JP5617564B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition comprising a photobase generator having a property of generating a base upon irradiation with active energy rays, and more specifically, includes a photobase generator having high solubility in an organic solvent. It is related with the photosensitive resin composition which becomes.

  For example, curing by a polymerization initiator that is sensitive to active energy rays such as infrared rays, visible rays, ultraviolet rays, and X-rays (hereinafter simply abbreviated as a photopolymerization initiator) (hereinafter abbreviated simply as photocuring may be sometimes used). Is low in temperature and short compared to curing by a heat-sensitive polymerization initiator (hereinafter sometimes simply referred to as “thermal polymerization initiator”) (hereinafter, sometimes simply referred to as “thermal curing”). The photosensitive resin composition containing these photopolymerization initiators can be used as a photocuring material as a paint, because it has many advantages such as being able to be cured in time and forming a fine pattern. Widely used in the field of surface processing of printing inks, dental materials, resists and the like.

  Photopolymerization initiators used in the photocuring technique can be roughly classified into three groups, photoradical generators, photoacid generators, and photobase generators, depending on the active species generated. Photoradical generators are photopolymerization initiators that generate radical species by irradiation with active energy rays, such as acetophenone, and have been widely used. However, radical species are lost by oxygen in the air. Since it has the property of being activated, there is a disadvantage that the polymerization reaction is inhibited and curing is suppressed in the presence of oxygen. For this reason, especially when it is going to produce a thin film using the photosensitive resin composition containing a photoradical generator, special devices, such as interrupting | blocking oxygen in air, are required. In addition, since the photoacid generator is a photopolymerization initiator that generates an acid upon irradiation with active energy rays, there is an advantage that it is not inhibited by oxygen. It is used for practical use. However, when the acid generated by irradiation with active energy rays remains in the system even after curing, the cured film after curing the photosensitive resin composition containing these photoacid generators is modified to form a film. In the field of semiconductors and the like such as performance degradation, the problem of corrosiveness to metal wiring on a semiconductor substrate due to acid has been pointed out. On the other hand, since the photobase generator generates a base by irradiation with active energy rays, it is not affected by oxygen in the air, and it is difficult to cause corrosion problems and denaturation of the cured film. In recent years, research and development has been actively conducted.

  As such a photobase generator, for example, in Patent Document 1, carbamate-based (urethane-based) photobase generators are proposed, and many photosensitive resin compositions containing these photobase generators have also been proposed ( For example, Patent Document 2). However, for example, conventional photobase generators such as Patent Documents 1 and 2 simultaneously generate carbon dioxide gas as a by-product because decarbonation occurs when a base is generated by irradiation with active energy rays. For this reason, when it is going to produce a cured film using the photosensitive resin composition containing these photobase generators, when the by-produced carbon dioxide gas becomes a bubble and remains in a cured film, it is a film | membrane. There is a problem that the strength may be reduced, or when the carbon dioxide gas is evaporated from the inside of the cured film to the outside, the surface of the cured film may be roughened.

  Recently, as a photobase generator for solving such problems, a photocyclization type photobase generator that does not involve decarboxylation when a base is generated by irradiation with active energy rays has been developed. A photosensitive resin composition containing a base generator has been proposed (for example, Patent Documents 3 and 4). However, for example, the photobase generators of Patent Documents 3 and 4 are not sufficiently soluble in organic solvents, and glycol solvents such as propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA), for example, It is particularly poorly soluble in organic solvents widely used in this field such as ester solvents such as γ-butyrolactone (γ-BL). For this reason, when it is going to dissolve the photosensitive resin composition containing these photobase generators in the above-mentioned organic solvent and to make a cured film, it is because only a small amount of photobase generator can be used. Therefore, the contrast between the exposed part (cured part) and the unexposed part (uncured part) becomes worse, or conversely, when a large amount of photobase generator is used to improve the contrast, the generator is precipitated as a solid. There is a problem such as that. For these reasons, the photosensitive resin composition containing these photobase generators has a problem that the usable organic solvent is limited and the versatility is low.

  Under such circumstances, for example, a photobase generator that is highly soluble in various organic solvents such as glycol solvents and ester solvents and does not generate carbon dioxide when generating a base by irradiation with active energy rays. The development of a photosensitive resin composition containing benzene is desired.

Japanese Patent Laid-Open No. 10-77264 JP 2006-189591 A JP 2009-80452 A International Publication No. WO2009 / 123122

  The problem to be solved by the present invention is a photosensitive resin containing a photobase generator that is highly soluble in various organic solvents and does not generate carbon dioxide when generating a base by irradiation with active energy rays. It is to provide a composition. That is, the present inventors include versatile photobase generators that are soluble in various organic solvents if the solubility of conventionally known photocyclization type photobase generators without decarboxylation is improved. Focusing on the possibility of providing a high-sensitivity photosensitive resin composition, the inventors have intensively studied the development of a photocyclization-type photobase generator that does not involve decarboxylation with improved solubility. As a result, by introducing a substituent on a specific carbon atom in the structure of the above-described conventionally known photobase generator, compared with the conventionally known photocyclization type photobase generator without decarboxylation. The present inventors have found that the solubility in organic solvents is dramatically improved. That is, the improved photobase generator in which a substituent is introduced on a specific carbon atom of a conventionally known photocyclization type photobase generator without decarboxylation is an organic solvent as compared with the conventional photobase generator. As a result, the present inventors have completed the present invention.

  The present invention is an invention of a photosensitive resin composition comprising a base generator represented by the following general formula [1] and a base reactive resin.

（式中、Ｒ^１及びＲ^２は夫々独立して、水素原子、炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基、置換基を有していてもよいフェニル基又はシアノ基を表し、Ｒ^３〜Ｒ^６は夫々独立して、水素原子、ハロゲン原子、炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基、炭素数１〜１０の直鎖状、分枝状若しくは環状のアルコキシ基、置換基を有していてもよい炭素数６〜１０のアリール基、ヒドロキシル基又はニトロ基を表し、Ｚは１級又は２級アミン由来の基を表し、Ｒ^２とＲ^３とで環状構造を形成していてもよいし、Ｒ^３〜Ｒ^６の２つ以上が結合してＲ^３〜Ｒ^６が結合しているベンゼン環と縮合環を形成していてもよい。ただし、Ｒ^１及びＲ^２が共に水素原子であるものを除く。）

(In the formula, R ¹ and R ² are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or cyano. R ^{3 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms, A branched or cyclic alkoxy group, an optionally substituted aryl group having 6 to 10 carbon atoms, a hydroxyl group or a nitro group; Z represents a group derived from a primary or secondary amine; may form a cyclic structure with the ² and R ^3, form a benzene ring and condensed ring which R ³ to R ⁶ 2 or more is bonded to the R ³ to R ⁶ are attached Except that R ¹ and R ² are both hydrogen atoms.)

  Moreover, this invention is invention of the pattern formation material which consists of the photosensitive resin composition characterized by containing the base generator shown by the said General formula [1], and base reactive resin.

  Furthermore, the present invention provides an active energy ray to a coating film or a molded product produced from a photosensitive resin composition, which contains a base generator represented by the above general formula [1] and a base reactive resin. It is invention of the resin hardening method characterized by including the process to irradiate.

  Furthermore, the present invention provides an active energy in a predetermined pattern on a coating film produced from a photosensitive resin composition comprising a base generator represented by the above general formula [1] and a base reactive resin. It is an invention of a pattern forming method comprising a step of irradiating a line and a step of developing a coating film or a molded body after the above step.

  Moreover, this invention is invention of the photobase generator for resin hardening shown by following General formula [5].

（式中、Ｒ^１'及びＲ^２'は夫々独立して、水素原子、炭素数１〜４の直鎖状若しくは分枝状のアルキル基、置換基を有していてもよいフェニル基又はシアノ基を表し、Ｒ^３'〜Ｒ^６'は夫々独立して、水素原子、ハロゲン原子、炭素数１〜４の直鎖状若しくは分枝状のアルキル基、炭素数１〜４の直鎖状若しくは分枝状のアルコキシ基、置換基を有していてもよい炭素数６〜１０のアリール基、ヒドロキシル基又はニトロ基を表し、Ｚ'は下記式［６］〜［１４］で示される基を表し、Ｒ^２'とＲ^３'とで環状構造を形成していてもよいし、Ｒ^３'〜Ｒ^６'の２つ以上が結合してＲ^３'〜Ｒ^６'が結合しているベンゼン環と縮合環を形成していてもよい。ただし、Ｒ^１'及びＲ^２'が共に水素原子であるものを除く。）

(Wherein R ¹ ′ and R ² ′ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, or cyano. R ³ ′ to R ⁶ ′ each independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear chain having 1 to 4 carbon atoms, A branched alkoxy group, an aryl group having 6 to 10 carbon atoms which may have a substituent, a hydroxyl group or a nitro group is represented, and Z ′ represents a group represented by the following formulas [6] to [14]. It represents, may form a cyclic structure de ^'and R ^3' R 2 and, benzene R ³ 'to R ^6' 2 or more is bonded to the the R ³ 'to R ^6' are attached A ring and a condensed ring may be formed, except that R ¹ ′ and R ² ′ are both hydrogen atoms.)

（式中、Ｙ'は下記一般式［５'］で示される基を表す。）

(In the formula, Y ′ represents a group represented by the following general formula [5 ′].)

（式中、Ｙ'は下記一般式［５'］で示される基を表す。）

(In the formula, Y ′ represents a group represented by the following general formula [5 ′].)

（式中、Ｒ^１'〜Ｒ^６'は上記に同じ。）

(In the formula, R ¹ ′ to R ⁶ ′ are the same as above.)

  Since the base generator represented by the general formula [1] according to the present invention has high solubility in various organic solvents, it can be widely used regardless of the kind of the solvent. For this reason, the photosensitive resin composition of the present invention containing such a base generator is highly versatile. Moreover, since a large amount of base generator can be contained in the composition, a large amount of base can be generated by irradiation with active energy rays. For this reason, as a result, the curing of the resin effectively proceeds in the exposed portion (cured portion), the contrast between the exposed portion (cured portion) and the unexposed portion (uncured portion) is improved, and a good pattern is formed. be able to. Furthermore, the base generator represented by the general formula [1] according to the present invention does not produce carbon dioxide as a by-product when generating a base by irradiation with active energy rays. For this reason, if the photosensitive resin composition of the present invention containing such a base generator is used, a cured film having high film strength can be obtained, and a cured film having a uniform surface can be obtained.

  Since the pattern forming material of the present invention is composed of the photosensitive resin composition of the present invention as described above, a pattern with high contrast can be produced.

  Since the resin curing method and pattern forming method of the present invention use the photosensitive resin composition of the present invention as described above, they are highly versatile methods regardless of the type of organic solvent. Furthermore, the following advantages arise by forming a pattern using the composition containing the alcohol type, ester type, or glycol type organic solvent among the photosensitive resin compositions of the present invention. That is, (1) since these organic solvents have a moderate boiling point, it is possible not only to stably prepare a composition usually performed at room temperature, but also because it is not necessary to increase the baking temperature during pre-baking. , Base generators, base-reactive resins, etc. are not easily affected by heat. (2) Since these organic solvents have good compatibility with the substrate and have a good elongation during spin coating, the composition (3) Since these organic solvents have higher solubility of the base generator than other organic solvents, for example, the coating film according to the pattern forming method of the present invention or The base generator is less likely to cause phase separation during the process of producing the molded body, and (4) excellent stability that the decomposition product does not show basicity like an amide solvent and has high stability. It is a method.

In Example 1, it is a figure showing the relationship between the irradiation time at the time of making the photosensitive resin composition containing the base generator of the synthesis example 3 into a coating film, and irradiating the said coating film with an active energy ray, and a residual film rate. is there. In Example 2, it is a figure showing the relationship between the irradiation time at the time of making the photosensitive resin composition containing the base generator of the synthesis example 5 into a coating film, and irradiating the said coating film with an active energy ray, and a remaining film rate. is there. In Example 3, it is a figure showing the relationship between the irradiation time at the time of making the photosensitive resin composition containing the base generator of the synthesis example 7 into a coating film, and irradiating an active energy ray to the said coating film, and a remaining film rate. is there. In Example 4, it is a figure showing the relationship between the irradiation time at the time of making the photosensitive resin composition containing the base generator of the synthesis example 5 into a coating film, and irradiating the said coating film with an active energy ray, and a residual film rate. is there.

  In the present invention, the active energy ray means not only the electromagnetic wave having a wavelength in the visible region (visible light) but also the electromagnetic wave having the wavelength in the infrared region (infrared ray) and the electromagnetic wave having a wavelength in the ultraviolet region, unless the wavelength is specified. (Ultraviolet rays), electromagnetic waves having wavelengths in the non-visible region such as X-rays are included. In the present invention, a base generator that is sensitive to active energy rays (a base generator that generates a base upon irradiation with active energy rays) may be referred to as a photobase generator. Note that active energy rays with wavelengths of 365 nm, 405 nm, and 436 nm may be referred to as i-line, h-line, and g-line, respectively.

In the base generator represented by the general formula [1], the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ¹ and R ² is specifically, for example, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group , Neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methyl Pentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl Group, neoheptyl group, cycloheptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl Group, tert-nonyl group, neononyl group, cyclononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group (bornan-χ-yl group) , An adamantyl group, a menthyl group (menta-χ-yl group) and the like. Among them, a methyl group, an ethyl group, and an n-propyl group, which are linear or branched alkyl groups having 1 to 4 carbon atoms. , An isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group are preferable, and a methyl group that is an alkyl group having 1 carbon atom is more preferable.

In the base generator represented by the general formula [1], specific examples of the substituent in the phenyl group optionally having the substituent represented by R ¹ and R ² include a hydroxyl group, a mercapto group, Cyano group, nitro group, for example, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group A linear or branched alkyl group having 1 to 4 carbon atoms such as tert-butyl group, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec- Examples thereof include linear or branched alkoxy groups having 1 to 4 carbon atoms such as butoxy group and tert-butoxy group.

In the base generator represented by the general formula [1], R ¹ and R ² are more preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.

In the base generator represented by the general formula [1], specific examples of the halogen atom represented by R ^{3 to} R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the base generator represented by the general formula [1], the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ^{3 to} R ⁶ is specifically, for example, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group , Neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methyl Pentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl , Neoheptyl group, cycloheptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl group , Tert-nonyl group, neononyl group, cyclononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group (bornan-χ-yl group), Adamantyl group, menthyl group (menta-χ-yl group) and the like, among them, a methyl group, ethyl group, n-propyl group, which is a linear or branched alkyl group having 1 to 4 carbon atoms, An isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group are preferable, and a methyl group and a tert-butyl group are more preferable.

In the base generator represented by the general formula [1], the linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms represented by R ^{3 to} R ⁶ is specifically, for example, a methoxy group , Ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, cyclobutoxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy Group, tert-pentyloxy group, neopentyloxy group, 2-methylbutoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, cyclopentyloxy group, n-hexyloxy group, isohexyloxy group, sec- Hexyloxy, tert-hexyloxy, neohexyloxy, 2-methylpentyloxy, 1,2-dimethylbutoxy, 2,3-dimethylbut Xyl group, 1-ethylbutoxy group, cyclohexyloxy group, n-heptyloxy group, isoheptyloxy group, sec-heptyloxy group, tert-heptyloxy group, neoheptyloxy group, cycloheptyloxy group, n-octyloxy Group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, neooctyloxy group, 2-ethylhexyloxy group, cyclooctyloxy group, n-nonyloxy group, isononyloxy group, sec-nonyloxy group, tert-nonyloxy group, neononyloxy group, cyclononyloxy group, n-decyloxy group, isodecyloxy group, sec-decyloxy group, tert-decyloxy group, neodecyloxy group, cyclodecyloxy group, norbornyloxy group , Bornyloxy group (bornane-χ-yloxy group), adamantyloxy group, Menthyloxy group (menta-χ-yloxy group), etc., among others, methoxy group, ethoxy group, n-propoxy group, isopropoxy, which are linear or branched alkoxy groups having 1 to 4 carbon atoms. Group, n-butoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group are preferable, and among them, a methoxy group which is an alkoxy group having 1 carbon atom is more preferable.

