JP2014097930A - Heat base generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat base generator which can efficiently generate an amine (a tertiary amine or an amidine) having a high catalytic activity by heating, has a high solubility in ethyl lactate and 2-methoxy-1-methylethyl acetate and has excellent storage stability.SOLUTION: There is provided a heat base generator represented by the general formula (1). [Wherein, Arrepresents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms or the like; Arrepresents an aryl group having 6 to 14 carbon atoms or the like; Rto Rrepresent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 14 carbon atoms; Ar, Rand Rmay be bonded together to form a ring structure; Rrepresents an alkyl group having 1 to 18 carbon atoms; n represents an integer of 1 to 4; and Yrepresents a quaternary ammonio group.]

Description

The present invention relates to a thermal base generator that generates a base by heating. More specifically, heating is performed through a material that is cured using a base generated by heating (for example, a coding agent or a paint), or by patterning using a difference in solubility between the exposed portion and the unexposed portion in the developer by light irradiation. Relates to a thermal base generator suitable for use in the manufacture of products or members (for example, electronic components, optical products, optical component forming materials, layer forming materials, or adhesives) formed by the above method.

It is a known technique to use an amine catalyst for the purpose of accelerating the polymerization reaction or crosslinking reaction of epoxide or isocyanate. From the strength of activity, strong bases (tertiary amines, pKa 8 to 11) and super strong bases (guanidine, amidine, etc., pKa 11 to 13) are preferably used.

When such an amine catalyst is used, so-called potential is required, for example, that the activity is low at room temperature and the reaction is accelerated only during heating and cured in a short time.

As a latent method, a method of forming a neutral salt with an acid (Patent Documents 1 to 3) and a method of quaternizing an amine to form an ammonium salt (Patent Document 4) are known.

However, in the method of using a neutralized salt with an acid, the potential can be controlled by the strength of the acid, but depending on the application, the acid may have problems such as corrosion, and the storage stability of the formulation is insufficient. There is a problem, and the salt of Patent Document 4 is low in solubility in monomers and solvents {ethyl lactate, 2-methoxy-1-methylethyl acetate (hereinafter abbreviated as PGMEA, etc.)}, and the application range is limited, so that the improvement is achieved. It was sought after.

JP-A-62-282929 Japanese Patent Laid-Open No. 9-274416 Japanese Patent Laid-Open No. 11-60869 JP 62-246925 A

The present invention has been made in view of the above-mentioned problems, and can be used for, for example, a crosslinking reaction of an epoxy compound, the strength of a generated base is high, and when applied to an epoxy compound or the like, An object of the present invention is to provide a base generator in which base generation reactions are performed in a chain, excellent in reaction efficiency and high in solubility in a solvent, and a thermosetting resin composition containing the base generator.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a thermal base generator having excellent characteristics.
That is, this invention is a thermal base generator characterized by being represented by General formula (1).

[In the formula (1), Ar ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, a nitro group, a hydroxyl group, a cyano group,- An alkoxy group represented by OR ¹¹ , an amino group represented by —NR ¹² R ¹³ , an acyloxy group represented by R ¹⁵ COO—, an alkylthio group or an arylthio group represented by —SR ¹⁶ , a halogen atom or a carbon number 6 to 14 aryl groups, wherein some of the hydrogen atoms in the aryl group are alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, carbon numbers 6-14 aryl group, nitro group, hydroxyl group, cyano group, alkoxy group represented by —OR ¹¹ , amino group represented by —NR ¹² R ¹³ , acyl group represented by R ¹⁴ CO—, R ¹⁵ CO An acyloxy group represented by O—, an alkylthio group or arylthio group represented by —SR ¹⁶ , or a halogen atom may be substituted; Ar ² is an aryl group having 6 to 14 carbon atoms, Some of the hydrogen atoms therein are alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, nitro groups, hydroxyl groups, Cyano group, alkoxy group represented by —OR ¹¹ , amino group represented by —NR ¹² R ¹³ , acyl group represented by R ¹⁴ CO—, acyloxy group represented by R ¹⁵ COO—, —SR ¹⁶ in represented by an alkylthio group or an arylthio group, or a halogen atom may be substituted by; R ¹ to R ² is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, aryl having 6 to 14 carbon atoms A ^{group, Ar 1, R 1, R} 2 are bonded to each other may form a ring structure; ^{R 3} is a number from 1 to 18 alkyl group carbon; n is an integer of from 1 to 4 R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are alkyl groups having 1 to 8 carbon atoms or aryl groups having 6 to 14 carbon atoms; R ¹² and R ¹³ are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms or carbon; Y ⁺ is a quaternary ammonio group represented by either of the following general formulas (2) or (3); in formula (2), R ^{4 to} R ⁵ are An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which may be bonded to each other to form a ring structure; Q is a methylene group (-CH ₂ -) m, or a group represented by the following general formula (4); m is an integer of 2 or 3; formula ^3), R 6 to R ⁸ is an alkyl group, an alkenyl group or an aryl group having 6 to 14 carbon atoms having 2 to 18 carbon atoms having 1 to 18 carbon atoms, have a ring structure with each other In formula (4), R ^{9 to} R ¹⁰ are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and may be bonded to each other to form a ring structure. Good. ]

  Furthermore, the present invention is a thermosetting composition comprising the above-described thermal base generator and a base-reactive compound.

  Furthermore, this invention is a hardening body obtained by hardening | curing the said thermosetting composition.

Since the thermal base generator of the present invention is not basic at room temperature, it can be heated without deteriorating the storage stability of the reactive composition even if it is contained in the reactive composition. Thus, amines (tertiary amines or amidines) with high catalytic activity can be generated efficiently.
Moreover, since the thermal base generator of the present invention does not contain a halogen ion or an acid as a counter anion, there is no fear of metal corrosion.
In addition, the thermal base generator of the present invention has high solubility in ethyl lactate, PGMEA and the like used for the patterning member, and not only in the thermosetting composition but also in the heating process after the patterning process in the photosensitive composition. Applicable.

  Hereinafter, embodiments of the present invention will be described in detail.

The thermal base generator means a substance that decomposes its chemical structure upon heating to generate a base (amine). The generated base can act as a catalyst for epoxy resin curing reaction, polyimide resin curing reaction, isocyanate and polyol urethanization reaction, acrylate crosslinking reaction, and the like.

The thermal base generator of the present invention is represented by the general formula (1).

