JP2018145156A - Heat latent polymerization initiator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a boron compound that can be used as e.g. a heat latent polymerization initiator.SOLUTION: A boron compound is used as a compound represented by the following formula (1) (where Ar, Arand Arare the same or different, to represent an optionally substituted aryl group, M is an n-valent metal, X is an anion, k and m represent a number greater than 0, where n is a number of 2 or greater). In the formula (1), at least one of Ar, Arand Armay be an aryl group having at least one halogen atom, and metal M may be magnesium.SELECTED DRAWING: None

Description

  The present invention relates to a novel boron compound and a composition containing this compound.

  Lewis acids are used as catalysts. For example, a Lewis acid such as tris (pentafluorophenyl) borane is used as a catalyst for polymerizing and curing a polymerizable compound (for example, a monomer such as an epoxy monomer, a vinyl monomer, an acrylic monomer, or a prepolymer that is an oligomer thereof). Used.

  However, the reaction of Lewis acids such as tris (pentafluorophenyl) borane starts from the point of contact with the polymerizable compound due to its excellent catalytic ability. Therefore, it is extremely difficult to mold and cure a mixture containing these catalysts and monomers and distribute them as a product.

  Therefore, a thermal latent polymerization initiator has been developed that does not exhibit catalytic activity at refrigerated storage temperature (-20 to 0 ° C.) or normal temperature, and exhibits catalytic ability by heating.

  For example, in Patent Document 1 (Patent No. 5579859), a composition in which an amine compound having a piperidine structure and tris (pentafluorophenyl) borane are combined does not start polymerization at room temperature, and polymerization is performed under heating. It is described that it can be used as a starting thermal latent polymerization initiator.

Japanese Patent No. 5579859

  An object of the present invention is to provide a novel boron compound, a thermal polymerization initiator (thermal latent polymerization initiator) composed of this compound, and a composition containing these compounds or agents.

  As described above, a technique using tris (pentafluorophenyl) borane as a thermal latent polymerization initiator that initiates polymerization under heating is known, but according to the study by the present inventors, such a technique is known. In technology, high temperature is required for heating, or depending on the type of polymerizable compound to be combined (for example, a specific epoxy resin such as bisphenol A type epoxy resin), sufficient polymerizability (polymerization initiating ability) may not be ensured. It was.

In view of such circumstances, as a result of intensive studies, the present inventors have determined that a specific anion (hydroxyborate anion) corresponding to a Lewis acid such as tris (pentafluorophenyl) borane and a specific cation (that is, , A metal cation) can function as a new thermal latent polymerization initiator, and such a compound can be polymerized at a low temperature or a conventional thermal latent polymerization can be initiated. The present inventors have found that various polymerization compounds for which sufficient polymerization was difficult to obtain with an agent have excellent polymerization initiation ability.
In addition to the above, the present inventor has obtained various new findings as described below, and has made further studies and completed the present invention.

  That is, the compound of the present invention is represented by the following formula (1).

(Wherein Ar ¹ , Ar ² and Ar ³ are the same or different aryl groups which may have a substituent, M is an n-valent metal, X is an anion, k and m are numbers greater than 0. Where n is a number of 2 or more.)

  In the present invention, a novel boron compound can be provided. Since such a boron compound can exhibit catalytic activity by heat, it can be used as a thermal polymerization initiator (thermal latent polymerization initiator).

[Compound]
The compound of the present invention is represented by the following formula (1).

(Wherein Ar ¹ , Ar ² and Ar ³ are the same or different aryl groups which may have a substituent, M is an n-valent metal, X is an anion, k and m are numbers greater than 0. Is shown.)

  The aryl group having a substituent refers to a group in which one or more hydrogen atoms constituting the aryl group having no substituent are substituted with a substituent. The substituent may be further substituted with a substituent.

In the above formula (1), in Ar ¹ , Ar ² and Ar ³ (aryl group which may have a substituent), examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group. A C _6-20 aryl group, preferably a C _6-12 aryl group, more preferably a C _6-10 aryl group.