In the base generator represented by the general formula [1], as the aryl group having 6 to 10 carbon atoms in the aryl group having 6 to 10 carbon atoms which may have a substituent represented by R ^{3 to} R ⁶ , Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like.

In the base generator represented by the general formula [1], specific examples of the substituent in the aryl group having 6 to 10 carbon atoms which may have a substituent represented by R ^{3 to} R ⁶ include, for example, Hydroxyl group, mercapto group, cyano group, nitro group, eg halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, eg methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl Group, sec-butyl group, tert-butyl group or the like, or a linear or branched alkyl group having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group And straight-chain or branched alkoxy groups having 1 to 4 carbon atoms such as isobutoxy group, sec-butoxy group and tert-butoxy group.

In the base generator represented by the general formula [1], R ² and R ³ may form a cyclic structure when R ² and R ³ are linked via an alkylene group having 2 to 5 carbon atoms. This means that the alkylene group may further form a cyclic structure with —C—C (═O) N— via R ² and R ³ . Specific examples of the alkylene group having 2 to 5 carbon atoms include a dimethylene group (ethylene group), a trimethylene group, a tetramethylene group, and a pentamethylene group.

In base generator represented by the general formula [1], and two or more are combined to R ³ to R ⁶ may form a benzene ring and condensed ring which is bonded in R ³ to R ⁶ is , two or more of R ³ to R ⁶ are linked via an alkylene group having 3 to 5 carbon atoms, further sharing a carbon atom of the benzene ring to which R ³ to R ⁶ is bonded to the alkylene group, For example, it means that condensed rings such as indene ring, indane ring, naphthalene ring, 1,2,3,4-tetrahydronaphthalene ring may be formed.

In the base generator represented by the general formula [1], R ^{3 to} R ⁶ are more preferably a hydrogen atom or a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms.

  In the base generator represented by the general formula [1], as the group derived from the primary or secondary amine represented by Z, specifically, for example, the following general formula [2], [3] or [4] Although the group shown is mentioned, it is not limited to these at all.

（式中、Ｒ^７及びＲ^８は夫々独立して、水素原子又は置換基を有していてもよい炭素数１〜１０の直鎖状、分枝状若しくは環状の炭化水素基を表すか、或いはこれらが結合している窒素原子と共に、置換基を有していてもよい炭素数２〜１０の含窒素脂肪族環又は含窒素芳香環を形成するものを表す。）

(Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, Or it represents what forms the C2-C10 nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring which may have a substituent with the nitrogen atom which these have couple | bonded.)

（式中、Ｒ^９及びＲ^１０は夫々独立して、水素原子又は置換基を有していてもよい炭素数１〜１０の直鎖状、分枝状若しくは環状の炭化水素基を表し、Ｖ_１は主鎖の炭素原子が酸素原子又はケイ素原子で置換されていてもよい炭素数２〜１０のアルキル基を表し、Ｙは下記一般式［１'］で示される基を表す。）

(Wherein R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and V ₁ represents an alkyl group having 2 to 10 carbon atoms in which the carbon atom of the main chain may be substituted with an oxygen atom or a silicon atom, and Y represents a group represented by the following general formula [1 ′].

（式中、Ｒ^１〜Ｒ^６は上記に同じ。）

(Wherein R ^{1 to} R ⁶ are the same as above)

（式中、Ｒ^１１〜Ｒ^１４は夫々独立して、水素原子又は炭素数１〜６の直鎖状、分枝状若しくは環状のアルキル基を表し、Ｖ_２は主鎖の炭素原子が酸素原子又はケイ素原子で置換されていてもよい炭素数１〜１０のアルキル基を表し、Ｙは下記一般式［１'］で示される基を表し、ｍ及びｎは夫々独立して、１〜２の整数を表す。）

(In the formula, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and V ₂ represents an oxygen atom as the main chain carbon atom. Or an alkyl group having 1 to 10 carbon atoms which may be substituted with a silicon atom, Y represents a group represented by the following general formula [1 ′], and m and n are each independently 1 to 2 Represents an integer.)

（式中、Ｒ^１〜Ｒ^６は上記に同じ。）

(Wherein R ^{1 to} R ⁶ are the same as above)

In the group derived from the primary or secondary amine represented by the general formula [2], a linear or branched group having 1 to 10 carbon atoms which may have a substituent represented by R ⁷ and R ⁸ , or Specific examples of the hydrocarbon group in the cyclic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Among them, an alkyl group, an aryl group, and an aralkyl group are preferable. Of these, an alkyl group is more preferred.

  Specific examples of the linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms in the case where the hydrocarbon group is an alkyl group include, for example, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1 , 2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group 2,3-dimethylbutyl, 1-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, neoheptyl, Loheptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group , Neononyl group, cyclononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group (bornan-χ-yl group), adamantyl group, menthyl group (Menta-χ-yl group) and the like. Among them, a linear alkyl group having 1 to 6 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, and n-butyl. Group, n-pentyl group and n-hexyl group are preferred.

  Specific examples of the linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms in the case where the hydrocarbon group is an alkenyl group include, for example, a vinyl group, a 1-propenyl group, and a 2-propenyl group. (Allyl group), isopropenyl group, n-butenyl group, n-pentenyl group, cyclopentenyl group, n-hexenyl group, cyclohexenyl group, n-heptenyl group, n-octenyl group, n-nonenyl group, n-decenyl group Groups and the like.

  Specific examples of the linear or branched alkynyl group having 2 to 10 carbon atoms when the hydrocarbon group is an alkynyl group include, for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group (propargyl group). Group), n-butynyl group, 1-methylpropargyl group, n-pentynyl group, n-hexynyl group, n-heptynyl group, n-octynyl group, n-noninyl group, n-decynyl group and the like.

  Specific examples of the aryl group having 6 to 10 carbon atoms when the hydrocarbon group is an aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

  Specific examples of the aralkyl group having 7 to 10 carbon atoms in the case where the hydrocarbon group is an aralkyl group include a benzyl group, a phenethyl group, an α-methylbenzyl group, a 3-phenylpropyl group, a 1-methyl- Examples include 1-phenylethyl group, 4-phenylbutyl group, 2-methyl-2-phenylpropyl group, 1,2,3,4-tetrahydronaphthyl group and the like.

In the group derived from the primary or secondary amine represented by the general formula [2], a linear or branched group having 1 to 10 carbon atoms which may have a substituent represented by R ⁷ and R ⁸ , or Specific examples of the substituent in the cyclic hydrocarbon group include hydroxyl groups, mercapto groups, cyano groups, nitro groups, and the above hydrocarbons such as halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms and iodine atoms. Examples include substituents (functional groups) other than hydrocarbon groups, which are bonded to the group. Therefore, in the present invention, the carbon number in the linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent means the carbon number of the hydrocarbon group portion. , The number of carbon atoms of the above substituent (cyano group or the like) is not included.

In primary or secondary amine groups derived from the general formula [2], together with the nitrogen atom to which they represented by R ⁷ and R ⁸ (R ⁷ and R ⁸⁾ are attached have a substituent What forms a nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring having 2 to 10 carbon atoms in the one that forms a nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring having 2 to 10 carbon atoms may be R ¹ and R ² is linked to form a saturated or unsaturated alkylene group (saturated or unsaturated alkanediyl group) bonded to a nitrogen atom together by two bonds, and more specifically, a hetero atom It means forming a saturated or unsaturated alkylene group (saturated or unsaturated alkanediyl group) having 2 to 10 carbon atoms which may be present in the chain. Specific examples of the saturated or unsaturated alkylene group (saturated or unsaturated alkanediyl group) having 2 to 10 carbon atoms that may have a hetero atom in the chain include, for example, a dimethylene group (ethylene group) and a trimethylene group. , Tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, 1-methyl-dimethylene group (1-methyl-ethylene group), 1-methyl-trimethylene group, 2 -Methyl-trimethylene group, 1,4-dimethyl-tetramethylene group, 1,4-diethyl-tetramethylene group, 1,4-dipropyl-tetramethylene group, 1,5-dimethyl-pentamethylene group, 1,5- Linear or branched carbon number of 2 or 2 having no hetero atom such as diethyl-pentamethylene group or 1,3,5-trimethyl-pentamethylene group in the chain 0 saturated alkylene group (saturated alkanediyl group), for example, methyleneoxymethylene group, methyleneoxydimethylene group (methyleneoxyethylene group), dimethyleneoxydimethylene group (ethyleneoxyethylene group), methylenethiomethylene group, methylenethio Dimethylene group (methylenethioethylene group), dimethylenethiodimethylene group (ethylenethioethylene group), 1,1′-dimethyl-dimethyleneoxydimethylene group (1,1′-dimethyl-ethyleneoxyethylene group), 1 , 1'-Diethyl-dimethyleneoxydimethylene group (1,1'-diethyl-ethyleneoxyethylene group), 1,1'-dipropyl-dimethyleneoxydimethylene group (1,1'-dipropyl-ethyleneoxyethylene group) Group), 1,1′-dimethyl-dimethylenethiodimethylene group (1,1′-dimethyl-ethyleneethylene) Oethylene group), 1,1'-diethyl-dimethylenethiodimethylene group (1,1'-diethyl-ethylenethioethylene group), 1,1'-dipropyl-dimethylenethiodimethylene group (1,1'-dipropyl- Linear or branched saturated alkylene group having 2 to 10 carbon atoms (saturated alkanediyl group) having a hetero atom (oxygen atom, sulfur atom, etc.) in the chain, such as buta-1 , 3-Diene-1,4-diyl group, 1,4-dimethyl-buta-1,3-diene-1,4-diyl group, 1,4-diethyl-buta-1,3-diene-1,4 A straight chain or branched chain having 2 to 10 carbon atoms having no hetero atom in the chain, such as a -diyl group and a 1,4-dipropyl-buta-1,3-diene-1,4-diyl group Saturated alkylene groups (unsaturated alkanediyl groups), such as 2-aza-buta-1,3-diene-1,4-diyl groups, 1,4-dimethyl-2-aza-buta-1,3-diene-1,4-diyl group, 1,4-diethyl-2-aza-buta-1,3-diene-1,4-diyl group, 1,4-dipropyl-2-aza-buta-1,3-diene-1,4-diyl group, 1-aza-buta-1,3-diene-1,4-diyl group, 2,4-dimethyl- 1-aza-buta-1,3-diene-1,4-diyl group, 2,4-diethyl-1-aza-buta-1,3-diene-1,4-diyl group, 2,4-dipropyl group 1-aza-buta-1,3-diene-1,4-diyl group or the like, a linear or branched unsaturated alkylene group having 2 to 10 carbon atoms having a hetero atom (such as a nitrogen atom) in the chain (Unsaturated alkanediyl group) and the like.

  Among these saturated or unsaturated alkylene groups (saturated or unsaturated alkanediyl groups), for example, dimethylene group (ethylene group), trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene Group, nonamethylene group, decamethylene group, 1-methyl-dimethylene group (1-methyl-ethylene group), 1-methyl-trimethylene group, 2-methyl-trimethylene group, 1,4-dimethyl-tetramethylene group, 1,4 -Diethyl-tetramethylene group, 1,4-dipropyl-tetramethylene group, 1,5-dimethyl-pentamethylene group, 1,5-diethyl-pentamethylene group, 1,3,5-trimethyl-pentamethylene group, etc. Linear or branched C2-C10 saturated alkylene group (saturated alkanediyl group) having no hetero atom in the chain, for example Methyleneoxymethylene group, methyleneoxydimethylene group (methyleneoxyethylene group), dimethyleneoxydimethylene group (ethyleneoxyethylene group), methylenethiomethylene group, methylenethiodimethylene group (methylenethioethylene group), dimethylenethiodi Methylene group (ethylenethioethylene group), 1,1′-dimethyl-dimethyleneoxydimethylene group (1,1′-dimethyl-ethyleneoxyethylene group), 1,1′-diethyl-dimethyleneoxydimethylene group ( 1,1'-diethyl-ethyleneoxyethylene group), 1,1'-dipropyl-dimethyleneoxydimethylene group (1,1'-dipropyl-ethyleneoxyethylene group), 1,1'-dimethyl-dimethylenethiodi Methylene group (1,1'-dimethyl-ethylenethioethylene group), 1,1'-diethyl-dimethylenethiodimethyl Heteroatoms (oxygen atoms, sulfur, etc.) such as a len group (1,1'-diethyl-ethylenethioethylene group) and 1,1'-dipropyl-dimethylenethiodimethylene group (1,1'-dipropyl-ethylenethioethylene group) A linear or branched saturated alkylene group having 2 to 10 carbon atoms (saturated alkanediyl group) having an atom etc. in the chain, among them, a tetramethylene group, a pentamethylene group, a hexamethylene group A straight-chain saturated alkylene group having 4 to 6 carbon atoms (saturated alkanediyl group) having no hetero atom in the chain is more preferred.

In primary or secondary amine groups derived from the general formula [2], together with the nitrogen atom to which they represented by R ⁷ and R ⁸ (R ⁷ and R ⁸⁾ are attached have a substituent Specific examples of the substituent in the nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring which may have 2 to 10 carbon atoms include a hydroxyl group, a mercapto group, a cyano group, a nitro group, such as a fluorine atom. And a substituent (functional group) other than a hydrocarbon group bonded to the above-mentioned nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring such as a halogen atom such as a chlorine atom, a bromine atom, and an iodine atom. Therefore, in the present invention, the number of carbon atoms in the nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring that may have a substituent is the nitrogen-containing aliphatic ring or nitrogen-containing aromatic. It means the number of carbon atoms of the portion forming the ring, and does not include the number of carbon atoms of the above substituent (such as a cyano group).

In the group derived from the primary or secondary amine represented by the general formula [2], R ⁷ and R ⁸ may be a linear or branched chain having 1 to 10 carbon atoms which may have a substituent. A cyclic hydrocarbon group, together with the nitrogen atom to which these (R ⁷ and R ⁸ ) are bonded, forms a nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring having 2 to 10 carbon atoms that may have a substituent. More preferred is

In the group derived from the primary or secondary amine represented by the general formula [3], a linear or branched group having 1 to 10 carbon atoms which may have a substituent represented by R ⁹ and R ¹⁰ , or Specific examples of the hydrocarbon group in the cyclic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Among them, an alkyl group, an aryl group, and an aralkyl group are preferable. Of these, an alkyl group is more preferred.

  Specific examples of the linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms in the case where the hydrocarbon group is an alkyl group include, for example, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1 , 2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group 2,3-dimethylbutyl, 1-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, neoheptyl, Loheptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group , Neononyl group, cyclononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group (bornan-χ-yl group), adamantyl group, menthyl group (Menta-χ-yl group) and the like. Among them, a linear alkyl group having 1 to 6 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, and n-butyl. Group, n-pentyl group and n-hexyl group are preferred.

  Specific examples of the linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms in the case where the hydrocarbon group is an alkenyl group include, for example, a vinyl group, a 1-propenyl group, and a 2-propenyl group. (Allyl group), isopropenyl group, n-butenyl group, n-pentenyl group, cyclopentenyl group, n-hexenyl group, cyclohexenyl group, n-heptenyl group, n-octenyl group, n-nonenyl group, n-decenyl group Groups and the like.

  Specific examples of the linear or branched alkynyl group having 2 to 10 carbon atoms when the hydrocarbon group is an alkynyl group include, for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group (propargyl group). Group), n-butynyl group, 1-methylpropargyl group, n-pentynyl group, n-hexynyl group, n-heptynyl group, n-octynyl group, n-noninyl group, n-decynyl group and the like.

  Specific examples of the aryl group having 6 to 10 carbon atoms when the hydrocarbon group is an aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

  Specific examples of the aralkyl group having 7 to 10 carbon atoms in the case where the hydrocarbon group is an aralkyl group include a benzyl group, a phenethyl group, an α-methylbenzyl group, a 3-phenylpropyl group, a 1-methyl- Examples include 1-phenylethyl group, 4-phenylbutyl group, 2-methyl-2-phenylpropyl group, 1,2,3,4-tetrahydronaphthyl group and the like.