[In the formula (1), Ar ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, a nitro group, a hydroxyl group, a cyano group,- An alkoxy group represented by OR ¹¹ , an amino group represented by —NR ¹² R ¹³ , an acyloxy group represented by R ¹⁵ COO—, an alkylthio group or an arylthio group represented by —SR ¹⁶ , a halogen atom or a carbon number 6 to 14 aryl groups, wherein some of the hydrogen atoms in the aryl group are alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, carbon numbers 6-14 aryl group, nitro group, hydroxyl group, cyano group, alkoxy group represented by —OR ¹¹ , amino group represented by —NR ¹² R ¹³ , acyl group represented by R ¹⁴ CO—, R ¹⁵ CO An acyloxy group represented by O—, an alkylthio group or arylthio group represented by —SR ¹⁶ , or a halogen atom may be substituted; Ar ² is an aryl group having 6 to 14 carbon atoms, Some of the hydrogen atoms therein are alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, nitro groups, hydroxyl groups, Cyano group, alkoxy group represented by —OR ¹¹ , amino group represented by —NR ¹² R ¹³ , acyl group represented by R ¹⁴ CO—, acyloxy group represented by R ¹⁵ COO—, —SR ¹⁶ in represented by an alkylthio group or an arylthio group, or a halogen atom may be substituted by; R ¹ to R ² is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, aryl having 6 to 14 carbon atoms A ^{group, Ar 1, R 1, R} 2 are bonded to each other may form a ring structure; ^{R 3} is a number from 1 to 18 alkyl group carbon; n is an integer of from 1 to 4 R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are alkyl groups having 1 to 8 carbon atoms or aryl groups having 6 to 14 carbon atoms; R ¹² and R ¹³ are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms or carbon; Y ⁺ is a quaternary ammonio group represented by either of the following general formulas (2) or (3); in formula (2), R ^{4 to} R ⁵ are An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which may be bonded to each other to form a ring structure; Q is a methylene group (-CH ₂ -) m, or a group represented by the following general formula (4); m is an integer of 2 or 3; formula ^3), R 6 to R ⁸ is an alkyl group, an alkenyl group or an aryl group having 6 to 14 carbon atoms having 2 to 18 carbon atoms having 1 to 18 carbon atoms, have a ring structure with each other In formula (4), R ^{9 to} R ¹⁰ are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and may be bonded to each other to form a ring structure. Good. ]

In the general formula (1), the alkyl group of Ar ¹ having 1 to 18 carbon atoms (preferably 1 to 12, more preferably 1 to 8) is a linear alkyl group (methyl, ethyl, n-propyl). , N-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl, etc., branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl) , Isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl), cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl) and bridged cyclic alkyl groups ( Norbornyl, adamantyl and pinanyl).
As the alkenyl group of Ar ¹ having 2 to 18 carbon atoms (preferably 2 to 12 and more preferably 2 to 8), linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl) 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, etc.), cyclo Examples include alkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl) and arylalkenyl groups (such as styryl and cinnamyl).
Examples of the alkynyl group of Ar ¹ having 2 to 18 carbon atoms (preferably 2 to 12 and more preferably 2 to 8) include linear or branched alkynyl groups (ethynyl, 1-propynyl, 2-propynyl, 1 -Butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1,1-dimethyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl- 2-butynyl, 3-methyl-1-butynyl, 1-decynyl, 2-decynyl, 8-decynyl, 1-dodecynyl, 2-dodecynyl and 10-dodecynyl) and arylalkynyl groups (phenylethynyl and the like). As the alkynyl group, in addition to the above, some of the hydrogen atoms of the alkynyl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group having 1 to 18 carbon atoms, and / or an alkylthio group having 1 to 18 carbon atoms, etc. A substituted alkynyl group substituted with may be used.
Alkoxy group represented by ^{-OR 11} of Ar ^{1, -NR} 12 amino group represented by ^{R 13,} an acyloxy group represented by R 15 COO-, carbon atoms in the alkylthio group represented by ^{-SR 16} 1 Examples of the alkyl group of ˜8 (preferably 1 to 4) include alkyl groups having 1 to 8 carbon atoms among the above alkyl groups. As the alkyl group, in addition to the above, a part of hydrogen atoms of the alkyl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an aryl group having 6 to 14 carbon atoms, an alkoxy group having 1 to 18 carbon atoms and / or A substituted alkyl group substituted with an alkylthio group having 1 to 8 carbon atoms or the like may be used.
C 6 in the alkoxy group represented by —OR ¹¹ of Ar ^1, the amino group represented by —NR ¹² R ¹³ , the acyloxy group represented by R ¹⁵ COO—, and the arylthio group represented by —SR ¹⁶ The following aryl groups are mentioned as the aryl group of -14. As the aryl group, in addition to the above, a part of the hydrogen atoms of the aryl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group having 1 to 18 carbon atoms, and / or an alkylthio group having 1 to 8 carbon atoms, etc. A substituted aryl group substituted with may be used.
Examples of the alkoxy group represented by —OR ¹¹ include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and 2- Examples include methylbutoxy.
Examples of the amino group represented by —NR ¹² R ¹³ include methylamino, ethylamino, propylamino, dimethylamino, diethylamino, methylethylamino, dipropylamino, dipropylamino and piperidino.
Examples of the acyloxy group represented by R ¹⁵ COO— include acetoxy, butanoyloxy and benzoyloxy.
Examples of the alkylthio group or arylthio group represented by —SR ¹⁶ include methylthio, ethylthio, butylthio, hexylthio, cyclohexylthio, benzylthio, phenylthio, biphenylthio and 4-methylphenylthio.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the aryl group having 6 to 14 carbon atoms of Ar ¹ and Ar ² include a monocyclic aryl group (such as phenyl), a condensed polycyclic aryl group (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl and naphthoquinolyl) and aromatic Heterocyclic hydrocarbon groups (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and other monocyclic heterocycles; and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl , Quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, coumarinyl, dibenzo Enyl, Kisantoniru, Chiokisantoniru, dibenzofuranyl, etc. fused polycyclic heterocyclic ring).
As the aryl group, in addition to the above, some of the hydrogen atoms in the aryl group are alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, and 6 carbon atoms. -14 aryl group, a nitro group, a hydroxyl group, a cyano group, an alkoxy group represented by ^{-OR 11,} amino group represented by ^-NR 12 ^{R 13,} an acyl group represented by R 14 ^CO-, R 15 COO - acyloxy group represented by may be substituted with an alkylthio group or an arylthio group represented by -SR ¹⁶ or a halogen atom.

