as an epoxy group is introduced by reacting epichlorohydrin with a functional group such as a hydroxyl group that has been introduced in advance as any of R ^{2 to} R ⁵ , or a protective group is introduced. May be.

(Example 1: Synthesis of base generator)
In a 1000 mL flask, 19.5 g of the following compound (6) (manufactured by Tokyo Chemical Industry, 2-hydroxy-4-methoxybenzaldehyde), 195 mL of dimethylformamide, 20.2 g of the following compound (7) (Tokyo Chemical Industry, 1-acetylpiperidine) The mixture was stirred and 40.3 g of potassium t-butoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The reaction was carried out at about 110 ° C. for about 4 hours. After cooling, 195 mL of water and 32.4 g of acetic acid were added in order, and the mixture was further cooled with ice, and the precipitated crystals were filtered. After heating and dissolving 20.0 g of the obtained crystals in 600 mL of methanol, the mixture was cooled and crystallized. After cooling with ice, the precipitated crystals were filtered and dried to obtain 27.6 g of a base generator represented by the chemical formula (8) (yield 82.5%). Solid waste did not occur.
The structure of the obtained base generator was confirmed by NMR (manufactured by JEOL, JNM-EX270) and LC-MS (manufactured by Waters, micromass ZQ).

( Reference Example 2 : Synthesis of base generator)
In a test tube, 3 mL of tetrahydrofuran was mixed with 0.304 g of the above compound (6) (2-hydroxy-4-methoxybenzaldehyde, manufactured by Tokyo Chemical Industry), 0.254 g of the above compound (7) (manufactured by Tokyo Chemical Industry, 1-acetylpiperidine). The mixture was stirred and 0.45 g of potassium t-butoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The reaction temperature was set to a maximum of 50 ° C., and the reaction was conducted for 47 hours. After cooling, 3 mL of water and 0.36 g of acetic acid were added in order, and the mixture was further cooled with ice, and the precipitated crystals were filtered. 0.35 g of the obtained crystal was heated and dissolved in 7 mL of methanol, then cooled and crystallized. After cooling with ice, the precipitated crystals were filtered and dried to obtain 0.28 g of a base generator represented by the above chemical formula (8) (yield 54%). Solid waste did not occur.
The synthesis of the base generator was confirmed by high performance liquid chromatography (manufactured by JASCO Corporation, Gulliver).

( Reference Example 3 : Synthesis of base generator)
In a test tube, 21 mL of toluene was charged with 2.13 g of the above compound (6) (manufactured by Tokyo Chemical Industry, 2-hydroxy-4-methoxybenzaldehyde), the above compound (7) (manufactured by Tokyo Chemical Industry, trade name: 1-acetylpiperidine). 1.78 g was added and stirred, and 3.14 g of potassium t-butoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The reaction temperature was up to 100 ° C., and the reaction was performed for 8 hours. After cooling, 21 mL of water and 1.7 g of acetic acid were sequentially added, and the mixture was further cooled with ice, and the precipitated crystals were filtered. After heating and dissolving 1.9 g of the obtained crystals in 38 mL of methanol, the mixture was cooled and crystallized. After cooling with ice, the precipitated crystals were filtered and dried to obtain 1.5 g of a base generator represented by the above chemical formula (8) (yield 41%). Solid waste did not occur.
It confirmed the synthesis of base generator by high performance liquid chromatography.

(Comparative Example 1: Synthesis of base generator)
In a test tube, 3 mL of dimethylformamide was combined with 0.304 g of the above compound (6) (manufactured by Tokyo Chemical Industry, 2-hydroxy-4-methoxybenzaldehyde), and the above compound (7) (manufactured by Tokyo Chemical Industry, trade name: 1-acetylpiperidine). ) 0.254 g was added and stirred, and 10 μL of concentrated sulfuric acid was added. The reaction temperature was up to 100 ° C., and the reaction was performed for 4 hours. When the obtained crystal was measured by high performance liquid chromatography, the production of the base generator represented by the chemical formula (8) was hardly observed.

(Comparative Example 2: Synthesis of base generator)
In a test tube, 0.304 g of compound (6) (manufactured by Tokyo Chemical Industry, 2-hydroxy-4-methoxybenzaldehyde) and 0.254 g of compound (7) (manufactured by Tokyo Chemical Industry, 1-acetylpiperidine) are added to 3 mL of tetrahydrofuran. Stir and add 10 μL of concentrated sulfuric acid. The reaction temperature was up to 65 ° C., and the reaction was performed for 4 hours. When the obtained crystal was measured by high performance liquid chromatography, the production of the base generator represented by the chemical formula (8) was hardly observed.