In the group derived from the primary or secondary amine represented by the general formula [3], a linear or branched group having 1 to 10 carbon atoms which may have a substituent represented by R ⁹ and R ¹⁰ , or Specific examples of the substituent in the cyclic hydrocarbon group include hydroxyl groups, mercapto groups, cyano groups, nitro groups, and the above hydrocarbons such as halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms and iodine atoms. Examples include substituents (functional groups) other than hydrocarbon groups, which are bonded to the group. Therefore, in the present invention, the carbon number in the linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent means the carbon number of the hydrocarbon group portion. , The number of carbon atoms of the above substituent (cyano group or the like) is not included.

In the group derived from a primary or secondary amine represented by the general formula [3], R ⁹ and R ¹⁰ are more preferably a hydrogen atom.

In the group derived from the primary or secondary amine represented by the general formula [3], the main chain carbon atom represented by V ₁ may be substituted with an oxygen atom or a silicon atom. Specifically, for example, dimethylene group (ethylene group), trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, the following general formula [A ] Etc. which are shown by these.

（式中、ｐ及びｑは夫々独立して、１〜３の整数を表す。）

(In the formula, p and q each independently represent an integer of 1 to 3.)

  In the group represented by the general formula [A], p and q are more preferably 3.

In the group derived from the secondary amine represented by the general formula [4], as the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms represented by R ^{11 to} R ¹⁴ , specifically, For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert -Pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, Examples include 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group and the like. Methyl group is preferred.

In the group derived from the secondary amine represented by the general formula [4], as R ^{11 to} R ¹⁴ , a hydrogen atom is more preferable.

In the group derived from the secondary amine represented by the general formula [4], as the alkyl group having 1 to 10 carbon atoms in which the carbon atom of the main chain represented by V ₂ may be substituted with an oxygen atom or a silicon atom, Specifically, for example, methylene group, dimethylene group (ethylene group), trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, the above general formula [A ] Etc. which are shown by these.

  In the group derived from the secondary amine represented by the general formula [4], m and n are more preferably 2.

In the group derived from the primary or secondary amine represented by the general formulas [3] and [4], R ^{1 to} R ⁶ in the general formula [1 ′] represented by Y are the same as those in the general formula [1]. the same as R ¹ to R ⁶ can be mentioned.

In the base generator represented by the general formula [1], Z is a group derived from a primary or secondary amine represented by the general formula [2], and R ⁷ and R ⁸ in the general formula [2] are A base formed from a nitrogen atom to which these (R ⁷ and R ⁸ ) are bonded together with a nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring having 2 to 10 carbon atoms which may have a substituent ( Specific example of primary or secondary amine), that is, a nitrogen-containing aliphatic amine or nitrogen-containing aromatic amine having 2 to 10 carbon atoms generated from a group derived from a primary or secondary amine represented by the general formula [2] Specific examples of these include, for example, aziridine (3-membered ring), azetidine (4-membered ring), pyrrolidine (5-membered ring), piperidine (6-membered ring), hexamethyleneimine (azepane ring; 7-membered ring), heptamethyleneimine. (Azocan ring; 8-membered ring), Octame Nitrogen-containing aliphatic amines having 2 to 10 carbon atoms such as renimine (azonan ring; 9-membered ring), nonamethyleneimine (azecan ring; 10-membered ring), decamethyleneimine (11-membered ring), such as 2-methylaziridine ( 3-membered ring), 2-methylazetidine (4-membered ring), 3-methylazetidine (4-membered ring), 2,5-dimethylpyrrolidine (5-membered ring), 2,5-diethylpyrrolidine (5-membered ring) 2,5-dipropylpyrrolidine (5-membered ring), 2,6-dimethylpiperidine (6-membered ring), 2,6-diethylpiperidine (6-membered ring), 2,4,6-trimethylpiperidine (6-membered ring) 3) a nitrogen-containing aliphatic amine having 3 to 10 carbon atoms in which a hydrogen atom bonded to a carbon atom constituting an aliphatic ring such as methyl group, ethyl group or propyl group is substituted, such as oxazolidine (5 Member ring), thiazolidine (5 member) Ring), morpholine (6-membered ring), nitrogen-containing aliphatic amine having 3 to 10 carbon atoms having a hetero atom (oxygen atom, sulfur atom, etc.) other than nitrogen atom such as thiomorpholine (6-membered ring) in the chain, For example, 2,6-dimethylmorpholine (6-membered ring), 2,6-diethylmorpholine (6-membered ring), 2,6-dipropylmorpholine (6-membered ring), 2,6-dimethylthiomorpholine (6-membered ring) , 2,6-diethylthiomorpholine (6-membered ring), 2,6-dipropylthiomorpholine (6-membered ring) and other hetero atoms other than nitrogen atoms (oxygen atom, sulfur atom, etc.) in the chain, A nitrogen-containing aliphatic amine having 4 to 10 carbon atoms in which a hydrogen atom bonded to a carbon atom constituting the aliphatic ring is substituted with an alkyl group such as a methyl group, an ethyl group or a propyl group, such as pyrrole (5-membered ring) , Imidazole (5-membered ring), pyrazole (5-membered) C3-C4 nitrogen-containing aromatic amine such as 2,5-dimethylpyrrole (5-membered ring), 2,5-diethylpyrrole (5-membered ring), 2,5-dipropylpyrrole (5-membered) Ring), 2,5-dimethylimidazole (5-membered ring), 2,5-diethylimidazole (5-membered ring), 2,5-dipropylimidazole (5-membered ring), 3,5-dimethylpyrazole (5-membered ring) ), 3,5-diethylpyrazole (5-membered ring), 3,5-dipropylpyrazole (5-membered ring), etc., hydrogen atoms bonded to carbon atoms constituting the aromatic ring are methyl groups, ethyl groups, propyl groups, etc. And a nitrogen-containing aromatic amine having 4 to 10 carbon atoms substituted on the alkyl group. That is, a nitrogen-containing aliphatic amine or nitrogen-containing carbon atom having 2 to 10 carbon atoms in which a hydrogen atom bonded to a carbon atom constituting an aliphatic ring or an aromatic ring is substituted with an alkyl group such as a methyl group, an ethyl group, or a propyl group A nitrogen-containing aliphatic amine having 2 to 10 carbon atoms having an aromatic amine or a hetero atom other than nitrogen atom (oxygen atom, sulfur atom, etc.) in the chain is also the nitrogen-containing aliphatic amine having 2 to 10 carbon atoms or Included in the concept of nitrogen-containing aromatic amines.

Among these nitrogen-containing aliphatic amines or nitrogen-containing aromatic amines having 2 to 10 carbon atoms, for example, aziridine (3-membered ring), azetidine (4-membered ring), pyrrolidine (5-membered ring), piperidine (6-membered ring) ), Hexamethyleneimine (azepan ring; 7-membered ring), heptamethyleneimine (azocan ring; 8-membered ring), octamethyleneimine (azonan ring; 9-membered ring), nonamethyleneimine (azecan ring; 10-membered ring), There are no heteroatoms (oxygen atoms, sulfur atoms, etc.) other than nitrogen atoms such as decamethyleneimine (11-membered ring) in the chain, and the hydrogen atom bonded to the carbon atom constituting the aliphatic ring is a methyl group, ethyl A nitrogen-containing aliphatic amine having 2 to 10 carbon atoms not substituted with an alkyl group such as a propyl group or a propyl group (so-called unsubstituted), such as 2-methylaziridine (3-membered ring), 2-methylazetidine (4 Ring), 3-methylazetidine (4-membered ring), 2,5-dimethylpyrrolidine (5-membered ring), 2,5-diethylpyrrolidine (5-membered ring), 2,5-dipropylpyrrolidine (5-membered ring) , 2,6-dimethylpiperidine (6-membered ring), 2,6-diethylpiperidine (6-membered ring), 2,4,6-trimethylpiperidine (6-membered ring) and other heteroatoms (oxygen atoms, Containing 3 to 10 carbon atoms in which a hydrogen atom bonded to a carbon atom constituting an aliphatic ring is substituted with an alkyl group such as a methyl group, an ethyl group or a propyl group. Nitrogen aliphatic amines such as oxazolidine (5-membered ring), thiazolidine (5-membered ring), morpholine (6-membered ring), thiomorpholine (6-membered ring) and other heteroatoms (oxygen atoms, sulfur atoms, etc.) In the chain and constituting an aliphatic ring The hydrogen atom to be bonded is not substituted with an alkyl group such as a methyl group, an ethyl group, or a propyl group (so-called unsubstituted) a nitrogen-containing aliphatic amine having 3 to 10 carbon atoms, such as 2,5-dimethylmorpholine (6-membered) Ring), 2,5-diethylmorpholine (6-membered ring), 2,5-dipropylmorpholine (6-membered ring), 2,5-dimethylthiomorpholine (6-membered ring), 2,5-diethylthiomorpholine (6 Member) and hetero atoms (oxygen atoms, sulfur atoms, etc.) other than nitrogen atoms such as 2,5-dipropylthiomorpholine (6-membered ring) in the chain and bonded to carbon atoms constituting the aliphatic ring Preferred is a nitrogen-containing aliphatic amine having 4 to 10 carbon atoms in which a hydrogen atom to be substituted is an alkyl group such as a methyl group, an ethyl group, or a propyl group. Among them, pyrrolidine (5-membered ring), piperidine (6-membered) Ring), hexamethylene (Azepan ring; 7-membered ring) other than the nitrogen atom other than the nitrogen atom (oxygen atom, sulfur atom, etc.) in the chain, the hydrogen atom bonded to the carbon atom constituting the aliphatic ring is a methyl group, ethyl A nitrogen-containing aliphatic amine having 4 to 6 carbon atoms which is not substituted with an alkyl group such as a group or a propyl group (so-called unsubstituted) is more preferable. The base generator represented by the general formula [1] having a group derived from the primary or secondary amine represented by the general formula [2] derived from the nitrogen-containing aliphatic amine of these preferred specific examples can be produced inexpensively and easily. In addition to the above, there are the following advantages as compared with those that generate nitrogen-containing aromatic amines. That is, since the aromatic ring has an action of absorbing active energy rays, when the structure (NR ⁷ R ⁸ ) of the amine moiety of the base generator represented by the general formula [1] is a nitrogen-containing aromatic ring, Absorption of the active energy ray of the benzene ring in the base generator is inhibited by the nitrogen-containing aromatic ring, whereas this is the case when the structure of the amine moiety (NR ⁷ R ⁸ ) is a nitrogen-containing aliphatic ring. Therefore, when the structure (NR ⁷ R ⁸ ) of the amine moiety of the base generator represented by the general formula [1] is a nitrogen-containing aliphatic ring, the active energy ray to the base generator It is useful in that the base is efficiently generated by irradiation.

  The nitrogen-containing aliphatic amine or nitrogen-containing aromatic amine having 2 to 10 carbon atoms may further have a substituent (functional group). Specific examples of the substituent (functional group) include the above. As mentioned, for example, hydroxyl group, mercapto group, cyano group, nitro group, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom and the like can be mentioned. Specific examples of the nitrogen-containing aliphatic amine or nitrogen-containing aromatic amine having 2 to 10 carbon atoms having the above substituent include 4-hydroxypiperidine (6-membered ring), 4-mercaptopiperidine (6-membered ring), 4 -Cyanopiperidine (6-membered ring), 4-nitropiperidine (6-membered ring), 4-chloropiperidine (6-membered ring), 4-bromopiperidine (6-membered ring), etc. Is not to be done.

  In the base generator represented by the general formula [1], a specific example of a base (primary or secondary amine) in which Z is derived from a group derived from a primary or secondary amine represented by the above general formula [3], that is, Specific examples of the diamine generated from the group derived from the primary or secondary amine represented by the general formula [3] include, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, Octamethylenediamine, nonamethylenediamine, decamethylenediamine, N, N′-dimethylethylenediamine, N, N′-dimethyltrimethylenediamine, N, N′-dimethyltetramethylenediamine, N, N′-dimethylpentamethylenediamine, N, N'-dimethylhexamethylenediamine, N, N'-dimethylheptamethyle Examples include diamine, N, N′-dimethyloctamethylenediamine, N, N′-dimethylnonamethylenediamine, N, N′-dimethyldecamethylenediamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and the like. However, the present invention is not limited to these examples.

  In the base generator represented by the general formula [1], Z is a specific example of the base (secondary amine) generated from the secondary amine-derived group represented by the general formula [4], that is, in the general formula [4]. Specific examples of the diamine generated from the group derived from the secondary amine shown include, for example, bis (3-pyrrolidyl) methane, 1,2-bis (3-pyrrolidyl) ethane, 1,3-bis (3-pyrrolidyl) propane. Bis (4-piperidyl) methane, 1,2-bis (4-piperidyl) ethane, 1,3-bis (4-piperidyl) propane, bis [3- (2,5-dimethylpyrrolidyl)] methane, , 2-bis [3- (2,5-dimethylpyrrolidyl)] ethane, 1,3-bis [3- (2,5-dimethylpyrrolidyl)] propane, bis [4- (2,6-dimethylpiperidyl) )] Methane, 1,2-bis [4- (2,6-dimethylpipe Jill)] ethane, 1,3-bis [4- (2,6-dimethyl-piperidyl)] propane, and the like, not in any way limited to these examples.

  In the base generator represented by the general formula [1], specific examples of the base (primary or secondary amine) generated from the group derived from the primary or secondary amine represented by Z are other than the above specific examples. In addition, for example, cyclic diamines such as piperazine, aromatic diamines such as phenylenediamine, and the like are exemplified, but the examples are not limited to these examples.

Among the base generators represented by the general formula [1], as a more specific base generator, R ¹ and R ² in the general formula [1] are each independently a hydrogen atom, having 1 to 4 carbon atoms. A linear, branched or cyclic alkyl group, an optionally substituted phenyl group or a cyano group (excluding those in which R ¹ and R ² are both hydrogen atoms); ^{3 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a linear, branched or cyclic group having 1 to 4 carbon atoms. An alkoxy group, an aryl group having 6 to 10 carbon atoms which may have a substituent, a hydroxyl group or a nitro group, and Z is a group represented by the following formulas [6] to [14]. Examples include a base generator represented by the following general formula [5]. These base generators are preferable base generators in that they can be easily and inexpensively produced in a short process and can be a more soluble base generator for curing a resin compared to other base generators. .

（式中、Ｒ^１'及びＲ^２'は夫々独立して、水素原子、炭素数１〜４の直鎖状若しくは分枝状のアルキル基、置換基を有していてもよいフェニル基又はシアノ基を表し、Ｒ^３'〜Ｒ^６'は夫々独立して、水素原子、ハロゲン原子、炭素数１〜４の直鎖状若しくは分枝状のアルキル基、炭素数１〜４の直鎖状若しくは分枝状のアルコキシ基、置換基を有していてもよい炭素数６〜１０のアリール基、ヒドロキシル基又はニトロ基を表し、Ｚ'は下記式［６］〜［１４］で示される基を表し、Ｒ^２'とＲ^３'とで環状構造を形成していてもよいし、Ｒ^３'〜Ｒ^６'の２つ以上が結合してＲ^３'〜Ｒ^６'が結合しているベンゼン環と縮合環を形成していてもよい。ただし、Ｒ^１'及びＲ^２'が共に水素原子であるものを除く。）

(Wherein R ¹ ′ and R ² ′ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, or cyano. R ³ ′ to R ⁶ ′ each independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear chain having 1 to 4 carbon atoms, A branched alkoxy group, an aryl group having 6 to 10 carbon atoms which may have a substituent, a hydroxyl group or a nitro group is represented, and Z ′ represents a group represented by the following formulas [6] to [14]. It represents, may form a cyclic structure de ^'and R ^3' R 2 and, benzene R ³ 'to R ^6' 2 or more is bonded to the the R ³ 'to R ^6' are attached A ring and a condensed ring may be formed, except that R ¹ ′ and R ² ′ are both hydrogen atoms.)

（式中、Ｙ'は下記一般式［５'］で示される基を表す。）

(In the formula, Y ′ represents a group represented by the following general formula [5 ′].)