Among the substituents, examples of the alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the alkynyl group having 2 to 18 carbon atoms, and the aryl group having 6 to 14 carbon atoms include the same ones as described above.
Among the substituents, an alkoxy group represented by ^{-OR 11,} amino group represented by ^-NR 12 ^{R 13,} an acyl group represented by R 14 ^CO-, acyloxy group represented by R 15 COO-, - Examples of the alkyl group having 1 to 8 carbon atoms (preferably 1 to 4) and the aryl group having 6 to 14 carbon atoms in the alkylthio group or arylthio group represented by SR ¹⁶ include the same ones as described above.
Examples of the acyl group represented by R ¹⁴ CO— include acetyl, propanoyl, butanoyl, pivaloyl and benzoyl.

In the general formula ^(1), of the R 1 to R ^2, the alkyl group having 1 to 18 carbon atoms (1 to 12 are preferred, more preferably 1-8.), For example, an alkyl group of the . As the alkyl group, in addition to the above, a part of hydrogen atoms of the alkyl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an aryl group having 6 to 14 carbon atoms, an alkoxy group having 1 to 18 carbon atoms and / or A substituted alkyl group substituted with an alkylthio group having 1 to 18 carbon atoms or the like may be used.
Among R ^{1 to} R ² , the aryl group having 6 to 14 carbon atoms includes the above aryl group. As the aryl group, in addition to the above, a part of the hydrogen atoms of the aryl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group having 1 to 18 carbon atoms, and / or an alkylthio group having 1 to 18 carbon atoms, etc. A substituted aryl group substituted with may be used.
These substituents R ^{1 to} R ² and Ar ¹ may be bonded to each other to form a ring structure.

In the general formula (1), among R ³ , the alkyl group having 1 to 18 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms) is exemplified as the alkyl group described above for R ^{1 to} R ^2. The same thing as a group is mentioned.

In the general formula (1), n represents the number of R ³ and Ar ² substituted on the borate anion, and is an integer of 1 to 4.

The quaternary ammonio group (Y ⁺ ) is eliminated as a corresponding amine (Y) by heating and functions as various reaction catalysts. On the other hand, since the quaternary ammonio group (Y ⁺ ) is not basic before heating, the storage stability of the reactive composition does not decrease even if it is contained in the reactive composition. .

The quaternary ammonio group (Y ⁺ ) is represented by either the following general formula (2) or general formula (3).
Among R ^{4 to} R ⁵ in the general formula (2), the alkyl group having 1 to 18 carbon atoms is the same as the above alkyl group, and the aryl group having 6 to 14 carbon atoms is the same as the above aryl group. It is. These substituents may be bonded to each other to form a ring structure.
In the general formula (2), Q is a methylene group (—CH ₂ —) m or a group represented by the following general formula (4), and m is an integer of 2 or 3.

The substituents R ^{9 to} R ¹⁰ in the general formula (4) are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and an aryl group having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms is the same as the above aryl group. These substituents may be bonded to each other to form a ring structure.

The substituents R ^{6 to} R ⁸ in the general formula (3) are an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an aryl group having 6 to 14 carbon atoms, which are bonded to each other to form a ring. A structure may be formed. The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, and the aryl group having 6 to 14 carbon atoms are each an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a carbon number. It is the same as the aryl group of 6-14.

As the quaternary ammonio group represented by the general formula (2), 1,8-diazabicyclo [5.4.0] -7-undecen-8-yl {group represented by the chemical formula (5)}, 1 , 5-diazabicyclo [4.3.0] -5-nonen-5-yl {group represented by the chemical formula (6)} and a group represented by the general formula (7). Specific examples include 1-methylimidazol-3-yl, 1,2-dimethylimidazol-3-yl, 1-methyl-2-ethylimidazol-3-yl and the like.

In the general formula (7), the substituent R ¹⁷ is an alkyl group having 1 to ¹⁸ carbon atoms, R ¹⁸ is an alkyl group having 1 to ¹⁸ carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms. And may be bonded to each other to form a ring structure. Examples of the alkyl group having 1 to 18 carbon atoms (preferably 1 to 12 and more preferably 1 to 8) include the same alkyl groups as those described above for R ^{1 to} R ² .
Examples of the alkenyl group having 2 to 18 carbon atoms include the above alkenyl groups.
Examples of the aryl group having 6 to 14 carbon atoms include the above aryl groups.

As the quaternary ammonio group represented by the general formula (3), 1-azabicyclo [2.2.2] octan-1-yl {group represented by the chemical formula (8)}, 3-hydroxy-1- Azabicyclo [2.2.2] octane-1-yl {group represented by the chemical formula (9)} and 1,4-diazabicyclo [2.2.2] octane-1-yl {represented by the chemical formula (10) Group, tributylammonio, trioctylammonio, octyldimethylammonio, diisopropylethylammonio and the like.

  Of these ammonio groups, 1,8-diazabicyclo [5.4.0] -7-undecen-8-yl (group represented by the chemical formula (5)), 1,5-diazabicyclo [4.3.0]. ] -5-Nonen-5-yl (group represented by chemical formula (6)), 1-methylimidazol-3-yl, 1,2-dimethylimidazol-3-yl, 1-methyl-2-ethylimidazole 3-yl, 1-azabicyclo [2.2.2] octane-1-yl (group represented by the chemical formula (8)), 3-hydroxy-1-azabicyclo [2.2.2] octane-1-yl (Group represented by chemical formula (9)), 1,4-diazabicyclo [2.2.2] octan-1-yl (group represented by chemical formula (10)) trioctylammonio and diisopropylethylammonio Preferably, more preferably 1,8-diazabicyclo [5.4.0] -7-undecene-8-yl (group represented by chemical formula (5)) and 1,5-diazabicyclo [5.4.0] -5-nonene-5 -Yl (group represented by chemical formula (6)) 1-methylimidazol-3-yl, 1,2-dimethylimidazol-3-yl.

In general formula (1),
Ar ¹ is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituent. And may be a phenyl group or a naphthyl group.
Preferred as Ar ² are a phenyl group and a naphthyl group which may have a substituent, and particularly preferred is a phenyl group which may have a substituent.
Preferable as R ^{1 to} R ² are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms, and particularly preferable ones may have a hydrogen atom, a methyl group, and a substituent. Good phenyl group.
R ³ is preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 4 to 6 carbon atoms.
Preferred as Y ⁺ is one represented by the general formula (2), and particularly preferred is one in which R ⁴ and R ⁵ in the formula (2) are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. is there.
n is preferably n = 1 to 3, and more preferably n = 1 or 3.

Preferred examples of the cation structure of the thermal base generator represented by the general formula (1) include those represented by the following chemical formulas (CA-1) to (CA-19).