The aryl group may have a substituent. The substituent is not particularly limited, for example, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, an alkoxy group (e.g., methoxy group, C _1-20, such as ethoxy groups An alkoxy group, preferably a C _1-10 alkoxy group, more preferably a C _1-4 alkoxy group), an aryloxy group (eg, a C _6-10 aryloxy group such as a phenoxy group), an acyl group (eg, an acetyl group, etc.) the _{C 1-10} alkylcarbonyl group; and _{C 6-10} arylcarbonyl group such as benzoyl group), an acyloxy group (e.g., _{C 1-10} alkylcarbonyloxy groups such as acetoxy group; _C, such as phenyl carbonyloxy group _{6- 10} such arylcarbonyloxy group), an alkoxycarbonyl group (e.g., Toki C _1-10 alkoxycarbonyl groups such as aryloxycarbonyl group), an aryloxycarbonyl group (e.g., C _6-10 aryloxycarbonyl groups such as phenoxycarbonyl group), C ₁ such as a mercapto group, an alkylthio group (e.g., methylthio group _-20 alkylthio group, preferably a _{C 1-10} alkylthio group, more preferably a _{C 1-4} alkylthio group), an arylthio group (e.g., _{C 6-10} arylthio group such as phenylthio group), an amino group, a substituted amino group (e.g. , Mono or di C _1-4 alkylamino group such as dimethylamino group), amide group (for example, mono or di C _1-4 alkylaminocarbonyl group such as N, N′-dimethylaminocarbonyl group), cyano group, nitro group, substituted sulfonyl group (eg, C ₁ such as mesyl group ₁₀ alkylsulfonyl group, C _6-10 arylsulfonyl group such as tosyl group), a hydrocarbon group {e.g., an aliphatic hydrocarbon group [e.g., an alkyl group (e.g., methyl group, ethyl group, n- propyl group, an isopropyl group C _1-20 alkyl groups such as n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group, Is a C _2-10 alkyl, more preferably a C _2-6 alkyl group), a cycloalkyl group (for example, a C _3-20 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, preferably a C _4-8 cycloalkyl group), aralkyl group (e.g., benzyl group, _{C 6-10} aryl _{C 1-4} alkyl group such as a phenethyl group), etc.], an aromatic hydrocarbon group [ Eg to an aryl group (e.g., phenyl group, tolyl group, xylyl group, _{C 6-20} aryl group such as a naphthyl group, preferably a _{C 6-12} aryl group, more preferably a _{C 6-10} aryl group), etc.], etc.} And a group (for example, a halogenated hydrocarbon group) in which these substituents are combined.

  These substituents may be used alone or in combination of two or more, and the aryl group may include one or more substituents.

In a preferred embodiment, an aryl group in which at least one of Ar ¹ , Ar ² and Ar ³ (preferably 2 or 3, more preferably 3) has a halogen atom (particularly a fluorine atom) [the groups exemplified above, for example, A fluorophenyl group, a chlorophenyl group, a (fluoroalkyl) phenyl group, a fluoro- (fluoroalkyl) phenyl group, and the like].

Of ^these, Ar 1, Ar ² and at least two Ar ³ Those aryl groups having more preferably an aryl ^group, are three of Ar 1, Ar ² and Ar ³ at least one halogen atom having at least one halogen atom More preferably. In the above embodiment, the Lewis acid strength increases and the properties as a polymerization initiator tend to be improved.

Of the aryl groups having a halogen atom, an aryl group having at least one halogen atom is preferred, an aryl group having at least 3 halogen atoms is more preferred, and an aryl group having at least 5 halogen atoms is more preferred.
^It Ar 1, Ar ² and at least two of Ar ^3, more preferably an aryl group having a halogen ^atom, are three of Ar 1, Ar ² and Ar ^3, is an aryl group having a halogen atom Is more preferable.
In the above embodiment, the Lewis acid tends to act on the polymerization reaction more efficiently, and the properties as a polymerization initiator tend to be improved.

  In the aryl group having a halogen atom, the halogen atom may be directly bonded to the aryl group, the halogen atom-containing group may be substituted with the aryl group, or a combination thereof. May be.