（式中、Ｙ'は下記一般式［５'］で示される基を表す。）

(In the formula, Y ′ represents a group represented by the following general formula [5 ′].)

（式中、Ｒ^１'〜Ｒ^６'は上記に同じ。）

(In the formula, R ¹ ′ to R ⁶ ′ are the same as above.)

A linear or branched alkyl group having 1 to 4 carbon atoms represented by R ¹ ′ and R ² ′ in the base generator represented by the general formula [5] and the group represented by the general formula [5 ′] Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like can be mentioned. A methyl group which is 1 alkyl group is preferred.

In the base generator represented by the general formula [5] and the group represented by the general formula [5 ′], as a substituent in the phenyl group which may have a substituent represented by R ¹ ′ and R ² ′, Specifically, for example, a hydroxyl group, a mercapto group, a cyano group, a nitro group, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like linear or branched alkyl group having 1 to 4 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, iso Examples thereof include linear or branched alkoxy groups having 1 to 4 carbon atoms such as propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group.

In the base generator represented by the general formula [5] and the group represented by the general formula [5 ′], R ¹ ′ and R ² ′ are a hydrogen atom, a linear or branched group having 1 to 4 carbon atoms. The alkyl group is more preferable.

In the base generator represented by the general formula [5] and the group represented by the general formula [5 ′], specific examples of the halogen atom represented by R ³ ′ to R ⁶ ′ include a fluorine atom and a chlorine atom. , Bromine atom, iodine atom and the like.

In the base generator represented by the general formula [5] and the group represented by the general formula [5 ′], a linear or branched alkyl group having 1 to 4 carbon atoms represented by R ³ ′ to R ⁶ ′ Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. A tert-butyl group is preferred.

In the base generator represented by the general formula [5] and the group represented by the general formula [5 ′], a linear or branched alkoxy group having 1 to 4 carbon atoms represented by R ³ ′ to R ⁶ ′. Specific examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, etc. The methoxy group which is the alkoxy group of number 1 is preferable.

In the base generator represented by the general formula [5] and the group represented by the general formula [5 ′], an aryl having 6 to 10 carbon atoms which may have a substituent represented by R ³ ′ to R ⁶ ′ Specific examples of the aryl group having 6 to 10 carbon atoms in the group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

In the base generator represented by the general formula [5] and the group represented by the general formula [5 ′], an aryl having 6 to 10 carbon atoms which may have a substituent represented by R ³ ′ to R ⁶ ′ Specific examples of the substituent in the group include a hydroxyl group, a mercapto group, a cyano group, a nitro group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, such as a methyl group, an ethyl group, and n A linear or branched alkyl group having 1 to 4 carbon atoms such as -propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, such as methoxy group, ethoxy group, Examples thereof include linear or branched alkoxy groups having 1 to 4 carbon atoms such as n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group.

In the base generator represented by the general formula [5] and the group represented by the general formula [5 ′], R ³ ′ to R ⁶ ′ are a hydrogen atom, a linear or branched group having 1 to 4 carbon atoms. The alkoxy group is more preferable.

A more preferred specific example of the base generator represented by the general formula [5] is a methyl group in which R ² ′ in the general formula [5] is a C 1 alkyl group, and R ¹ ′, R ³ ′, R ⁴ ′, R ⁵ ′ and R ⁶ ′ are all hydrogen atoms, and Z ′ is a group represented by the above formula [7]. More specifically, 15]

で示される塩基発生剤が、より好ましいものとして挙げられる。

The base generator shown by these is mentioned as a more preferable thing.

As a precaution, the base generator represented by the formula [15] is a methyl group in which R ² is an alkyl group having 1 carbon atom in the base generator represented by the general formula [1]. R ¹ , R ³ , R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms, Z is a group derived from a primary or secondary amine represented by the above general formula [2], R ⁷ and R ⁸ in formula [2] do not have a hetero atom other than the nitrogen atom (oxygen atom, sulfur atom, etc.) in the chain together with the nitrogen atom to which these (R ⁷ and R ⁸ ) are bonded, Piperidine which is a nitrogen-containing aliphatic amine having 5 carbon atoms in which a hydrogen atom bonded to a carbon atom constituting an aliphatic ring is not substituted with an alkyl group such as a methyl group, an ethyl group or a propyl group (so-called unsubstituted) This corresponds to a group derived from a 6-membered ring.

Furthermore, other preferable specific examples of the base generator represented by the above general formula [5] include a methyl group in which R ¹ ′ in the general formula [5] is an alkyl group having 1 carbon atom, and R ⁵ ′. Is a hydrogen atom or a methoxy group which is a C 1 alkoxy group, R ² ′, R ³ ′, R ⁴ ′ and R ⁶ ′ are all hydrogen atoms, and Z ′ is the above formula [7] And, more specifically, a group represented by the formula [16]

で示される化合物及び式［１７］

And a compound represented by the formula [17]

で示される塩基発生剤が、より好ましいものとして挙げられる。

The base generator shown by these is mentioned as a more preferable thing.

As a precautionary note, the base generator represented by the above formulas [16] and [17] is the same as the base generator represented by the general formula [1] in which R ¹ is an alkyl group having 1 carbon atom. A methyl group, R ⁵ is a hydrogen atom or a methoxy group which is an alkoxy group having 1 carbon atom, R ² , R ³ , R ⁴ and R ⁶ are all hydrogen atoms, and Z is the above general formula [ 2] is a group derived from a primary or secondary amine, wherein R ⁷ and R ⁸ in the general formula [2] are a nitrogen atom together with the nitrogen atom to which these (R ⁷ and R ⁸ ) are bonded. Other than the hetero atoms (oxygen atoms, sulfur atoms, etc.) in the chain, the hydrogen atom bonded to the carbon atom constituting the aliphatic ring is substituted with an alkyl group such as a methyl group, an ethyl group, or a propyl group. No (so-called unsubstituted) nitrogen-containing aliphatic amine having 5 carbon atoms It corresponds to a group derived from piperidine (6-membered ring).

  In addition to the specific examples described above, primary or secondary derived from a high-boiling base (primary or secondary amine), for example, to generate a high-boiling base (primary or secondary amine). When an amine-derived group is required, for example, a group derived from a nitrogen-containing aliphatic amine or nitrogen-containing aromatic amine to which a substituent (functional group) such as a hydroxyl group is bonded may be preferable. Examples of base generators represented by the general formula [1] other than those described above and those described above are, for example, those represented by the following chemical formulas, but are not limited to these examples.

  The base generator represented by the general formula [1] according to the present invention generates a base by irradiation with active energy rays, and more specifically generates a base by irradiation with active energy rays having a wavelength of 150 to 500 nm. In the region of the wavelength of 150 to 500 nm, there is an absorption wavelength region where the molar extinction coefficient is 5000 or more, so that a base can be generated efficiently. In addition, the base generator according to the present invention is preferably one that absorbs at least one active energy ray of i-line, h-line, and g-line in the above-described wavelength region from the viewpoint of versatility. The base generator represented by the general formula [1] according to the present invention preferably generates a base by irradiation with an active energy ray, but excludes generation of a base by applying energy such as heating. It is not a thing.

  The base generator represented by the general formula [1] according to the present invention generates a base by irradiation with active energy rays, and photocyclization in the molecule proceeds to produce a coumarin derivative. In this photocyclization, a base (primary or secondary amine) is generated without decarboxylation. Therefore, unlike conventional photobase generators with decarboxylation, the film strength of the cured film by carbon dioxide gas by-product is increased. Reduction and film roughness of the cured film surface can be suppressed.

  The base generator represented by the general formula [1] according to the present invention is described as a trans isomer for convenience of explanation, but both the trans isomer and the cis isomer are isomerized by irradiation with active energy rays. , Base (primary or secondary amine) is generated and photocyclization in the molecule proceeds. For this reason, the base generator represented by the general formula [1] according to the present invention may be a trans isomer, a cis isomer, or a mixture thereof.

  The base generator represented by the general formula [1] according to the present invention has a temperature at which 5% weight is reduced from the initial weight by heating (hereinafter sometimes referred to as 5% weight reduction temperature) is 100. It is preferable that the temperature is at least ° C. When producing a coating film using the photosensitive resin composition of the present invention, the organic solvent contained in the photosensitive resin composition of the present invention may be volatilized during baking, but 5% by weight of the base generator When the decrease temperature is high, even when the organic solvent has a high boiling point, the temperature at the time of baking can be set high, so that the residual organic solvent after baking can be minimized. Thereby, the deterioration of the contrast between the exposed part (cured part) and the unexposed part (uncured part) due to the residual organic solvent can be suppressed.

  Next, a method for producing the base generator according to the present invention will be described. As a method for producing the base generator represented by the general formula [1] according to the present invention, for example, the general formula [18]

（式中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は上記に同じ。）で示されるアルデヒド又はケトンと一般式［１９］

(Wherein R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as above) and the general formula [19]

（式中、Ｒ'は１価の炭化水素基を表し、Ｒ^１は上記に同じ。）で示されるWittig試薬を反応させ、要すればカルボン酸エステルの加水分解を行い、一般式［２０］

(Wherein R ′ represents a monovalent hydrocarbon group, R ¹ is the same as above), the carboxylic acid ester is hydrolyzed if necessary, and the general formula [20]

（式中、Ｒ''は水素原子又は１価の炭化水素基を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は上記に同じ。）で示されるカルボン酸又はカルボン酸エステルを得、当該カルボン酸又はカルボン酸エステルと一般式［２１］

(Wherein R ″ represents a hydrogen atom or a monovalent hydrocarbon group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as above) An acid ester is obtained, and the carboxylic acid or carboxylic acid ester and the general formula [21]

（式中、Ｒ^７及びＲ^８は上記に同じ。）で示されるアミン、一般式［２２］

(Wherein R ⁷ and R ⁸ are the same as above), an amine represented by the general formula [22]

（式中、Ｒ^９、Ｒ^１０及びＶ_１は上記に同じ。）で示されるアミン又は一般式［２３］

(Wherein R ⁹ , R ¹⁰ and V ₁ are the same as above) or the general formula [23]

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｖ_２、ｍ及びｎは上記に同じ。）で示されるアミンを反応させ、目的とする一般式［１］で示される塩基発生剤を合成すればよい。より具体的な製造方法としては、例えば上記一般式［１８］で示されるアルデヒド又はケトンを、当該アルデヒド又はケトンに対して、通常０．８〜１０．０当量、好ましくは０．８〜３．０当量の上記一般式［１９］で示されるWittig試薬と反応させ（Wittig反応）、要すればカルボン酸エステルの加水分解反応を行って、上記一般式［２０］で示されるカルボン酸又はカルボン酸エステルを得る（第一工程）。次いで第一工程で得られた一般式［２０］で示されるカルボン酸又はカルボン酸エステルを、当該カルボン酸又はカルボン酸エステルに対して、通常０．８〜１０．０当量、好ましくは０．８〜３．０当量の上記一般式［２１］で示されるアミン、或いは当該カルボン酸又はカルボン酸エステルに対して、通常０．４〜５．０当量、好ましくは０．４〜１．５当量の上記一般式［２２］又は一般式［２３］で示されるアミンと反応させることにより（第二工程）、本発明に係る一般式［１］で示される塩基発生剤を得ることができる。

(Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , V ₂ , m and n are the same as described above) are reacted with an amine represented by the target general formula [1] Can be synthesized. As a more specific production method, for example, the aldehyde or ketone represented by the general formula [18] is usually 0.8 to 10.0 equivalents, preferably 0.8 to 3. Reaction with 0 equivalent of the Wittig reagent represented by the above general formula [19] (Wittig reaction), and if necessary, hydrolysis reaction of the carboxylic acid ester is performed to obtain the carboxylic acid or carboxylic acid represented by the above general formula [20]. An ester is obtained (first step). Next, the carboxylic acid or carboxylic acid ester represented by the general formula [20] obtained in the first step is usually 0.8 to 10.0 equivalents, preferably 0.8 to the carboxylic acid or carboxylic acid ester. Usually, 0.4 to 5.0 equivalents, preferably 0.4 to 1.5 equivalents of the amine represented by the general formula [21], or the carboxylic acid or carboxylic acid ester, is represented by -3.0 equivalents. The base generator represented by the general formula [1] according to the present invention can be obtained by reacting with the amine represented by the general formula [22] or the general formula [23] (second step).

  Specific examples of the monovalent hydrocarbon group represented by R ′ in the general formula [19] and R ″ in the general formula [20] include, for example, a linear, branched or branched group having 1 to 10 carbon atoms. Examples thereof include a cyclic alkyl group and an aryl group having 6 to 10 carbon atoms. Specific examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl , Cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl Group, cyclohexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, neoheptyl group, cycloheptyl group, n-octyl group, isooctyl Group, sec-octyl group, tert-octyl group, neooctyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, neononyl group, cyclononyl group, n- Decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, cyclodecyl group, norbornyl group, bornyl group (bornan-χ-yl group), adamantyl group, menthyl group (menta-χ-yl group), etc. Is mentioned. Specific examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. The specific examples described above are merely examples, and the alkyl group, the aryl group, and the like as described above have a substituent such as a nitro group as long as they do not adversely affect the first step. May be.

  As the aldehyde or ketone represented by the general formula [18] used in the first step, a commercially available product may be used. Specifically, for example, 2-hydroxybenzaldehyde (salicylaldehyde), 2-hydroxy-3-methoxy Benzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-5-methoxybenzaldehyde, 2-hydroxy-3-methylbenzaldehyde, 2-hydroxy-3-methylbenzaldehyde, 2-hydroxy-5-methylbenzaldehyde, 3-allyl -2-hydroxybenzaldehyde, 3-tert-butyl-2-hydroxybenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2 , 4-Dihydro Ci-5-methylbenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 3-fluoro-2-hydroxybenzaldehyde, 5-fluoro-2-hydroxy Benzaldehyde, 3,5-difluoro-2-hydroxybenzaldehyde, 2-chloro-6-hydroxybenzaldehyde, 3-chloro-2-hydroxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 5-bromo-2-hydroxybenzaldehyde, 2 Aldehydes such as 1-hydroxy-1-naphthaldehyde, 1-hydroxy-2-naphthaldehyde, methyl-3-formyl-4-hydroxybenzoate, such as methyl-2-hydroxyphenyl ketone (2′-hydroxyacetophenone), 2 ′, 4'-dihydroxya Tophenone, 2 ′, 5′-dihydroxyacetophenone, 2 ′, 3 ′, 4′-trihydroxyacetophenone, 2′-hydroxy-5′-methylacetophenone, 2 ′, 4′-dihydroxy-3′-methylacetophenone, 2 ', 4'-dihydroxy-3'-ethylacetophenone, 2'-hydroxy-4'-methoxyacetophenone, 2'-hydroxy-5'-methoxyacetophenone, 2'-hydroxy-6'-methoxyacetophenone, 2'-hydroxy -4'-ethoxyacetophenone, 2'-hydroxy-5'-ethoxyacetophenone, 2'-hydroxy-5'-nitroacetophenone, 4'-fluoro-2'-hydroxyacetophenone, 5'-fluoro-2'-hydroxyacetophenone 5'-chloro-2'-hydroxyacetophenone, 5'-bromo-2'-hydroxyacetophenone, 2'-hydroxypropiophenone, 2 ', And ketones such as 4'-dihydroxypropiophenone, 2 ', 4'-dihydroxy-6'-methylpropiophenone, 1'-hydroxy-2'-acetonaphthone, 2'-hydroxy-1'-acetonaphthone, etc. . When the aldehyde or ketone represented by the general formula [18] is not commercially available, 2-hydroxybenzaldehyde (salicylaldehyde) or methyl-2-hydroxyphenylketone (2′-hydroxyacetophenone) is used. What is necessary is just to use suitably what introduce | transduced the target substituent into the benzene ring by the well-known method.

  The Wittig reagent represented by the above general formula [19] used in the first step may be a commercially available one. Specifically, for example, (ethoxycarbonylmethyl) triphenylphosphorane, (ethoxycarbonylethyl) triphenyl Examples include phosphorane, methoxycarbonylmethyl (triphenyl) phosphonium bromide, ethoxycarbonylmethyl (triphenyl) phosphonium bromide, and the like. In addition, when the Wittig reagent represented by the general formula [19] is not commercially available, a Wittig reagent synthesized by a conventionally known method may be appropriately used.