Preferred examples of the anion structure of the thermal base generator represented by the general formula (1) include those represented by the following chemical formulas (A-1) to (A-11).

The thermal base generator of the present invention can be produced by a known method. An example is shown in the following chemical reaction formula. Corresponding to a compound (E) substituted with a leaving group (Z) having substituents (Ar ¹ , R ¹ and R ² ) corresponding to the desired thermal base generator, and a quaternary ammonio group (Y ⁺ ) The cation intermediate having Z ⁻ as a counter anion is obtained by reacting with the amine (Y) to be reacted directly or in a solvent. This cation intermediate and a borate metal salt having a substituent (Ar ² , R ³ ) corresponding to the target thermal base generator produced separately by a known method are subjected to anion exchange in an organic solvent or water to achieve the target heat. A base generator can be obtained.

[Wherein, Ar ¹ , Ar ² , R ¹ , R ² , R ³ , Y ⁺ are the same as those in the general formula (1), Z is a leaving group, and Z ⁻ is a pair generated by elimination] An anion, Y is an amine corresponding to quaternary ammonium, and M ⁺ is a metal cation. ]

  As the amine (Y), an amine represented by the chemical formula (11) {1,8-diazabicyclo [5,4,0] -undecene-7 (DBU; “DBU” is a registered trademark of San Apro Co., Ltd.)} , Amine represented by chemical formula (12) {1,5-diazabicyclo [4,3,0] -nonene-5 (DBN)}, amine represented by chemical formula (13) {each symbol is the same as chemical formula (3) is there. For example, 1-azabicyclo [2.2.2] octane, 3-hydroxy-1-azabicyclo [2.2.2] octane and 1,4-diazabicyclo [2.2.2] octane and the like cyclic amines and trialkylamines (Tributylamine, trioctylamine, octyldimethylamine, diisopropylethylamine, etc.), trialkenylamine (triallylamine, etc.) and triarylamine (triphenylamine, tri-p-tolylamine, diphenyl p-tolylamine, etc., chain amines, etc.) and Amines represented by chemical formula (14) {each symbol is the same as in chemical formula (7). For example, 1-methylimidazol-3-yl, 1,2-dimethylimidazol-3-yl, 1-methyl-2-ethyl Imidazol-3-yl) and the like}.

  Examples of the leaving group (Z) include a halogen atom (such as a chlorine atom and a bromine atom), a sulfonyloxy group (such as trifluoromethylsulfonyloxy, 4-methylphenylsulfonyloxy and methylsulfonyloxy), and an acyloxy (acetoxy and trifluoromethyl). Carbonyloxy and the like). Of these, a halogen atom and a sulfonyloxy group are preferred from the viewpoint of ease of production.

  As the solvent, water or an organic solvent can be used. Organic solvents include hydrocarbons (hexane, heptane, toluene, xylene, etc.), cyclic ethers (tetrahydrofuran, dioxane, etc.), chlorinated solvents (chloroform, dichloromethane, etc.), alcohols (methanol, ethanol, isopropyl alcohol, etc.), ketones ( Acetone, methyl ethyl ketone and methyl isobutyl ketone), nitriles (acetonitrile, etc.) and polar organic solvents (dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, etc.). These solvents may be used alone or in combination of two or more.

  As reaction temperature (degreeC) of the compound (E) used as the raw material of a cation intermediate, and amine (Y), -10-100 are preferable, More preferably, it is 0-80. It is preferable to dissolve the compound (E) in an organic solvent and add an amine thereto. The amine may be added dropwise or may be added dropwise after dilution with an organic solvent.

The compound (E) can be produced by a known method. Compound (E) can be obtained, for example, by halogenating (preferably brominating) carbon substituted with (Ar ¹ ). Halogenation (bromination is preferred) can be carried out by various methods, but a method using halogen (preferably bromine) or a method using N-bromosuccinimide in combination with a radical generator is preferred and preferred (fourth) Edition Experimental Chemistry Lecture 19 Japanese Chemical Society, p422).

  A borate metal salt which is an anionic component is obtained by using a known method (for example, Journal of Polymer Science: Part A: Polymer Chemistry, vol 34, 2817 (1996) or the like) and alkyl or aryl organometallic compound and alkyl or aryl. It can be obtained by reacting a boron compound or a boron halide compound in an organic solvent. As the organometallic compound to be used, lithium compounds such as alkyl lithium and aryl lithium, and magnesium compounds (Grignard reagent) such as alkyl magnesium halide and aryl magnesium halide are preferably used.

The reaction between the boron compound and the organometallic compound is −80 ° C. to 100 ° C., preferably −50 ° C. to 50 ° C., and most preferably −30 ° C. to 30 ° C. As the organic solvent to be used, hydrocarbons (hexane, heptane, toluene, xylene, etc.), cyclic ethers (tetrahydrofuran, dioxane, etc.), and chlorinated solvents (chloroform, dichloromethane, etc.) are preferably used.

  The borate metal salt obtained above is preferably an alkali metal salt from the viewpoint of stability and solubility. In the case of reacting with a Grignard reagent, it is preferable to perform metal exchange during the reaction or after the reaction by adding sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide or the like. Furthermore, it is preferable to obtain it as an aqueous solution from the convenience of the subsequent anion exchange reaction. In order to obtain an aqueous solution, the organic solvent used in the reaction is distilled off to obtain a solid once, which may be dissolved in water, or may be dissolved in the aqueous layer by a liquid separation method.

Anion exchange is performed by mixing the aqueous solution of the borate metal salt obtained above with an organic solvent or aqueous solution containing an intermediate.
The anion exchange may be carried out after the intermediate is obtained, or the intermediate may be isolated and purified and then dissolved in an organic solvent again to carry out the anion exchange.

  The thermal base generator obtained as described above may be purified after being separated from the organic solvent. Separation from the organic solvent can be performed directly (or after concentration) with respect to the organic solvent solution containing the thermal base generator by adding a poor solvent to precipitate the thermal base generator. Examples of the poor solvent used here include chain ethers (such as diethyl ether and dipropyl ether), esters (such as ethyl acetate and butyl acetate), aliphatic hydrocarbons (such as hexane and cyclohexane), and aromatic hydrocarbons (toluene and Xylene and the like).

  When the thermal base generator is an oily substance, the precipitated oily substance is separated from the organic solvent solution, and the organic solvent contained in the oily substance is distilled off to obtain the thermal base generator of the present invention. On the other hand, when the thermal base generator is a solid, the precipitated solid is separated from the organic solvent solution, and the organic solvent contained in the solid is distilled off to obtain the thermal base generator of the present invention.