(Comparative Example 3: Synthesis of base generator)
In a test tube, 0.304 g of compound (6) (manufactured by Tokyo Chemical Industry, 2-hydroxy-4-methoxybenzaldehyde) and 0.254 g of compound (7) (manufactured by Tokyo Chemical Industry, 1-acetylpiperidine) are added to 3 mL of toluene. Stir and add 10 μL of concentrated sulfuric acid. The reaction temperature was up to 100 ° C., and the reaction was performed for 4 hours. When the obtained crystal was measured by high performance liquid chromatography, the production of the base generator represented by the chemical formula (8) was hardly observed.

(Comparative Example 4: Synthesis of base generator)
In a test tube, 0.34 g of compound (6) (manufactured by Tokyo Chemical Industry Co., Ltd., 2-hydroxy-4-methoxybenzaldehyde) and 0.354 g of compound (7) (manufactured by Tokyo Chemical Industry Co., Ltd., 1-acetylpiperidine) were added to 3 mL of dimethylformamide. The mixture was stirred and 0.027 g of aluminum chloride (Wako Pure Chemical Industries, Ltd.) was added. The reaction temperature was up to 100 ° C., and the reaction was performed for 8 hours. When the obtained crystal was measured by high performance liquid chromatography, the production of the base generator represented by the chemical formula (8) was hardly observed.

(Comparative Example 5: Synthesis of base generator)
In a test tube, 0.304 g of compound (6) (manufactured by Tokyo Chemical Industry, 2-hydroxy-4-methoxybenzaldehyde) and 0.254 g of compound (7) (manufactured by Tokyo Chemical Industry, 1-acetylpiperidine) are added to 3 mL of tetrahydrofuran. The mixture was stirred and 0.027 g of aluminum chloride (Wako Pure Chemical Industries, Ltd.) was added. The reaction temperature was up to 65 ° C., and the reaction was performed for 8 hours. When the obtained crystal was measured by high performance liquid chromatography, the production of the base generator represented by the chemical formula (8) was hardly observed.

(Comparative Example 6: Synthesis of base generator)
In a test tube, 0.304 g of compound (6) (manufactured by Tokyo Chemical Industry, 2-hydroxy-4-methoxybenzaldehyde) and 0.254 g of compound (7) (manufactured by Tokyo Chemical Industry, 1-acetylpiperidine) are added to 3 mL of toluene. The mixture was stirred and 0.027 g of aluminum chloride (Wako Pure Chemical Industries, Ltd.) was added. The reaction temperature was up to 100 ° C., and the reaction was performed for 8 hours. When the obtained crystal was measured by high performance liquid chromatography, the production of the base generator represented by the chemical formula (8) was hardly observed.

(Comparative Example 7: Synthesis of base generator)
In a test tube, 0.304 g of compound (6) (manufactured by Tokyo Chemical Industry, 2-hydroxy-4-methoxybenzaldehyde) and 0.254 g of compound (7) (manufactured by Tokyo Chemical Industry, 1-acetylpiperidine) are added to 3 mL of toluene. The mixture was stirred and 0.190 g of p-toluenesulfonic acid hydrate (Wako Pure Chemical Industries, Ltd.) was added. The reaction temperature was up to 120 ° C., and the reaction was performed for 5 hours. When the obtained crystal was measured by high performance liquid chromatography, the production of the base generator represented by the chemical formula (8) was hardly observed.

Claims (3)

Benzaldehyde derivatives table by the following general formula (A), in dimethylformamide, in the presence of a base, characterized by having a step of reacting the acetamide derivative as tables in the following general formula (B), the following general formula The manufacturing method of the base generator represented by (1).

(In General Formula (A), General Formula (B), and General Formula (1), R ¹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves. R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group Phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, azide group or organic group, which may be the same or different, and R ² , R ³ , R ⁴ and R ⁵ are Two or more may combine to form a cyclic structure, and may include a heteroatom bond, and R ⁶ and R ⁷ are each independently a hydrogen atom or an organic group, and are the same. The May be different .R ⁶ and R ^7, which may be they are attached to form a cyclic structure, may contain a binding heteroatom. Provided that at least one of R ⁶ and R ⁷ Is an organic group.)   The method for producing a base generator according to claim 1, wherein the base is a metal alkoxide.   The method for producing a base generator according to claim 1 or 2, wherein the base is potassium-t-butoxide.