  The first step using the Wittig reagent is preferably performed in an organic solvent, and the organic solvent used in that case is an aldehyde or ketone represented by the general formula [18] as a reaction raw material, a general formula [19 ] If it is an organic solvent which does not react with the Wittig reagent shown, there will be no restriction | limiting in particular, For example, nonpolar organic solvents, such as hexane, benzene, toluene, a dichloromethane, dichloroethane, chloroform, diethyl ether, tetrahydrofuran (THF), etc. And aprotic polar organic solvents such as dioxane, and dehydrated organic solvents obtained by dehydrating these organic solvents. These organic solvents may be used alone or in combination of two or more, and the amount of the organic solvent used is not particularly limited. For example, with respect to 1 mmol of aldehyde or ketone represented by the general formula [18], Usually 0.1 to 10 mL, preferably 0.2 to 5 mL.

  The reaction temperature in the first step using the Wittig reagent may be set to a temperature at which the aldehyde or ketone represented by the general formula [18] reacts with the Wittig reagent represented by the general formula [19]. Alternatively, the temperature is preferably set to a temperature at which the ketone and the Wittig reagent efficiently react to synthesize the carboxylic acid ester with a high yield. Specifically, it is 0-140 degreeC normally, for example, Preferably it is 20-120 degreeC.

  The reaction time in the first step using the Wittig reagent is the type and amount of the Wittig reagent represented by the general formula [19] with respect to the aldehyde or ketone represented by the general formula [18], the type and amount of the organic solvent, and the reaction temperature. However, it is generally not set in the range of 0.1 to 24 hours, preferably 0.2 to 12 hours.

  If necessary, the hydrolysis reaction is a step of hydrolyzing a carboxylic acid ester to produce a carboxylic acid, and is obtained, for example, by concentrating the solution after completion of the reaction in the first step using the Wittig reagent. The reaction may be carried out by adding an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to the concentrated residue. What is necessary is just to set suitably according to the hydrolysis reaction normally performed in this field | area as reaction temperature and reaction time in that case, As reaction temperature, it is 0-80 degreeC normally, for example, Preferably it is 10-60 degreeC, The reaction time is usually set in the range of 0.1 to 24 hours, preferably 0.1 to 12 hours.

  In the first step, as a method for isolating and purifying the carboxylic acid or carboxylic acid ester represented by the general formula [9], which is the product of the first step, from the solution after completion of the reaction, general post-treatment, purification Operation is enough. Specifically, for example, when the carboxylic acid ester is hydrolyzed to obtain a carboxylic acid, the solution (aqueous solution) after the reaction is extracted with, for example, dichloromethane, and then the extracted layer is extracted with, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid. Then, an acid such as oxalic acid or citric acid is added, and the resulting crystals are collected by filtration and washed with a suitable organic solvent for efficient purification. On the other hand, when the carboxylic acid ester is isolated without hydrolysis, the concentrated residue obtained by washing the solution after completion of the reaction with, for example, water and concentrating the organic layer after washing. May be purified by a method such as column chromatography.

Specific examples of the amine represented by the general formula [21] used in the second step include, for example, ammonia, such as mono- or dimethylamine, mono- or diethylamine, mono- or di-n-propylamine, mono- or diisopropylamine, mono- Or di-n-butylamine, mono or diisobutylamine, mono or di-sec-butylamine, mono or di-tert-butylamine, mono or dicyclobutylamine, mono or di-n-pentylamine, mono or diisopentylamine, Mono or di-sec-pentylamine, mono or di-tert-pentylamine, mono or dineopentylamine, mono or di-2-methylbutylamine, mono or di-1,2-dimethylpropylamine, mono or di- 1-ethylpropylamine, mono- or dicyclopentylamine, mono- or di-n-hexylamine, Or diisohexylamine, mono or di-sec-hexylamine, mono or di-tert-hexylamine, mono or dineohexylamine, mono or di-2-methylpentylamine, mono or di-1,2-dimethyl Butylamine, mono or di-2,3-dimethylbutylamine, mono or di-1-ethylbutylamine, mono or dicyclohexylamine, mono or di-n-heptylamine, mono or diisoheptylamine, mono or di-sec-heptyl Amine, mono or di-tert-heptylamine, mono or dineoheptylamine, mono or dicycloheptylamine, mono or di-n-octylamine, mono or diisooctylamine, mono or di-sec-octylamine, Mono- or di-tert-octylamine, mono- or dineooctylamine, mono- or di-2-ethylhexylamine, mono- or di- Is dicyclooctylamine, mono or di-n-nonylamine, mono or diisononylamine, mono or di-sec-nonylamine, mono or di-tert-nonylamine, mono or dineononylamine, mono or dicyclononylamine, mono Or di-n-decylamine, mono or diisodecylamine, mono or di-sec-decylamine, mono or di-tert-decylamine, mono or dineodecylamine, mono or dicyclodecylamine, mono or dinorbornylamine, mono Or carbon number such as dibornylamine, mono- or diadamantylamine, mono- or dimenthylamine, ethylmethylamine, methyl-n-propylamine, methylisopropylamine, ethyl-n-propylamine, ethylisopropylamine, n-propylisopropylamine 1-10 linear, branched or young Is a cyclic mono- or dialkylamine, such as mono- or divinylamine, mono- or di-1-propenylamine, mono- or di-2-propenyl group (mono- or diallylamine), mono- or diisopropenylamine, mono- or di-n- Butenylamine, mono or di-n-pentenylamine, mono or dicyclopentenylamine, mono or di-n-hexenylamine, mono or dicyclohexenylamine, mono or di-n-heptenylamine, mono or di-n-octenylamine, C2-C10 linear, branched or cyclic mono or dialkenyl amines such as mono or di-n-nonenylamine, mono or di-n-decenylamine, such as mono or diethynylamine, mono or di- 1-propynylamine, mono or di-2-propynylamine (mono or dipropargylamine), mono Or di-n-butynylamine, mono- or di-1-methylpropargylamine, mono- or di-n-pentynylamine, mono- or di-n-hexynylamine, mono- or di-n-heptynylamine, mono- or di-n-octynylamine A linear, branched or cyclic mono- or dialkynyl amine having 2 to 10 carbon atoms such as mono- or di-n-nonynylamine, mono- or di-n-decynylamine, such as mono- or diphenylamine, mono- or di-1 6- to 10-carbon mono- or diarylamines such as -naphthylamine, mono- or di-2-naphthylamine, such as mono- or dibenzylamine, mono- or diphenethylamine, mono- or di-α-methylbenzylamine, mono- or di-3 -Phenylpropylamine, mono- or di-1-methyl-1-phenylethylamine, mono- or di-4-phenylbutylamino Mono- or di-2-methyl-2-phenylpropylamine, mono- or di-1,2,3,4-tetrahydronaphthylamine and other amines such as mono- or diaralkylamine having 7 to 10 carbon atoms, that is, the general formula [ In the base generator represented by 1], a group derived from a primary or secondary amine represented by Z is a group derived from a primary or secondary amine represented by the general formula [2], and the general formula [2 ] Wherein R ⁷ and R ⁸ are each independently a hydrogen atom or a base (primary or secondary amine) derived from a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms. Can be mentioned.

Among the specific examples of the amine represented by the general formula [21] used in the second step, in the base generator represented by the general formula [1], Z is a primary represented by the general formula [2]. or a secondary amine groups derived from, together with the nitrogen atom to which R ⁷ and R ⁸ in the general formula [2] is bonded these (R ⁷ and R ^8), may have a substituent Specific examples of bases (primary or secondary amines) corresponding to those forming a nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring having 2 to 10 carbon atoms, that is, primary or 2 represented by the general formula [2] Specific examples of the amine represented by the above general formula [21] corresponding to a nitrogen-containing aliphatic amine or nitrogen-containing aromatic amine having 2 to 10 carbon atoms generated from a group derived from a secondary amine include, for example, aziridine (3-membered ring) ), Azetidine (4-membered ring), pyrrolidine (5-membered ring) Piperidine (6-membered ring), hexamethyleneimine (azepan; 7-membered ring), heptamethyleneimine (azocan; 8-membered ring), octamethyleneimine (azonan; 9-membered ring), nonamethyleneimine (azecan; 10-membered ring) , A nitrogen-containing aliphatic amine having 2 to 10 carbon atoms such as decamethyleneimine (11-membered ring), such as 2-methylaziridine (3-membered ring), 2-methylazetidine (4-membered ring), 3-methylazetidine (4-membered ring), 2,5-dimethylpyrrolidine (5-membered ring), 2,5-diethylpyrrolidine (5-membered ring), 2,5-dipropylpyrrolidine (5-membered ring), 2,6-dimethylpiperidine ( 6-membered ring), 2,6-diethylpiperidine (6-membered ring), 2,4,6-trimethylpiperidine (6-membered ring) and other hydrogen atoms bonded to carbon atoms constituting the aliphatic ring are methyl groups, ethyl Group, propyl group, etc. A nitrogen-containing aliphatic amine having 3 to 10 carbon atoms substituted on the alkyl group, such as oxazolidine (5-membered ring), thiazolidine (5-membered ring), morpholine (6-membered ring), thiomorpholine (6-membered ring), etc. A nitrogen-containing aliphatic amine having 3 to 10 carbon atoms having a hetero atom (oxygen atom, sulfur atom, etc.) other than the nitrogen atom, such as 2,5-dimethylmorpholine (6-membered ring), 2,5-diethylmorpholine (6 Membered ring), 2,5-dipropylmorpholine (6-membered ring), 2,5-dimethylthiomorpholine (6-membered ring), 2,5-diethylthiomorpholine (6-membered ring), 2,5-dipropylthio There are heteroatoms (oxygen atoms, sulfur atoms, etc.) other than nitrogen atoms, such as morpholine (6-membered ring), and hydrogen atoms bonded to carbon atoms constituting the aliphatic ring are methyl groups, ethyl groups, propyl groups, etc. Charcoal substituted with an alkyl group A nitrogen-containing aliphatic amine having 4 to 10 carbon atoms, for example, a nitrogen-containing aromatic amine having 3 to 4 carbon atoms such as pyrrole (5-membered ring), imidazole (5-membered ring), pyrazole (5-membered ring), for example 2,5 -Dimethylpyrrole (5-membered ring), 2,5-diethylpyrrole (5-membered ring), 2,5-dipropylpyrrole (5-membered ring), 2,5-dimethylimidazole (5-membered ring), 2,5- Diethylimidazole (5-membered ring), 2,5-dipropylimidazole (5-membered ring), 3,5-dimethylpyrazole (5-membered ring), 3,5-diethylpyrazole (5-membered ring), 3,5-di A nitrogen-containing aromatic amine having 4 to 10 carbon atoms in which a hydrogen atom bonded to a carbon atom constituting an aromatic ring such as propylpyrazole (5-membered ring) is substituted with an alkyl group such as a methyl group, an ethyl group or a propyl group Etc.

  Furthermore, in the base generator represented by the general formula [1], specific examples of the amine represented by the above general formula [22] in which Z corresponds to a group derived from a primary or secondary amine represented by the general formula [3] In other words, specific examples of the base corresponding to the base (primary or secondary amine) generated from the group derived from the primary or secondary amine represented by the general formula [3] include, for example, ethylenediamine, trimethylenediamine, Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, N, N'-dimethylethylenediamine, N, N'-dimethyltrimethylenediamine, N, N ' -Dimethyltetramethylenediamine, N, N'-dimethylpentamethylenediamine, N, N'-dimethylhexamethyl Range amine, N, N′-dimethylheptamethylenediamine, N, N′-dimethyloctamethylenediamine, N, N′-dimethylnonamethylenediamine, N, N′-dimethyldecamethylenediamine, 1,3-bis (3 And diamines such as (aminopropyl) tetramethyldisiloxane.

  Furthermore, in the base generator represented by the general formula [1], specific examples of the amine represented by the above general formula [23] in which Z corresponds to a group derived from a secondary amine represented by the general formula [4] Specifically, specific examples of the base (secondary amine) generated from the secondary amine-derived group represented by the general formula [4] include bis (3-pyrrolidyl) methane, 1,2-bis ( 3-pyrrolidyl) ethane, 1,3-bis (3-pyrrolidyl) propane, bis (4-piperidyl) methane, 1,2-bis (4-piperidyl) ethane, 1,3-bis (4-piperidyl) propane, Bis [3- (2,5-dimethylpyrrolidyl)] methane, 1,2-bis [3- (2,5-dimethylpyrrolidyl)] ethane, 1,3-bis [3- (2,5-dimethyl) Pyrrolidyl)] propane, bis [4- (2,6-dimethylpiperidyl) Methane, 1,2-bis [4- (2,6-dimethyl-piperidyl)] ethane, 1,3-bis [4- (2,6-dimethyl-piperidyl)], and diamines such propane.

Specific examples of other amines other than those described above include, for example, mono- or diethanolamine, mono- or diethanethiolamine, such as mono- or diperfluoromethylamine, mono- or diperfluoroethylamine, mono- or diperfluoro-n-propyl. Amine, mono or diperfluoroisopropylamine, mono or diperfluoro-n-butylamine, mono or diperfluoroisobutylamine, mono or diperfluoro-sec-butylamine, mono or diperfluoro-tert-butylamine, mono or diperfluorocyclobutylamine, etc. Mono or diperfluoroalkylamines such as mono or di-o-nitrophenylamine, mono or di-m-nitrophenylamine, mono or di-p-nitrophenylamine, mono or di-o-cyanophenylamine Mono- or di-m-cyanophenylamine, mono- or di-p-cyanophenylamine, mono- or di-o-nitrobenzylamine, mono- or di-m-nitrobenzylamine, mono- or di-p-nitrobenzylamine In the base generator represented by the general formula [1] such as mono- or di-o-cyanobenzylamine, mono- or di-m-cyanobenzylamine, mono- or di-p-cyanobenzylamine, Z is represented by the general formula [ 2] a group derived from a primary or secondary amine, wherein R ⁷ in the general formula [2] is a hydrogen atom or a C 1-10 linear, branched or cyclic group having a substituent. An amine represented by the above general formula [21] corresponding to a linear, branched, or cyclic hydrocarbon group having 1 to 10 carbon atoms and R ⁸ having a substituent, such as 4- Hydroxypiperidine (6 members ) 4-mercaptopiperidine (6-membered ring), 4-cyanopiperidine (6-membered ring), 4-nitropiperidine (6-membered ring), 4-chloropiperidine (6-membered ring), 4-bromopiperidine (6-membered ring) In the base generator represented by the general formula [1], such as Z), Z is a group derived from a primary or secondary amine represented by the general formula [2], and R ⁷ and R in the general formula [2] ^The above general formula [8] corresponding to the one in which 8 forms a nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring having 2 to 10 carbon atoms having a substituent together with the nitrogen atom to which these (R ⁷ and R ⁸ ) are bonded. 21], for example, cyclic diamines such as piperazine, aromatic diamines such as phenylenediamine, and the like, but are not limited to these examples. These amines may be used by appropriately selecting one of the above amines according to the structure of the target base generator represented by the general formula [1]. In addition, it is sufficient if these amines are commercially available.

  In the second step, of the carboxylic acid or carboxylic acid ester represented by the general formula [20], when carboxylic acid is used, the carboxylic acid is once converted into, for example, a mixed acid anhydride and activated to activate the carboxylic acid. You may make it react with the amine shown by general formula [21], [22] or [23]. Specific examples of the activator used for activating the carboxylic acid include, for example, methyl chloroformate, methyl bromate, ethyl chloroformate, ethyl bromate, propyl chloroformate, propyl bromate, butyl chloroformate, Alkyl formates such as butyl bromoformate, for example phenyl chloroformate, phenyl bromoformate, chloroformate-2-chlorophenyl, bromoformate-2-chlorophenyl, chloroformate-4-chlorophenyl, bromoformate-4-chlorophenyl, chloroformate- 2-bromophenyl, bromoformate-2-bromophenyl, chloroformate-4-bromophenyl, bromoformate-4-bromophenyl, chloroformate-2-nitrophenyl, bromoformate-2-nitrophenyl, chloroformate-4- Nitrophenyl, 4-nitrophenyl bromoformate, naphthyl chloroformate, Halogen formate esters of halogen formate aryl such as Romogi acid naphthyl. These halogenated formates may be used alone or in combination of two or more. In addition, the amount of the halogenated formate used is not particularly limited. For example, the amount of the halogenated formate is usually 0.8 to 10.0 equivalents, preferably 0.8 to 3. 0 equivalents. It is sufficient to use commercially available halogenated formate esters.