  Purification can be performed by recrystallization (a method using a difference in solubility due to cooling, a method of adding a poor solvent to precipitate, and a combination thereof). When the hot base generator is an oily substance (when it is not crystallized), it can be purified by a method of washing the oily substance with water or a poor solvent.

The thermal base generator of the present invention can be applied to a latent base catalyst (a catalyst that does not have a catalytic action before heating, but develops a basic catalytic action by heating), etc., and is a base-reactive compound and a thermosetting resin composition. It can be used as a curing catalyst for products. For example, a base resin whose curing is accelerated by a base, the thermal base generator of the present invention, and, if necessary, a thermosetting resin composition containing a solvent and / or an additive can be easily configured. Since such a thermosetting resin composition contains the thermal base generator of the present invention, it has excellent storage stability and excellent curability.

The resin composition whose curing is accelerated by a base generated by heating is not limited as long as it is a resin that is cured by a base. For example, it is composed of a curable urethane resin {(poly) isocyanate and a curing agent (polyol, thiol, etc.). Resins, etc.}, curable epoxy resins {resins composed of (poly) epoxides and curing agents (acid anhydrides, carboxylic acids, (poly) epoxides, thiols, etc.) and resins composed of epichlorohydrin and carboxylic acids}, curability Acrylic resin {acrylic monomer and / or acrylic oligomer and curing agent (thiol, malonic ester, acetylacetonate, etc.)}, curable polyepisulfide {(poly) episulfide and curing agent (acid anhydride, carboxylic acid, (poly) Resins comprising epoxide, (poly) episulfide, thiol, etc.)} resin polysiloxa (Cured to a crosslinked polysiloxane.), Polyimide resin or the like.

In addition, the thermal base generator of the present invention includes a radical photopolymerization composition (a composition comprising a photopolymerization initiator and a photosensitive resin that cures by a radical reaction), light, together with a resin composition that cures with a base. By using in combination with a cationic polymerization composition (a composition comprising a photocationic polymerization initiator and a photosensitive resin that cures by a cationic polymerization reaction), or a photosensitive resin composition that produces a difference in solubility in a developer before and after light irradiation. The patterning member can be used. That is, it can be applied to a resin curing catalyst or the like by heating after a patterning step (light irradiation step, development step). Furthermore, the thermal base generator of the present invention has high solubility in ethyl lactate and PGMEA, and can be suitably used for patterning members in which those solvents are essential. In addition, the said photosensitive resin composition can use a well-known thing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not intending to be limited to this. Unless otherwise specified, “%” means “% by weight”.

Production Example 1 Synthesis of lithium n-hexyltriphenylborate

100 mL of 0.25 molL- ¹ triphenylborane tetrahydrofuran solution (made by Aldrich) was added to the nitrogen-substituted 4-necked reaction vessel, and it cooled to -20 degreeC. Thereto, 11 mL of 2.3 mol L- ¹ hexyl lithium hexane solution (manufactured by Aldrich) was gradually added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, and further 100 mL of hexane was added, followed by filtration. The organic layer was concentrated to give a white solid. The solution was immediately dissolved in 33.4 g of water to obtain a 20% aqueous solution of lithium n-hexyltriphenylborate.

Production Examples 2 to 4
The same procedure as in Production Example 1 was carried out except that the reaction conditions and raw materials were changed, and a lithium sec-butyltriphenylborate 20% aqueous solution, a lithium n-butyltriphenylborate 20% aqueous solution, and a lithium ethyltriphenylborate 20% aqueous solution were obtained. It was.

Production Example 5 Synthesis of lithium di-n-butyldiphenylborate: 2.7 g of chloroborane methyl sulfide complex (manufactured by Aldrich) was added to a four-necked reaction vessel, and 100 mL of tetrahydrofuran was added. Thereto, 5 g of 1-hexene (manufactured by Tokyo Chemical Industry) was added little by little. After reacting at room temperature for 1 hour, it was cooled to −20 ° C., and 50 mL of a 2.0 mol L- ¹ butyl lithium cyclohexane solution (manufactured by Aldrich) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, and further 100 mL of hexane was added, followed by filtration. The organic layer was concentrated to give a white solid. The solution was immediately dissolved in 28.6 g of water to obtain a 20% aqueous solution of lithium di-n-butyldiphenylborate.

Production Examples 6 to 10
In Production Example 1, except that the reaction conditions and raw materials were changed, the same method was used, except that a lithium dicyclohexyldiliphenylborate 20% aqueous solution, a lithium di-n-butyldimesitylborate 20% aqueous solution, a lithium tri-n-butylphenylborate 20% aqueous solution, A lithium n-butyltri-p-anisylborate 20% aqueous solution and a lithium n-butyltri-p-fluorophenylborate 20% aqueous solution were obtained.

Production Example 11 Synthesis of Lithium Tetra-n-butylborate: To a four-necked reaction vessel, 3.5 g of boron trifluoride ether complex was added, and 100 mL of tetrahydrofuran was further added and stirred. It cooled to -20 degreeC and 50 mL of 2.0 molL- ¹ butyl lithium cyclohexane solutions (made by Aldrich) were dripped there. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, and 100 mL of hexane was added for filtration. The white solid obtained by concentrating the organic layer was quickly dissolved in 24.6 g of water to obtain a 20% aqueous solution of lithium tetra n-butyl borate.

Example 1
Synthesis of Compound a101 (1) Synthesis of Intermediate (a-1) 17.1 g of benzyl bromide was dissolved in 100 g of dichloromethane, and 1,8-diazabicyclo [5.4.0] -7-undecene (DBU, Sunapro) was dissolved therein. Product) 15.2 g was added dropwise and stirred at room temperature for 2 hours. The solvent was distilled off to obtain a white solid. This white solid was recrystallized from tetrahydrofuran / dichloromethane to obtain 30 g of a white solid. This white solid was confirmed to be an intermediate (a-1) by 1H-NMR.

(2) Synthesis of Compound (a101) To the aqueous solution of lithium n-hexyltriphenylborate (50 g) synthesized in Production Example 1, 8.8 g of intermediate (a-1) previously dissolved in 100 g of chloroform was added little by little. And stirred at room temperature for 1 hour. A white solid was obtained by washing with water three times and concentrating the organic layer. This white solid was recrystallized from acetonitrile / ether to obtain 13.5 g of a white solid. This white solid was confirmed to be the compound (a101) by 1H-NMR. The structure of the compound (a101) is shown in Table 1.

Examples 2-11
In Example 1, compounds (a102) to (a111) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (a102) to (a111) are shown in Table 1.

Example 12
Synthesis of Compound a201 (1) Synthesis of Intermediate (a-2) Example 1- (1) In the synthesis of intermediate (a-1), 1,8-diazabicyclo [5.4.0] -7-undecene ( DBU, manufactured by San Apro) was the same as Example 1- (1) except that 15.2 g was changed to 12.4 g of 1,5-diazabicyclo [4.3.0] -5-nonene (San Apro). 25 g of a white solid was obtained. This white solid was confirmed to be intermediate (a-2) by 1H-NMR.

(2) Synthesis of Compound a201 The same as Example 1- (2) except that 8.8 g of intermediate (a-1) was changed to 7.9 g of intermediate (a-2) in Example 1- (2). Operation was performed to obtain 12.4 g of a white solid. This white solid was confirmed to be the compound (a201) by 1H-NMR. The structure of the compound (a201) is shown in Table 1.

Examples 13-22
In Example 12, compounds (a202) to (a211) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (a202) to (a211) are shown in Table 1.

Example 23
Synthesis of Compound a301 (1) Synthesis of Intermediate (a-3) Example 1- (1) In the synthesis of intermediate (a-1), 1,8-diazabicyclo [5.4.0] -7-undecene ( The same operation as in Example 1- (1) was carried out except that 15.2 g of DBU (manufactured by San Apro) was changed to 8.2 g of 1-methylimidazole (manufactured by Tokyo Chemical Industry) to obtain 22 g of a white solid. This white solid was confirmed to be an intermediate (a-3) by 1H-NMR.

(2) Synthesis of Compound a301 Same as Example 1- (2), except that 8.8 g of intermediate (a-1) was changed to 6.8 g of intermediate (a-3) in Example 1- (2). Operation was performed to obtain 11.2 g of a slightly yellow solid. This slightly yellow solid was confirmed to be compound (a301) by 1H-NMR. The structure of the compound (a301) is shown in Table 1.

Examples 24-33
In Example 23, compounds (a302) to (a311) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (a302) to (a311) are shown in Table 1.

Example 34
Synthesis of Compound a401 (1) Synthesis of Intermediate (a-4) Example 1- (1) In the synthesis of intermediate (a-1), 1,8-diazabicyclo [5.4.0] -7-undecene ( The same operation as in Example 1- (1) was carried out except that 15.2 g of DBU (manufactured by San Apro) was changed to 9.6 g of 1,2-dimethylimidazole (manufactured by Tokyo Chemical Industry) to obtain 24 g of a white solid. This white solid was confirmed to be an intermediate (a-4) by 1H-NMR.

(2) Synthesis of Compound a401 The same as Example 1- (2) except that 8.8 g of intermediate (a-1) was changed to 7.2 g of intermediate (a-4) in Example 1- (2). Operation was performed to obtain 10.8 g of a slightly yellow solid. This slightly yellow solid was confirmed to be the compound (a401) by 1H-NMR. The structure of the compound (a401) is shown in Table 1.

Examples 35-44
In Example 34, compounds (a402) to (a411) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (a402) to (a411) are shown in Table 1.

Example 45
Synthesis of Compound a501 (1) Synthesis of Intermediate (a-5) Example 1- (1) In the synthesis of intermediate (a-1), 1,8-diazabicyclo [5.4.0] -7-undecene ( The same operation as in Example 1- (1) was performed except that 15.2 g of DBU (manufactured by San Apro) was changed to 11.3 g of quinuclidine (manufactured by Aldrich) to obtain 25 g of a white solid. This white solid was confirmed to be an intermediate (a-5) by 1H-NMR.

(2) Synthesis of Compound a501 The same as Example 1- (2) except that 8.8 g of intermediate (a-1) was changed to 7.7 g of intermediate (a-5) in Example 1- (2). Operation was performed to obtain 11 g of a white solid. This white solid was confirmed to be the compound (a501) by 1H-NMR. The structure of the compound (a501) is shown in Table 2.

Examples 46-55
In Example 45, compounds (a502) to (a511) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (a502) to (a511) are shown in Table 2.

Example 56
Synthesis of Compound a601 (1) Synthesis of Intermediate (a-6) Example 1- (1) In the synthesis of intermediate (a-1), 1,8-diazabicyclo [5.4.0] -7-undecene ( The same operation as in Example 1- (1) was carried out except that 15.2 g of DBU (manufactured by San Apro) was changed to 12.9 g of diisopropylethylamine (manufactured by Tokyo Chemical Industry) to obtain 29 g of a white solid. It was confirmed by 1H-NMR that this white solid was an intermediate (a-6).

(2) Synthesis of Compound a601 The same as Example 1- (2) except that 8.8 g of intermediate (a-1) was changed to 8.1 g of intermediate (a-6) in Example 1- (2). Operation was performed to obtain 12.2 g of a white solid. This white solid was confirmed to be the compound (a601) by 1H-NMR. The structure of the compound (a601) is shown in Table 2.

Examples 57-66
In Example 56, compounds (a602) to (a611) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (a602) to (a611) are shown in Table 2.

Example 67
Synthesis of Compound b101 (1) Synthesis of Intermediate (b-1) Example 1- (1) In the synthesis of intermediate (a-1), 17.1 g of benzyl bromide was changed to 18.5 g of (1-bromoethyl) benzene. Except for the above, the same operation as in Example 1- (1) was performed to obtain 30 g of a yellowish white solid. It was confirmed by 1H-NMR that this yellowish white solid was an intermediate (b-1).

(2) Synthesis of compound b101 The same as Example 1- (2) except that 8.8 g of intermediate (a-1) was changed to 9.1 g of intermediate (b-1) in Example 1- (2). Operation was performed to obtain 12.5 g of a white solid. This white solid was confirmed to be the compound (b101) by 1H-NMR. The structure of the compound (b101) is shown in Table 2.

Examples 68-72
In Example 67, compounds (b201) to (b601) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (b201) to (b601) are shown in Table 2.

Examples 73-78
In Examples 67 to 72, compounds (b107) to (b607) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (b107) to (b607) are shown in Table 2.

Examples 79-84
In Examples 67 to 72, compounds (b108) to (b608) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (b108) to (b608) are shown in Table 2.

Examples 85-90
In Examples 67 to 72, compounds (b111) to (b611) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (b111) to (b611) are shown in Table 2.

Example 91
Synthesis of Compound c101 (1) Synthesis of Intermediate (c-1) Example 1- (1) In the synthesis of intermediate (a-1), 17.1 g of benzyl bromide was replaced with 22 g of 2-nitrobenzyl bromide (manufactured by Aldrich). Except that, the same operation as in Example 1- (1) was performed to obtain 27 g of a yellow solid. This yellow solid was confirmed to be an intermediate (c-1) by 1H-NMR.