  In the second step, when an activator such as a halogenated formate as described above is used, for example, triethylamine, pyridine, N, N-dimethylaminopyridine, N-methylmorpholine, 1,8-diazabicyclo [5.4 It is desirable to use a tertiary amine such as 0.0] undec-7-ene (DBU) or 1,5-diazabicyclo [4.3.0] non-5-ene (DBN). These tertiary amines may be used alone or in combination of two or more. Further, the amount of the tertiary amine used is not particularly limited, but for example, generally 0.8 to 10.0 equivalents, preferably 0.8 to 3.0, with respect to the carboxylic acid represented by the general formula [20]. Is equivalent. In addition, it is sufficient for these tertiary amines to use commercially available ones.

  In the second step, the reaction may be performed in an organic solvent or may be performed without a solvent, but the reaction is preferably performed in an organic solvent so that the reaction proceeds smoothly. The organic solvent used in that case does not react with the carboxylic acid or carboxylic acid ester represented by the general formula [20] or the amine represented by the general formula [21], [22] or [23] as the reaction raw material. There are no particular limitations as long as it is an organic solvent, and specific examples include non-polar organic solvents such as hexane, benzene, toluene, dichloromethane, dichloroethane, chloroform, diethyl ether, tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane. And aprotic polar organic solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, and dehydrated organic solvents obtained by dehydrating these organic solvents. These organic solvents may be used alone or in combination of two or more, and the amount of the organic solvent used is not particularly limited. For example, 1 mmol of the carboxylic acid or carboxylic acid ester represented by the general formula [20] is used. On the other hand, it is usually 0.1 to 10 mL, preferably 0.2 to 5 mL.

  The reaction temperature in the second step is set to a temperature at which the carboxylic acid or carboxylic acid ester represented by the general formula [20] reacts with the amine represented by the general formula [21], [22] or [23]. However, it is preferable to set the temperature so that the carboxylic acid or carboxylic acid ester and the amine can efficiently react to synthesize the target base generator represented by the general formula [1] with high yield. Specifically, for example, it is usually −40 to 120 ° C., preferably −20 to 100 ° C.

  The reaction time in the second step is the kind and amount of amine represented by general formula [21], [22] or [23] relative to the carboxylic acid or carboxylic acid ester represented by general formula [20], alkyl halide formate. However, it may vary depending on the presence or absence of the activator, the type and amount thereof, the type and amount of organic solvent used, the reaction temperature, etc. Set in the range of 2-12 hours.

  In the second step, the method for isolating and purifying the base generator represented by the general formula [1], which is the product of the second step, from the solution after completion of the reaction may be a general post-treatment or purification operation. . Specifically, for example, an appropriate organic solvent such as dichloromethane is added to the solution after completion of the reaction, the solution is washed with sodium bicarbonate, water, etc., and the concentrated residue obtained by concentrating the solution after washing is recrystallized, What is necessary is just to isolate by performing suitable refinement | purification operations, such as column chromatography.

In addition, said manufacturing method is an example to the last, Comprising: You may synthesize | combine the base generator shown by General formula [1] by another method. Specifically, for example, after protecting the hydroxyl group of the aldehyde or ketone represented by the general formula [7], the first step is performed, and then the hydroxyl group is appropriately deprotected before and after the second step. A base generator represented by the general formula [1] may be synthesized. Even if it is not a process using the Wittig reagent as described above, for example, a Knoevenagel reaction, a Perkin reaction, a Horner-Wadsworth-Emmons reaction, and a Heck reaction are performed depending on the type of R ¹ and / or R ² in the general formula [1]. You may synthesize. Furthermore, the second step is not limited to the mixed acid anhydride method, and may be performed by a method using a condensing agent such as (water-soluble) carbodiimide and various dehydration catalysts.

  The base-reactive resin according to the present invention is not particularly limited as long as it reacts with a base (primary or secondary amine) generated from the base generator represented by the general formula [1] as described above. Those used in known resist compositions and photosensitive resin compositions can be used. In addition, for example, those in which a base (primary or secondary amine) acts as a catalyst and a base-reactive resin finally reacts are also included in the base-reactive resin. Specific examples of the base-reactive resin according to the present invention will be given below, but the base-reactive resin is not limited to these.

  Specific examples of the base-reactive resin according to the present invention include, for example, a resin having a base-reactive functional group and causing a polymerization reaction, a resin having a base-reactive functional group and causing an intermolecular crosslinking reaction, and base reactivity Examples thereof include a resin having a functional group and causing a hydrolysis / condensation reaction, and a resin having a base-reactive functional group and causing a cyclization reaction. Here, examples of the base-reactive functional group include an epoxy group, an oxetane group, a thiirane group, a hydroxyl group, a mercapto group, a siloxy group, a carboxyl group, a cyano group, an isocyanate group, and an amino group.

  Examples of the resin having a base-reactive functional group and causing a polymerization reaction include monomers having at least two epoxy groups in the molecule, monomers having at least two thiirane groups in the molecule, and the like. In the invention, a monomer having at least two epoxy groups in the molecule is defined as an epoxy resin, and a monomer having at least two thiirane groups in the molecule is defined as an episulfide resin. Specific examples of such epoxy resins include glycidyl ester epoxy resins such as poly (glycidyl (meth) acrylate), glycidyl ether epoxy resins such as Epiol G-100, and glycidyl amine epoxy resins such as jER630. Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, for example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type Examples thereof include novolak epoxy resins such as epoxy resins, and these epoxy resins may be halogenated or hydrogenated. In the present invention, the (meth) acrylate means acrylate and / or methacrylate. Specific examples of the episulfide resin include an episulfide resin in which the oxygen atom of the epoxy resin as described above is substituted with a sulfur atom. As commercially available products of these epoxy resins and episulfide resins, for example, AER series (250) manufactured by Asahi Kasei Chemicals Corporation, for example, Adeka Resin EP-4100 series, EP-4500 series, EP-4000 series, EPU series manufactured by ADEKA Corporation, EPR series, for example, jER series (827, 828, 801N, 801PN, 1001, 1002, 806, 807, 4004P, 152, 154, 604, 630, 871, YX8000, YX8034, YX4000, etc.) manufactured by Mitsubishi Chemical Corporation, for example EPICLON series (830, 840, N-660, etc.) manufactured by DIC Corporation, DER series (6116, 6155, etc.) manufactured by Dow Chemical Corporation, YD series, YDF series, YD manufactured by Nippon Steel Corporation CN series, YDB series, Nippon Kayaku Co., Ltd. EOCN, EPPN, NC series, BREN series, NOF Corporation Epiol series (G-100, E-100, E-400, NPG-100), etc. However, it is not limited to these.

  The weight-average molecular weight of a resin having a base-reactive functional group such as an epoxy resin or an episulfide resin that causes a polymerization reaction is the heat resistance of the photosensitive resin composition of the present invention, applicability, solubility in an organic solvent described later, From the viewpoint of solubility in a developer, etc., it is preferably 300 to 100,000, more preferably 300 to 30,000. If the weight average molecular weight is less than 300, the strength of the coating film or molded product obtained from the photosensitive resin composition of the present invention may be insufficient, and if it exceeds 100,000, the viscosity of the resin itself. This is not preferable because not only the solubility increases but the solubility becomes worse, and it becomes difficult to obtain a film having a uniform cured film surface and a constant film thickness. The weight average molecular weight is a value measured by gel permeation chromatography and converted to standard polystyrene.

  Examples of the resin having a base-reactive functional group and causing an intermolecular crosslinking reaction include, for example, a combination of a monomer having at least two isocyanate groups in the molecule and a monomer having at least two hydroxyl groups in the molecule, And a combination of a monomer having at least two or more isocyanate groups in the molecule and a monomer having at least two or more mercapto groups in the molecule. By reacting the isocyanate group with a hydroxyl group or a mercapto group, (thio) A urethane bond is formed and can be a polymer. In the present invention, the above (thio) urethane bond means a urethane bond and / or a thiourethane bond. Here, in the present invention, a monomer having at least two or more isocyanate groups in the molecule is an isocyanate resin, a monomer having at least two or more hydroxyl groups in the molecule is a polyol resin, and at least two or more monomers are in the molecule. A monomer having a mercapto group is defined as a polythiol resin. Specific examples of such isocyanate resins include, for example, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, Examples include 1,5-naphthalene diisocyanate and hexamethylene diisocyanate. These isocyanate resins may be halogenated or hydrogenated. Specific examples of the polyol resin include a low-molecular polyol resin such as ethylene glycol, propylene glycol, glycerin, diglycerin and pentaerythritol, as well as a hydroxyl group at the side chain or terminal of a polymer having a weight average molecular weight of 3000 or more. An existing polymer may be used. Furthermore, specific examples of the polythiol resin include polythiol resins in which the oxygen atom of the polyol resin as described above is substituted with a sulfur atom. Examples of commercially available products comprising a combination of these isocyanate resins and polyol resins or polythiol resins include, but are not limited to, Millionate MS-50 manufactured by Nippon Polyurethane Co., Ltd.

  The weight average molecular weight of a resin having a base-reactive functional group such as an isocyanate resin, a polyol resin, or a polythiol resin that causes an intermolecular cross-linking reaction is the heat resistance of the photosensitive resin composition of the present invention, coating properties, and an organic solvent described later. From the viewpoints of solubility in a developer, solubility in a developer, and the like, it is preferably 300 to 100,000, more preferably 300 to 30,000. If the weight average molecular weight is less than 300, the strength of the coating film or molded product obtained from the photosensitive resin composition of the present invention may be insufficient, and if it exceeds 100,000, the viscosity of the resin itself. This is not preferable because not only the solubility increases but the solubility becomes worse, and it becomes difficult to obtain a film having a uniform cured film surface and a constant film thickness. The weight average molecular weight is a value measured by gel permeation chromatography and converted to standard polystyrene.

  Examples of the resin having a base-reactive functional group and causing hydrolysis and polycondensation reaction include monomers having at least two or more siloxy groups in the molecule, and in the present invention, at least two in the molecule. The monomer having the above siloxy group is defined as a polysiloxane resin. Specific examples of such polysiloxane resins include poly (meth) acryloxypropyltrimethoxysilane and the like. These polysiloxane resins may be halogenated or hydrogenated. . Examples of commercial products of these polysiloxane resins include, but are not limited to, SQ series manufactured by Toa Gosei Co., Ltd.

  The weight-average molecular weight of a resin having a base-reactive functional group such as a polysiloxane resin that undergoes hydrolysis / condensation polymerization reaction is the heat resistance of the photosensitive resin composition of the present invention, coatability, and dissolution in an organic solvent described later. From the viewpoints of solubility and solubility in a developing solution, it is preferably 300 to 100,000, and more preferably 300 to 30,000. If the weight average molecular weight is less than 300, the strength of the coating film or molded product obtained from the photosensitive resin composition of the present invention may be insufficient, and if it exceeds 100,000, the viscosity of the resin itself. This is not preferable because not only the solubility increases but the solubility becomes worse, and it becomes difficult to obtain a film having a uniform cured film surface and a constant film thickness. The weight average molecular weight is a value measured by gel permeation chromatography and converted to standard polystyrene.

  Examples of the resin having a base-reactive functional group that causes a cyclization reaction include polyamic acid resins, and conventionally known polyamic acid resins obtained by reaction of acid anhydrides with diamines can be used. Specifically, for example, pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic Acid dianhydride, 4- (1,2-dicarboxyethyl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5- (1,2-dicarboxyethyl)- And polyamic acid resins obtained by reacting tetracarboxylic dianhydrides such as 3-methylcyclohexane-1,2-dicarboxylic dianhydride with diamines such as phenylenediamine, diaminobiphenyl ether, and diaminobenzophenone. The polyamic acid resin may be halogenated or hydrogenated. . In addition, these polyamic acid resins may be composed of a single repeating unit or may be composed of two or more kinds of repeating units. Examples of commercially available products of these polyamic acid resins include, but are not limited to, Upilex manufactured by Ube Industries, Ltd. and Kapton manufactured by Toray DuPont Co., Ltd.

  The weight average molecular weight of a resin having a base-reactive functional group such as a polyamic acid resin that causes a cyclization reaction is the heat resistance, coating property, solubility in an organic solvent described later, and development of the photosensitive resin composition of the present invention. From the viewpoint of solubility in the liquid, etc., it is preferably 300 to 100,000, more preferably 300 to 30,000. If the weight average molecular weight is less than 300, the strength of the coating film or molded product obtained from the photosensitive resin composition of the present invention may be insufficient, and if it exceeds 100,000, the viscosity of the resin itself. This is not preferable because not only the solubility increases but the solubility becomes worse, and it becomes difficult to obtain a film having a uniform cured film surface and a constant film thickness. The weight average molecular weight is a value measured by gel permeation chromatography and converted to standard polystyrene.

  The photosensitive resin composition of the present invention may be composed of a base generator represented by the general formula [1] and a base-reactive resin. However, the applicability of the photosensitive resin composition of the present invention is considered. In such a case, a composition containing an organic solvent may be desirable among the photosensitive resin compositions of the present invention. Such an organic solvent is not particularly limited as long as it is an organic solvent usually used in this field, since the base generator according to the present invention exhibits high solubility in various organic solvents. Solvents can be used. Specifically, for example, alcohol solvents such as methanol, ethanol, isopropyl alcohol and tert-butyl alcohol, ester solvents such as ethyl acetate, butyl acetate, ethyl lactate and γ-butyrolactone, propylene glycol monomethyl ether (PGME), propylene Glycol solvents such as glycol monomethyl ether acetate (PGMEA), ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide Amide solvents such as N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosphoramide, N-methylpyrrolidone (NMP), and sulfoxides such as dimethyl sulfoxide Solvents, and the like. Among these organic solvents, alcohol solvents, ester solvents, and glycol solvents are preferable. Alcohol-based, ester-based, and glycol-based organic solvents (1) have a moderate boiling point, so that not only can the composition normally prepared at room temperature be stably prepared, but the baking temperature during pre-baking is high. Therefore, the base generator, the base-reactive resin, and the like are not easily affected by heat, and (2) the composition is excellent in compatibility with the substrate and has a good elongation during spin coating. Can be easily applied on the substrate, (3) since the solubility of the base generator is high compared to other organic solvents, for example, in the process of producing a coating film according to the pattern forming method of the present invention In particular, the base generator is less likely to cause phase separation, and (4) the decomposition product does not show basicity like an amide solvent, so that the stability is high. In addition, you may use these organic solvents individually or in combination of 2 or more types, respectively.

  The photosensitive resin composition of the present invention includes, for example, 9-fluorenylmethyl carbamate as an auxiliary role of the base generator represented by the general formula [1] according to the present invention as long as the effects of the present invention are not hindered. A base proliferating agent such as benzophenone or diethylthioxanthone may be added.

  In the photosensitive resin composition of the present invention, the base generator represented by the general formula [1] preferably contains 1 to 80% by weight of the base generator with respect to the base reactive resin. Of these, it is more preferable to contain 10 to 30% by weight of a base generator. When the content of the base generator is less than 1% by weight, the photo-curing of the photosensitive resin composition of the present invention may be insufficient, and when it exceeds 80% by weight, the base generator itself. May adversely affect the solubility of the base-reactive resin, and is not preferable from the viewpoint of economy.