(4) Synthesis of Compound c101 The same as Example 1- (2) except that 8.8 g of intermediate (a-1) was changed to 9.8 g of intermediate (c-1) in Example 1- (2). Operation was performed to obtain 13 g of a yellow solid. This yellow solid was confirmed to be the compound (c101) by 1H-NMR. The structure of the compound (c101) is shown in Table 3.

Examples 92-96
In Example 91, compounds (c201) to (c601) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (c201) to (c601) are shown in Table 3.

Examples 97-103
In Examples 91 to 96, compounds (c107) to (c607) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of compounds (c107) to (c607) are shown in Table 3.

Examples 103-108
In Examples 91 to 96, compounds (c108) to (c608) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of compounds (c108) to (c608) are shown in Table 3.

Examples 109-114
In Examples 91 to 96, compounds (c111) to (c611) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (c111) to (c611) are shown in Table 3.

Example 115
Synthesis of Compound d101 (1) Synthesis of Intermediate (d-1) Example 1- (1) In the synthesis of intermediate (a-1), except that 17.1 g of benzyl bromide was changed to 20 g of p-methoxybenzyl bromide The same operation as in Example 1- (1) was performed to obtain 33 g of a yellowish white solid. It was confirmed by 1H-NMR that the yellowish white solid was an intermediate (d-1).

(2) Synthesis of compound d101 The same as Example 1- (2) except that 8.8 g of intermediate (a-1) was changed to 9.5 g of intermediate (d-1) in Example 1- (2). Operation was performed to obtain 13.8 g of a yellowish white solid. It was confirmed by 1H-NMR that the yellowish white solid was the compound (d101). The structure of the compound (d101) is shown in Table 3.

Examples 116-120
In Example 115, compounds (d201) to (d601) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (d201) to (d601) are shown in Table 3.

Examples 121-126
In Examples 115 to 120, compounds (d107) to (d607) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (d107) to (d607) are shown in Table 3.

Examples 127-132
In Examples 115 to 120, compounds (d108) to (d608) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (d108) to (d608) are shown in Table 3.

Examples 133-138
In Examples 115 to 120, compounds (d111) to (d611) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (d111) to (d611) are shown in Table 3.

Example 139
Synthesis of Compound e101 (1) Synthesis of Intermediate (e-1) Example 1- (1) In the synthesis of intermediate (a-1), except that 17.1 g of benzyl bromide was changed to 22 g of 2- (bromomethyl) naphthalene The same operation as in Example 1- (1) was performed to obtain 34 g of a white solid. This white solid was confirmed to be intermediate (e-1) by 1H-NMR.

(2) Synthesis of Compound e101 The same operation as in Example 1- (2) was carried out except that 8.8 g of intermediate (a-1) was changed to 10 g of intermediate (e-1) in Example 1- (2). This gave 15 g of a white solid. This white solid was confirmed to be the compound (e101) by 1H-NMR. The structure of the compound (e101) is shown in Table 4.

Examples 140-144
In Example 139, compounds (e201) to (e601) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (e201) to (e601) are shown in Table 4.

Examples 145-150
In Examples 139 to 144, compounds (e107) to (e607) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (e107) to (e607) are shown in Table 4.

Examples 151-156
In Examples 139 to 144, compounds (e108) to (e608) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of compounds (e108) to (e608) are shown in Table 4.

Examples 157-162
In Examples 139 to 144, compounds (e111) to (e611) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (e111) to (e611) are shown in Table 4.

Example 163
Synthesis of Compound f101 (1) Synthesis of Intermediate (f-1) Example 1- (1) In the synthesis of intermediate (a-1), 17.1 g of benzyl bromide was changed to 25 g of diphenylbromomethane (manufactured by Tokyo Chemical Industry). Except for the above, the same operation as in Example 1- (1) was performed to obtain 28 g of a light brown solid. It was confirmed by 1H-NMR that this light brown solid was an intermediate (f-1).

(2) Synthesis of Compound f101 The same operation as in Example 1- (2) was carried out except that 8.8 g of the intermediate (a-1) was changed to 11 g of the intermediate (f-1) in Example 1- (2). This gave 13.1 g of a yellow solid. This yellow solid was confirmed to be the compound (f101) by 1H-NMR. The structure of the compound (f101) is shown in Table 4.

Examples 164-168
In Example 163, compounds (f201) to (f601) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (f201) to (f601) are shown in Table 4.

Examples 169-174
In Examples 163 to 168, compounds (f107) to (f607) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (f107) to (f607) are shown in Table 4.

Examples 175-180
In Examples 163 to 168, compounds (f108) to (f608) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (f108) to (f608) are shown in Table 4.

Examples 181 to 186
In Examples 163 to 168, compounds (f111) to (f611) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (f111) to (f611) are shown in Table 4.

Example 187
Synthesis of Compound g101 (1) Synthesis of Intermediate (g-1) Example 1- (1) Example 1- (1) except that 17.1 g of benzyl bromide was changed to 15 g of iodomethane in the synthesis of intermediate (a-1). The same operation as in 1) was performed to obtain 28 g of a light brown solid. It was confirmed by 1H-NMR that this light brown solid was an intermediate (g-1).

(2) Synthesis of Compound g101 The same procedure as in Example 1- (2) was carried out except that 8.8 g of intermediate (a-1) was changed to 11 g of intermediate (g-1) in Example 1- (2). This gave 13.1 g of a light brown solid. This pale brown solid was confirmed to be the compound (g101) by 1H-NMR. The structure of the compound (g101) is shown in Table 5.

Examples 188-192
In Example 187, compounds (g201) to (g601) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of compounds (g201) to (g601) are shown in Table 5.

Examples 193-198
In Examples 187 to 192, compounds (g107) to (g607) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of compounds (g107) to (g607) are shown in Table 5.

Examples 199-204
In Examples 187 to 192, compounds (g108) to (g608) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of compounds (g108) to (g608) are shown in Table 5.

Examples 204-210
In Examples 187 to 192, compounds (g111) to (g611) were obtained in the same manner except that the reaction conditions and raw materials were changed. The structures of the compounds (g111) to (g611) are shown in Table 5.

The structures of amine A in Tables 1 to 5 are as follows.

Comparative Example 1
A base generator having the following structure described in Patent Document 4 (Japanese Patent Laid-Open No. 62-246925) was prepared.

<Evaluation of solubility in organic solvents>
Thermal base generators of Examples 1-210 (a101 to a111, a201 to a211, a301 to a311, a401 to a411, a501 to a511, a601 to a611, b101 to b601, b107 to b607, b108 to b608, b111 to b611 , C101 to c601, c107 to c607, c108 to c608, c111 to c611, d101 to d601, d107 to d607, d108 to d608, d111 to d611, e101 to e601, e107 to e607, e108 to e608, e111 to e611, f101 To f601, f107 to f607, f108 to f608, f111 to f611, g101 to g601, g107 to g607, g108 to g608, g111 to g611) and the thermal base generator (H-1) of Comparative Example 1 Each organic solvent (methyl lactate, PGMEA) appearance when adding 1-5 wt% on was visually observed and evaluated according to the following criteria. The results are shown in Tables 6-10.
(Criteria)
A: Transparent, uniform (dissolved 5% or more)
○: Transparent, uniform (1-5% dissolution)
X: cloudiness or phase separation

  From the results of Tables 6 to 10, the thermal base generator of the present invention has high solubility in ethyl lactate and PGMEA. When a thermal base generator is used for the patterning member, it must be highly soluble in ethyl lactate, PGMEA, etc., and the thermal base generator of the present invention is excellent. On the other hand, the thermal base generator (H-1) of Comparative Example 1 has low solubility and is difficult to use for the patterning member.

<Thermal decomposition evaluation>
The thermal decomposition temperatures of the thermal base generators of Examples 1-210 and the base generator of Comparative Example 1 were measured. For the measurement, a differential thermal / thermogravimetric simultaneous measurement apparatus (TG / DTA6200: manufactured by SII Nano Technology) was used. The results are shown in Tables 6-10.

[Check resin curability]
In order to confirm the effects of the base generators of Examples and Comparative Examples, the following thermosetting resin compositions were prepared, and the curability was confirmed by the presence or absence of surface tack. The results are shown in Tables 6-10.
(Resin composition)
Bisphenol A type epoxy resin 100g
(JER-828; made by Japan Epoxy Resin)
Acid anhydride (HN5500E; manufactured by Hitachi Chemical) 90g
Solvent (PGMEA) 200g
Thermal base generator 5g

(Test method)
The above composition was uniformly mixed, uniformly applied to a glass substrate (100 mm × 100 mm) with a bar coater, dried for 30 minutes with a hot plate heated to 150 ° C., and the presence or absence of surface tack was confirmed.
In the base generator of the example, a transparent cured product was obtained, whereas in the base generator of the comparative example, the surface of the cured product was not tacky because of poor solubility, but it was opaque and had a rough surface appearance. A cured product was obtained.
From the results of Tables 6 to 10, the base generators of the examples have high solvent solubility, and can be suitably used in thermosetting compositions containing a solvent that is particularly essential for patterning materials.

The thermal base generator of the present invention is a patterning step utilizing a difference in solubility in a developing solution of a material (for example, a coating agent or a paint) that is cured using a base generated by heating, or an exposed portion or an unexposed portion. It is suitably used for the manufacture of a product or member (for example, an electronic component, an optical product, an optical component forming material, a layer forming material, or an adhesive) formed through a heating step.

Claims (10)

A thermal base generator represented by the general formula (1).

[In the formula (1), Ar ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, a nitro group, a hydroxyl group, a cyano group,- An alkoxy group represented by OR ¹¹ , an amino group represented by —NR ¹² R ¹³ , an acyloxy group represented by R ¹⁵ COO—, an alkylthio group or an arylthio group represented by —SR ¹⁶ , a halogen atom or a carbon number 6 to 14 aryl groups, wherein some of the hydrogen atoms in the aryl group are alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, carbon numbers 6-14 aryl group, nitro group, hydroxyl group, cyano group, alkoxy group represented by —OR ¹¹ , amino group represented by —NR ¹² R ¹³ , acyl group represented by R ¹⁴ CO—, R ¹⁵ CO An acyloxy group represented by O—, an alkylthio group or arylthio group represented by —SR ¹⁶ , or a halogen atom may be substituted; Ar ² is an aryl group having 6 to 14 carbon atoms, Some of the hydrogen atoms therein are alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, nitro groups, hydroxyl groups, Cyano group, alkoxy group represented by —OR ¹¹ , amino group represented by —NR ¹² R ¹³ , acyl group represented by R ¹⁴ CO—, acyloxy group represented by R ¹⁵ COO—, —SR ¹⁶ in represented by an alkylthio group or an arylthio group, or a halogen atom may be substituted by; R ¹ to R ² is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, aryl having 6 to 14 carbon atoms A ^{group, Ar 1, R 1, R} 2 are bonded to each other may form a ring structure; ^{R 3} is a number from 1 to 18 alkyl group carbon; n is an integer of from 1 to 4 R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are alkyl groups having 1 to 8 carbon atoms or aryl groups having 6 to 14 carbon atoms; R ¹² and R ¹³ are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms or carbon; Y ⁺ is a quaternary ammonio group represented by either of the following general formulas (2) or (3); in formula (2), R ^{4 to} R ⁵ are An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, which may be bonded to each other to form a ring structure; Q is a methylene group (-CH ₂ -) m, or a group represented by the following general formula (4); m is an integer of 2 or 3; formula ^3), R 6 to R ⁸ is an alkyl group, an alkenyl group or an aryl group having 6 to 14 carbon atoms having 2 to 18 carbon atoms having 1 to 18 carbon atoms, have a ring structure with each other In formula (4), R ^{9 to} R ¹⁰ are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and may be bonded to each other to form a ring structure. Good. ]

^2. The thermal base generator according to claim ¹ , wherein in the general formula (1), R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The thermal base generator according to claim 1 or 2, wherein in the general formula (1), Ar ¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In general formula (1), Ar < ² > is the phenyl group or naphthyl group which may have a substituent. The thermal base generator in any one of Claims 1-3. In general formula (1), R < ³ > is a C1-C8 alkyl group, The thermal base generator in any one of Claims 1-4. In general formula (1), n is 1 or 3, The thermal base generator in any one of Claims 1-5. The thermal base generator according to any one of claims 1 to 6, wherein Y ⁺ is represented by the general formula (2). The thermal base generator according to claim 7, wherein Y ⁺ is selected from the group of the following formulas (5) to (7).

[In the formula (7), R ¹⁷ is an alkyl group having 1 to ¹⁸ carbon atoms, R ¹⁸ is an alkyl group having 1 to ¹⁸ carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms. , May be bonded to each other to form a ring structure. ] A thermosetting composition comprising the thermal base generator according to claim 1 and a base-reactive compound. A cured product obtained by curing the thermosetting composition according to claim 9.