  In the photosensitive resin composition of the present invention, among the photosensitive resin compositions, in the case of a composition containing an organic solvent, the base-reactive resin according to the present invention is 0 with respect to 1 mL of the organic solvent. It is preferable to contain 0.1-1.0 g of base-reactive resin, and it is more preferable to contain 0.1-0.5 g of base-reactive resin. When the content of the base-reactive resin is less than 0.1 g, film formation itself may be difficult when a coating film is produced using the photosensitive resin composition of the present invention, and 1.0 g In the case of exceeding the range, not only the base-reactive resin itself may not be dissolved in the organic solvent, but also the content of the organic solvent is relatively reduced and the coating property is deteriorated, which is not preferable.

  The resin curing method of the present invention is characterized by using the photosensitive resin composition of the present invention, and includes a step of irradiating an active energy ray to a coating film or a molded body produced from the photosensitive resin composition. More specifically, for example, the photosensitive resin composition of the present invention is applied to a predetermined substrate to form a coating film, or formed into a specific shape to prepare a molded body, and prebaked as necessary. Etc. are performed to remove the solvent, and then, after irradiation with active energy rays, post-baking or the like is performed as necessary to cure the coating film or molded body to produce a cured film or cured molded body.

  The pattern forming method of the present invention is characterized in that the photosensitive resin composition of the present invention is used, and the coating film produced from the photosensitive resin composition is irradiated with active energy rays in a predetermined pattern; And a step of developing the coating film after the step. More specifically, for example, the photosensitive resin composition of the present invention is applied to a predetermined substrate to prepare a coating film, and then prebaked or the like as necessary to remove the solvent. Next, after irradiating active energy rays through a photomask having a predetermined pattern, post-baking is performed to cure the exposed portion. Further, the unexposed part (uncured part) is washed away by developing with a solution (developer) having a difference in solubility between the exposed part (cured part) and the unexposed part (uncured part). Thereby, the cured film which has a pattern of a predetermined shape is producible.

  Application to the substrate when preparing a coating film or a molded body may be performed by a known method, and specific examples include spin coating, roll coating, blade coating, and dipping. Moreover, the pre-baking performed as needed after the production of the coating film or the molded body is performed mainly for the purpose of evaporating the organic solvent according to the present invention, for example, on the substrate on which the coating film or the molded body is produced. There are known methods such as a method of applying heating and drying air using a heating device such as a clean oven, for example, a method of heating a substrate or the like on which a coating film or a molded body has been produced on a hot plate. What is necessary is just to set the heating temperature in the case of prebaking suitably according to the kind of base generator shown by General formula [1] which concerns on this invention, the kind of base reactive resin, and the kind of organic solvent. The specific heating temperature is usually 50 to 300 ° C, preferably 80 to 150 ° C. The specific heating time is usually 1 to 120 minutes, preferably 1 to 60 minutes. The heating temperature may be maintained at a desired temperature from the initial stage of heating, or may be raised stepwise to a desired temperature.

  The exposure apparatus and exposure method used when irradiating an active energy ray to a coating film or a molded object are not specifically limited, What is necessary is just to perform with a well-known exposure apparatus and exposure method. Since the base generator represented by the general formula [1] according to the present invention is preferably a base generator that is sensitive to an active energy ray having a wavelength of 150 to 500 nm, an exposure apparatus that irradiates such a wavelength is used. It is preferable. Further, the exposure method may be contact exposure or indirect exposure, and an active energy ray having an unnecessary wavelength may be blocked using a cut filter or the like, and only an active energy ray having a desired wavelength may be irradiated.

  As the post-baking performed as necessary after irradiating the active energy ray, for example, a known method such as a method of applying heating and drying air to the substrate after irradiating the active energy ray using a heating device such as a clean oven is used. Can be mentioned. What is necessary is just to set the heating temperature in the case of post-baking suitably according to the kind of base generator shown by General formula [1] which concerns on this invention, the kind of base reactive resin, and the kind of organic solvent. The specific heating temperature is usually 50 to 300 ° C, preferably 80 to 150 ° C. The specific heating time is usually 1 to 120 minutes, preferably 1 to 60 minutes. The heating temperature may be maintained at a desired temperature from the initial stage of heating, or may be raised stepwise to a desired temperature. The post-baking performed here causes the organic solvent according to the present invention to evaporate by heating at a higher temperature than the pre-baking, and is represented by the general formula [1] according to the present invention in the exposed portion (cured portion). It is to promote the reaction to the base-reactive resin by the base (primary or secondary amine) generated from the base generator, and to further increase the curing.

  In the pattern forming method of the present invention, development used when developing with a solution having a difference in solubility between an exposed part (cured part) and an unexposed part (uncured part) to wash away the unexposed part (uncured part) What is necessary is just to select suitably according to the kind of base reactive resin used, for example, an organic solvent, basic aqueous solution, etc. are mentioned as a liquid.

  Although it does not specifically limit as said organic solvent, Specifically, For example, alcohol solvents, such as methanol, ethanol, isopropyl alcohol, For example, Ketone solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, For example, N Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and dimethylacrylamide, sulfoxide solvents such as dimethyl sulfoxide, ester solvents such as ethyl acetate, ethyl lactate and γ-butyrolactone, For example, glycol solvents such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. ether solvents such as diethyl ether, tetrahydrofuran, dioxane, etc. Chloromethane, dichloroethane, halogenated solvents such as chloroform, include, for example, nitriles such as acetonitrile. These organic solvents may be used alone or in combination of two or more.

  Although it does not specifically limit as said basic aqueous solution, Specifically, for example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethyl Examples include aqueous solutions of organic alkalis such as ammonium hydroxide, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, and diethylethanolamine. Moreover, as a density | concentration of said alkaline aqueous solution, it is 1-50 weight% normally, Preferably it is 5-25 weight%. In addition, these basic aqueous solutions are used as an alkaline developer obtained by adding an appropriate amount of a surfactant such as a nonionic surfactant having an action of promoting development residue removal, or a water-soluble organic solvent such as methanol or ethanol. It is also possible to do. These basic aqueous solutions may be used alone or in combination of two or more.

  As a developing method in the developing step as described above, a conventionally known method such as a dipping method, a shower method, a spray method or the like may be adopted as appropriate, and the developing time related to the developing step is usually 1 to 10 minutes. is there.

  The pattern forming method of the present invention may include a washing step (rinsing step) and a heating step after development in addition to the steps as described above. The washing process (rinsing process) has the effect of washing away unnecessary portions that could not be removed by development and removing the developer adhering to the coating film, and the washing time for the washing process (rinsing process) Is usually 0.5 to 1 minute. Moreover, a heating process is suitably performed in order to make the produced cured resin pattern have heat resistance, and, specifically, for example, usually at a temperature of 50 to 200 ° C., preferably 100 to 150 ° C., 0.5. A highly heat-resistant cured resin pattern can be obtained by heating for 1 hour.

  The cured resin or cured resin pattern obtained in this way is provided as all or part of articles usually used in this field, such as paints, printing inks, dental materials, resists, and the like. That is, the photosensitive resin composition of the present invention can be used as a photocurable material such as paints, printing inks, dental materials, resists, among others, for example, resist materials in the manufacturing process of semiconductor elements, surfaces of semiconductor elements It can be suitably used as a protective film, an interlayer insulating film, an antireflection film, an alignment film, an insulating material for electronic parts, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited at all by these examples.

Synthesis Example 1 Synthesis of 2-acetylphenylacetate 6.8 g of 2-hydroxyacetophenone (50.0 mmol; manufactured by Wako Pure Chemical Industries, Ltd.), 5.0 g (50.0 mmol) of triethylamine and N, N-dimethylaminopyridine 0 Acetic anhydride (5.1 g, 50.0 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to a solution of 0.61 g (5.0 mmol) dissolved in acetone (20 mL), and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was concentrated under reduced pressure, dichloromethane was added to the concentrated residue, and the solution was washed successively with a saturated aqueous sodium hydrogen carbonate solution and ion-exchanged water. Crystals precipitated by concentrating the organic phase after washing under reduced pressure were collected by filtration, and then dried to give 8.81 g (49.4 mmol, yield: 98.9) of 2-acetylphenyl acetate as white crystals. %). The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 2.35 (3H, s, CH ₃ ), 2.64 (3H, s, CH ₃ ), 7.11 (1H, d, ArH), 7.34 (1H, t, ArH), 7.52 (1H, t, ArH), 7.82 (1H, d, ArH)

Synthesis Example 2 Synthesis of (E) -3- (2-hydroxyphenyl) -2-butenoic acid In 50 mL of toluene, out of 8.81 g of 2-acetylphenyl acetate obtained in Synthesis Example 1, 8.50 g (47. 7 mmol) and (ethoxycarbonylmethyl) triphenylphosphorane 25.3 g (72.6 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) were added and heated to reflux for 5 hours. After completion of the reaction, 30 mL of 25% aqueous sodium hydroxide solution was added to the concentrated residue obtained by concentrating the reaction solution under reduced pressure, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was extracted with dichloromethane, and the crystals precipitated when the aqueous solution was acidified by adding an aqueous citric acid solution were collected by filtration, and then dried to obtain white crystals. 4.21 g (23.6 mmol, yield: 49.5%) of (E) -3- (2-hydroxyphenyl) -2-butenoic acid was obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, d-DMSO) δ (ppm): 2.40 (3H, s, CH ₃ ), 5.81 (1H, s, CH), 6.77 (1H, t, ArH), 6.84 (1H, d, ArH), 7.08 (1H, d, ArH), 7.16 (1H, t, ArH), 9.64 (1H, brs, ArOH), 12.08 (1H, brs, COOH)

Synthesis Example 3 Synthesis of (E) -1- [3- (2-hydroxyphenyl) -2-butenoyl] -piperidine (base generator represented by the general formula [1] according to the present invention) Obtained in Synthesis Example 2 Of 4.21 g of (E) -3- (2-hydroxyphenyl) -2-butenoic acid, 2.99 g (16.8 mmol) and 3.39 g (33.6 mmol) of N-methylmorpholine; Wako Pure Chemical Industries, Ltd. ) Was dissolved in 20 mL of 1,2-dimethoxyethane, and 4.58 g (33.6 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of chloroformate was added dropwise under ice-cooling. Stir for 5 hours. After completion of the reaction, N-methylmorpholine hydrochloride generated by the reaction was removed by filtration, and 2.86 g (33.6 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of piperidine was added to the filtrate obtained there, and For 1 hour. After completion of the reaction, dichloromethane was added to the reaction solution, and the solution was washed successively with a saturated aqueous sodium hydrogen carbonate solution and ion-exchanged water. Crystals precipitated by concentrating the organic phase after washing under reduced pressure are collected by filtration, and the crystals are washed with diisopropyl ether and dried to give a white crystal represented by the above formula [15] (E) -1 There was obtained 1.27 g (5.1 mmol, yield: 30.3%) of-[3- (2-hydroxyphenyl) -2-butenoyl] -piperidine. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.58-1.69 (6H, m, CH ₂ × 3), 2.20 (3H, s, CH ₃ ), 3.46 (2H _{, m, CH 2), 3.64} (2H, m, CH 2), 6.13 (1H, s, CH), 6.56 (1H, brs, ArOH), 6.86-6.92 (2H , M, ArH × 2), 7.12-7.26 (2H, m, ArH × 2)

Synthesis Example 4 Synthesis of (E) -3- (2-hydroxyphenyl) -2-methyl-2-propenoic acid 6.10 g (50.0 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) in 50 mL of toluene Then, 19.9 g (55.0 mmol; manufactured by Aldrich) of (ethoxycarbonylethyl) triphenylphosphorane was added and heated to reflux for 3 hours. After completion of the reaction, 20 mL of 25% aqueous sodium hydroxide solution was added to the concentrated residue obtained by concentrating the reaction solution under reduced pressure, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was extracted with dichloromethane, and the crystals precipitated when hydrochloric acid was added to the extract to make the solution acidic, and the crystals were collected by filtration and dried to give white crystals (E ) -3- (2-hydroxyphenyl) -2-methyl-2-propenoic acid 5.87 g (32.9 mmol, yield: 65.8%) was obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, d-DMSO) δ (ppm): 1.97 (3H, s, CH ₃ ), 6.84 (1H, t, ArH), 6.90 (1H, d, ArH), 7.18 (1H, t, ArH), 7.30 (1H, d, ArH), 7.74 (1H, s, CH), 9.82 (1H, brs, ArOH), 12.34 (1H, brs, COOH)

Synthesis Example 5 Synthesis of (E) -1- [3- (2-hydroxyphenyl) -2-methyl-2-propenoyl] -piperidine (base generator represented by the general formula [1] according to the present invention) Synthesis Example (E) -3- (2-hydroxyphenyl) -2-methyl-2-propenoic acid 6.15 g (34.5 mmol) and N-methylmorpholine 3.54 g (35.0 mmol; 4.78 g of isobutyl chloroformate (35.0 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) was dropped into a solution prepared by dissolving Wako Pure Chemical Industries, Ltd. in 20 mL of 1,2-dimethoxyethane under ice cooling. And stirred at room temperature for 0.5 hour. After completion of the reaction, N-methylmorpholine hydrochloride generated by the reaction was removed by filtration, and 5.96 g (70.0 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of piperidine was added to the filtrate obtained there For 1 hour. After completion of the reaction, dichloromethane was added to the reaction solution, and the solution was washed successively with a saturated aqueous sodium hydrogen carbonate solution and ion-exchanged water. The organic phase after washing is concentrated under reduced pressure, and the concentrated residue is purified by silica gel column chromatography to give (E) -1- [3- (2-hydroxyphenyl) represented by the above formula [16] as a slightly yellow powder. -2-Methyl-2-propenoyl] -piperidine (2.33 g, 15.3 mmol, yield: 30.8%) was obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.59-1.66 (6H, m, CH ₂ × 3), 1.96 (3H, s, CH ₃ ), 3.58 (4H , M, CH ₂ × 2), 6.61 (1H, s, CH), 6.83 (1H, t, ArH), 6.94 (1H, d, ArH), 7.12-7.26 ( 2H, d, ArH × 2), 7.92 (1H, brs, ArOH)

Synthesis Example 6 Synthesis of (E) -3- (2-hydroxy-4-methoxyphenyl) -2-methyl-2-propenoic acid 2.44 g (20.0 mmol) of 2-hydroxy-4-methoxybenzaldehyde in 20 mL of toluene ; Wako Pure Chemical Industries, Ltd.) and (ethoxycarbonylethyl) triphenylphosphorane 7.97 g (22.0 mmol; Wako Pure Chemical Industries, Ltd.) were added and heated to reflux for 3 hours. After completion of the reaction, 10 mL of a 25% aqueous sodium hydroxide solution was added to the concentrated residue obtained by concentrating the reaction solution under reduced pressure, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was extracted with dichloromethane, and the crystals precipitated when the solution was made acidic by adding hydrochloric acid to the extract were collected by filtration and then dried to give slightly yellow crystals ( E) 3.49 g (16.7 mmol, yield: 83.5%) of 3- (2-hydroxy-4-methoxyphenyl) -2-methyl-2-propenoic acid was obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, d-DMSO) δ (ppm): 1.96 (3H, s, CH ₃ ), 3.76 (3H, s, OCH ₃ ), 5.71 (1H, s, CH) , 6.44-6.49 (2H, m, ArH × 2), 7.25 (1H, d, ArH), 9.92 (1H, brs, ArOH), 12.17 (1H, brs, COOH)

Synthesis Example 7 (E) -1- [3- (2-hydroxy-4-methoxyphenyl) -2-methyl-2-propenoyl] -piperidine (base generator represented by the general formula [1] according to the present invention) (E) -3- (2-hydroxy-4-methoxyphenyl) -2-methyl-2-propenoic acid 3.49 g (16.7 mmol) and N-methylmorpholine 1.69 g obtained in Synthesis Example 6 ( 12.8 mmol; manufactured by Wako Pure Chemical Industries, Ltd. in a solution of 20 mL of 1,2-dimethoxyethane, 2.28 g (16.7 mmol; Wako Pure Chemical Industries, Ltd.) of isobutyl chloroformate under ice cooling Product) was added dropwise, followed by stirring at room temperature for 0.5 hour. After completion of the reaction, N-methylmorpholine hydrochloride generated in the reaction was removed by filtration, and 2.84 g (33.4 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of piperidine was added to the filtrate obtained there For 1 hour. After completion of the reaction, dichloromethane was added to the reaction solution, and the solution was washed successively with a saturated aqueous sodium hydrogen carbonate solution and ion-exchanged water. The organic phase after washing is concentrated under reduced pressure, and the concentrated residue is purified by silica gel column chromatography to give (E) -1- [3- (2-hydroxy-4- 0.98 g (3.5 mmol, yield: 20.9%) of methoxyphenyl) -2-methyl-2-propenoyl] -piperidine was obtained. The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.60-1.72 (6H, m, CH ₂ × 3), 2.17 (3H, s, CH ₃ ), 3.57-3 .60 (4H, m, CH ₂ × 2), 3.76 (3H, s, OCH ₃ ), 6.41-6.51 (3H, m, CH, ArH × 2), 7.03 (1H, d, ArH), 7.76 (1H, brs, ArOH)

Evaluation Example 1 Ultraviolet-Visible Absorption Spectrum Measurement Test Acetonitrile solution of the base generator represented by the general formula [1] according to the present invention obtained in Synthesis Examples 3, 5, and 7 (about 5 × 10 ⁻⁵ mol / L) ) Were prepared and injected into a quartz cell TOS-UV-10 (1 cm × 1 cm × 4 cm) (manufactured by Toshin Riko Co., Ltd.), and then a spectrophotometer UV-2550 (manufactured by Shimadzu Corporation) was used. Then, an ultraviolet-visible absorption spectrum was measured. Table 1 shows the maximum absorption wavelength (nm) and the molar extinction coefficient (ε) at each maximum absorption wavelength for each base generator.

Evaluation Example 2 Thermal stability measurement test TG-DTA2000SA (manufactured by BRUKER AXS Co., Ltd.) was used for the base generator represented by the general formula [1] according to the present invention obtained in Synthesis Examples 3, 5, and 7. TG-DTA measurement was performed from 30 ° C. to 500 ° C. at a rate of temperature increase of 10 ° C./min, 5% weight loss temperature of each base generator was calculated, and heat resistance was evaluated. The results are shown in Table 2.

Evaluation Example 3 Solubility Test in Organic Solvent The base generator represented by the general formula [1] according to the present invention obtained in Synthesis Examples 3, 5, and 7 has a solubility in an organic solvent according to the present invention at room temperature. While confirming, the solubility with respect to the base generator for a comparison shown by Formula [101]-[103] was similarly confirmed at room temperature. The structure of the base generator represented by the formulas [101] to [103] is shown below, and the solubility evaluation results are shown in Table 3.

Examples 1-3 Curing Test with Poly (Glycidyl Methacrylate) Synthesis Example 3, 5, 20% by weight based on 0.2 g of poly (glycidyl methacrylate) and 0.2 g of poly (glycidyl methacrylate) having a weight average molecular weight of about 17000 A solution of 1 mL of N-methylpyrrolidone (NMP) containing the base generator obtained in 7 was prepared. That is, the photosensitive resin composition of the present invention prepared using the base generator represented by the formula [15] in Synthesis Example 3 was used as the base generator represented by the formula [16] in Example 1 and Synthesis Example 5. The photosensitive resin composition of the present invention prepared by using the base generator represented by the formula [17] of Example 2 and Synthesis Example 7 was used as Example 3. Next, the photosensitive resin compositions of Examples 1 to 3 were spin-coated on a silicon wafer and heated at 80 ° C. for 1 minute to produce a coating film having a thickness of about 1.5 μm. This coating film was irradiated with ultraviolet rays for a predetermined time using a UV irradiation light source device having a specific exposure intensity, that is, UIS-5011DUB4 (manufactured by USHIO INC.), And the photosensitive resin composition of Examples 1 to 3 Each of the bases was generated, and the coating film was cured by heating at 120 ° C. for 20 minutes for Examples 1 and 2 and 5 minutes at 120 ° C. for Example 3. Furthermore, the thickness of the coating film was measured by immersing this coating film in acetone for 30 seconds and developed, and the film thickness of the coating film before and after development was determined as the remaining film ratio. Table 4 shows the exposure intensity of the light source device UIS-5011DUB4 at a specific wavelength, and FIGS. 1 to 3 show the measurement results of the remaining film ratio with respect to ultraviolet irradiation every predetermined time.

Example 4 Curing test with poly (glycidyl methacrylate) 0.2 g of poly (glycidyl methacrylate) and 20% by weight of the above obtained in Synthesis Example 5 with respect to 0.2 g of poly (glycidyl methacrylate) having a weight average molecular weight of about 17000 A solution of 1 mL of propylene glycol monomethyl ether acetate (PGMEA) containing a base generator represented by the formula [16] was prepared to obtain a photosensitive resin composition of the present invention. Next, the photosensitive resin composition was spin-coated on a silicon wafer and heated at 100 ° C. for 1 minute to produce a coating film having a thickness of about 1.5 μm. This coating film is irradiated with ultraviolet rays for a predetermined time using a UV irradiation light source device having the exposure intensity shown in Table 4, ie, UIS-5011DUB4 (USHIO INC.) To generate a base from the photosensitive resin composition. The film was cured by heating at 120 ° C. for 20 minutes. Furthermore, the thickness of the coating film was measured by immersing this coating film in acetone for 30 seconds and developed, and the film thickness of the coating film before and after development was determined as the remaining film ratio. The measurement result of the remaining film rate with respect to ultraviolet irradiation for every predetermined time is shown in FIG.

Comparative Example 1 Curing Test with Poly (Glycidyl Methacrylate) 0.2% of poly (glycidyl methacrylate) and 20% by weight of the above formula [101] with respect to 0.2 g of poly (glycidyl methacrylate) having a weight average molecular weight of about 17000 A 1 mL solution of propylene glycol monomethyl ether acetate (PGMEA) containing a base generator ((E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] -piperidine) was prepared, and the photosensitivity for comparison was prepared. A resin composition was obtained. Next, a coating film using the photosensitive resin composition was tried, but the base generator represented by the formula [101] was not completely dissolved in propylene glycol monomethyl ether acetate (PGMEA). A coating film could not be produced.

Example 5 Viscosity Test with Bisphenol A Type Epoxy Resin Adeka Resin EP-4100 (manufactured by ADEKA Co., Ltd.) with respect to 15.0 g, 30 wt% of the base represented by the above formula [16] obtained in Synthesis Example 5 The generator was dissolved in Adeka Resin EP-4100 to prepare the photosensitive resin composition of the present invention. Next, 3.0 g of the photosensitive resin composition was molded on a petri dish, and the obtained molded product was an ultraviolet irradiation light source device having the exposure intensity shown in Table 4, ie, UIS-5011DUB4 (manufactured by Ushio Electric Co., Ltd.). Was irradiated with ultraviolet rays for 30 minutes to generate a base from the photosensitive resin composition, and the molded body was further heated at 120 ° C. for 20 minutes. Next, this molded product was diluted with 1.5 g of N-methylpyrrolidone (NMP), and the viscosity of the diluted molded product was measured using RE-85R (1 ° 34 '× R24) (manufactured by Toki Sangyo Co., Ltd.). It was measured. As a result of the viscosity measurement, the viscosity of the molded product not irradiated with ultraviolet rays was 130 mPa · s, whereas the viscosity of the molded product irradiated with ultraviolet rays for 30 minutes was 222 mPa · s. An improvement in viscosity was observed.

  From the results of Evaluation Example 1, it can be seen that the base generator according to the present invention has a high photosensitive region at a wavelength of 200 nm or more, such as 254 nm, and is sensitive to an active energy ray of 300 nm or more. From this, it was found that the base generator according to the present invention generates a base upon irradiation with an active energy ray having a wavelength of 200 nm or more. This result is supported by the fact that the photosensitive resin composition of Examples 1 to 3, that is, a base sufficient to cure the resin from the photosensitive resin composition of the present invention is generated and a cured film can be formed. ing. Moreover, since the 5% weight reduction | decrease temperature of the base generator which concerns on this invention exceeds 180 degreeC from the result of the evaluation example 2, it turns out that it is comparatively stable with respect to a heat | fever. Therefore, when the base generator according to the present invention is used, even when the organic solvent according to the present invention is a high-boiling organic solvent, the temperature during baking can be set high. Thereby, the residue of the organic solvent after baking can be reduced as much as possible, and it can be expected that the deterioration of the contrast between the exposed portion (cured portion) and the unexposed portion (uncured portion) due to the residual organic solvent is suppressed. Furthermore, from the results of Evaluation Example 3, the base generator according to the present invention is highly versatile because it exhibits high solubility in various organic solvents, whereas conventional base generators are mostly organic solvents. Therefore, it was found that the desired solubility was exhibited only in a specific organic solvent and the versatility was poor. This result is clear from the results of Example 4 and Comparative Example 1 using N-methylpyrrolidone (NMP) as the organic solvent. That is, the photosensitive resin composition of the present invention using N-methylpyrrolidone (NMP) as an organic solvent can produce a coating film (cured film) without problems, but a photosensitive resin composition containing a conventional base generator. The product is also supported by the inability to produce a coating film (cured film) because the base generator does not dissolve in N-methylpyrrolidone (NMP). Furthermore, from the results of Example 5, the base generator according to the present invention exhibits high solubility, so that depending on the type of the base reactive resin according to the present invention, the base generator may include a base generator. Therefore, even if it was the photosensitive resin composition of this invention which does not contain an organic solvent, it turned out that a coating film (cured film) or a molded object (cured molded object) can be produced without a problem. From the above results, it was found that the photosensitive resin composition of the present invention is useful as a highly versatile photocurable pattern forming material.

  The photosensitive resin composition of the present invention has high solubility in various organic solvents such as alcohol solvents, glycol solvents, ester solvents and the like. When generating a base by irradiation with active energy rays, carbon dioxide gas Since it is a photosensitive resin composition containing a photobase generator that is not accompanied by generation, it is useful as a photocurable pattern forming material such as paint, printing ink, dental material, resist, and the like.

  The resin curing method and pattern forming method using the photosensitive resin composition of the present invention are highly versatile methods because various organic solvents can be used.

Claims (18)

A photosensitive resin composition comprising a base generator represented by the following general formula [1] and a base-reactive resin.

(In the formula, R ¹ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group or a cyano group, and R ² represents a hydrogen atom. Represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group or a cyano group, and R ^{3 to} R ⁶ each independently represent a hydrogen atom , A halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms, and a substituent. Represents a good aryl group having 6 to 10 carbon atoms, a hydroxyl group or a nitro group, Z represents a group derived from a primary or secondary amine, and R ² and R ³ may form a cyclic structure; a benzene ring condensed ^{to R} 3 to R ⁶ 2 or more is bonded to the R ³ to R ⁶ are attached Ring may be a to form. However, all of R ³ to R ⁶ are excluding are hydrogen atom.) In the base generator represented by the general formula [1], R ¹ Is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group or a cyano group, and R ² Is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group or cyano group, and R ³ ~ R ⁶ At least one of them has a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms, and a substituent. The photosensitive resin composition of Claim 1 which is a C6-C10 aryl group, hydroxyl group, or nitro group which may be carried out. In the base generator represented by the general formula [1], R ⁵ Has a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms, and a substituent. An aryl group having 6 to 10 carbon atoms, a hydroxyl group or a nitro group, and R ³ , R ⁴ And R ⁶ The photosensitive resin composition of Claim 1 whose is a hydrogen atom. In the base generator represented by the general formula [1], R ⁵ Is a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms, and R ³ , R ⁴ And R ⁶ The photosensitive resin composition of Claim 1 whose is a hydrogen atom. In the base generator represented by the general formula [1], R ⁵ Is a linear or branched alkoxy group having 1 to 4 carbon atoms, and R ³ , R ⁴ And R ⁶ The photosensitive resin composition of Claim 1 whose is a hydrogen atom. In the base generator represented by the general formula [1], R ¹ The photosensitive resin composition according to any one of claims 1 to 5, wherein is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. In the base generator represented by the general formula [1], R ¹ The photosensitive resin composition of any one of Claims 1-5 whose is a C1-C4 linear or branched alkyl group. In the base generator represented by the general formula [1], R ² The photosensitive resin composition of any one of Claims 1-7 whose is a hydrogen atom or a C1-C10 linear, branched or cyclic alkyl group. In the base generator represented by the general formula [1], R ² The photosensitive resin composition of any one of Claims 1-7 whose is a hydrogen atom or a C1-C4 linear or branched alkyl group. The base generator represented by the general formula [1], wherein the primary or secondary amine-derived group represented by Z is represented by the following general formula [2] . 2. The photosensitive resin composition according to item 1.

(Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, Or it represents what forms the C2-C10 nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring which may have a substituent with the nitrogen atom which these have couple | bonded.) The base generator represented by the general formula [1], wherein the primary or secondary amine-derived group represented by Z is represented by the following general formula [3] . 2. The photosensitive resin composition according to item 1.

(Wherein R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and V _1, the carbon atoms in the main chain represent an alkyl group having an oxygen atom or a silicon atom optionally 2 to 10 carbon atoms which may be substituted with, Y represents a group represented by the following general formula [1 '].)

(In the formula, R ^{1 to} R ⁶ are the same as above.) The base generator represented by the general formula [1], wherein the primary or secondary amine-derived group represented by Z is represented by the following general formula [4] . 2. The photosensitive resin composition according to item 1.

(Wherein R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms , and V ₂ represents a main chain carbon atom that is oxygen. represents an atom or a silicon atom optionally substituted by an alkyl group having 1 to 10 carbon atoms, Y represents a group represented by the following general formula [1 '], m and n are each independently 1 or 2)

(In the formula, R ^{1 to} R ⁶ are the same as above.) The photosensitive resin composition according to claim 1, wherein the base generator represented by the general formula [1] is represented by the following general formula [5].

(In the formula, R ¹ ′ represents a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, or a cyano group, and R ² ′ represents a hydrogen atom. Represents a linear or branched alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group or a cyano group, and R ³ ′ to R ⁶ ′ each independently represents a hydrogen atom , A halogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, and optionally having 6 carbon atoms To 10 aryl groups, hydroxyl groups or nitro groups, Z ′ represents a group represented by the following formulas [6] to [14], and R ² ′ and R ³ ′ may form a cyclic structure. it may, R ^{3 '~R} 6' 2 or more is bonded to the R ^{3 '~R} 6' form a benzene ring and condensed ring bonded Can have. However, all of ^{R 3 '~R 6'} excluding a hydrogen atom.)

(Wherein, Y 'is represented by the following general formula [5' represents a group represented by.)

(Wherein, Y 'is represented by the following general formula [5' represents a group represented by.)

(In the formula, R ¹ ′ to R ⁶ ′ are the same as above.) The photosensitive resin composition of Claim 1 whose base generator shown by the said General formula [1] is what is shown by Formula [17] .

A pattern forming material comprising the photosensitive resin composition according to claim 1. The coating film or molded article made from the photosensitive resin composition according to claim 1, a resin curing method which comprises a step of irradiating an active energy ray. A step of irradiating the coating film prepared from the photosensitive resin composition according to claim 1 with active energy rays in a predetermined pattern,
Developing the coating film after the process,
A pattern forming method comprising: A photobase generator for resin curing represented by the following general formula [5].

(In the formula, R ¹ ′ represents a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, or a cyano group, and R ² ′ represents a hydrogen atom. Represents a linear or branched alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group or a cyano group, and R ³ ′ to R ⁶ ′ each independently represents a hydrogen atom , A halogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, and optionally having 6 carbon atoms To 10 aryl groups, hydroxyl groups or nitro groups, Z ′ represents a group represented by the following formulas [6] to [14], and R ² ′ and R ³ ′ may form a cyclic structure. it may, R ^{3 '~R} 6' 2 or more is bonded to the R ^{3 '~R} 6' form a benzene ring and condensed ring bonded Can have. However, all of ^{R 3 '~R 6'} excluding a hydrogen atom.)

(Wherein, Y 'is represented by the following general formula [5' represents a group represented by.)

(Wherein, Y 'is represented by the following general formula [5' represents a group represented by.)

(In the formula, R ¹ ′ to R ⁶ ′ are the same as above.)

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