Examples of the halogen atom-containing group include a halogen-containing hydrocarbon group [for example, a haloalkyl group (for example, a haloC _1-20 alkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a perfluorooctyl group). , Preferably a fluoro C _1-10 alkyl group, more preferably a C _1-4 fluoroalkyl group, usually a perfluoroalkyl group), a halocycloalkyl group (for example, a perfluorocyclopropyl group, a perfluorocyclobutyl group, a perfluoro group). Halo C _3-20 cycloalkyl group such as cyclopentyl group, perfluorocyclohexyl group, preferably fluoro C _4-8 cycloalkyl group, usually perfluorocycloalkyl group)], haloalkoxy group (for example, trifluoromethoxy group, Pentafull Roetokishi group, heptafluoropropoxy group, halo _{C 1-20} Arukikokishi group such as perfluoro-octoxy group, preferably fluoro _{C 1-10} alkoxy group, more preferably a _{C 1-4} fluoroalkoxy group, usually perfluoroalkoxy group) And halogenated sulfanyl group (for example, pentafluorosulfanyl group (—SF ₅ ) and the like).

Specific examples of the aryl group having a halogen atom (particularly a fluorine atom) include, for example, a fluoroaryl group [for example, a pentafluorophenyl group, a 2-fluorophenyl group, a 2,3-difluorophenyl group, and a 2,4-difluorophenyl group. Group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,6-trifluorophenyl group, 2, 3,4,6-tetrafluorophenyl group, 2,3,5,6-tetrafluorophenyl group, 2,2 ′, 3,3 ′, 4,4 ′, 5,5 ′, 6-nonafluoro-1, 1'-biphenyl group, preferably pentafluorophenyl group, 2,6-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,5,6-tetrafluoro Phenyl group, 2,2 ′, 3,3 ′, 4,4 ′, 5,5 ′, 6-nonafluoro-1,1′-biphenyl group, etc.], (fluoroalkyl) aryl group [for example, 2-trifluoro Methylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2-pentafluoroethylphenyl group, 3-pentafluoroethylphenyl group, 4-pentafluoroethylphenyl group, 2,4-bis ( Trifluoromethyl) phenyl group, 2,5-bis (trifluoromethyl) phenyl group, 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4, 6-tris (trifluoromethyl) phenyl group, preferably 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) Phenyl, 2,4,6-tris (trifluoromethyl) phenyl group, etc.], fluoro - (fluoroalkyl) aryl [e.g., fluoro - trifluoromethylphenyl group _{(-C 6 H 3 FCF 3)} , fluoro - Bis (trifluoromethyl) phenyl group (—C ₆ H ₂ F (CF ₃ ) ₂ ), fluoro-pentafluoroethylphenyl group (—C ₆ H ₃ FCF ₃ CF ₂ ), fluoro-bis (pentafluoroethyl) phenyl Fluoro- (fluoroC _1-20 alkyl) C _6-10 aryl groups such as the group (—C ₆ H ₂ F (CF ₃ CF ₂ ) ₂ ), preferably fluoro- (fluoroC _1-10 alkyl) C _{6− 10} aryl group, more preferably fluoro - _{(C 1-4} fluoroalkyl) phenyl group, typically fluoro - perfluoro Alkylaryl group etc.], chloroaryl group [for example, pentachlorophenyl group, 2-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3 , 5-dichlorophenyl group, 2,3,6-trichlorophenyl group, 2,4,6-trichlorophenyl group, 2,3,4,6-tetrachlorophenyl group, 2,3,5,6-tetrachlorophenyl group, Preferably a pentachlorophenyl group, 2,6-dichlorophenyl group, 2,4,6-trichlorophenyl group, etc.], (fluorosulfanyl) aryl group [for example, 2-pentafluorosulfanylphenyl group, 3-pentafluorosulfanylphenyl group, 4-pentafluorosulfanylphenyl group, 2,4 Bis (pentafluorosulfanyl) phenyl group, 2,5-bis (pentafluorosulfanyl) phenyl group, 2,6-bis (pentafluorosulfanyl) phenyl group, 3,5-bis (pentafluorosulfanyl) phenyl group, 2, 4,6-tris (pentafluorosulfanyl) phenyl group, preferably 2,6-bis (pentafluorosulfanyl) phenyl group, 3,5-bis (pentafluorosulfanyl) phenyl group, 2,4,6-tris (penta Fluorosulfanyl) phenyl group, etc.].

  Among these, in particular, pentafluorophenyl group, 2,6-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, 2,2 ′, 3, 3 ′, 4,4 ′, 5,5 ′, 6-nonafluoro-1,1′-biphenyl group, pentachlorophenyl group, 2,6-dichlorophenyl group, 2,4,6-trichlorophenyl group, 2,6- Bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group and the like are preferable.

When at least one of Ar ¹ , Ar ² and Ar ³ has an aryl group having a halogen atom (particularly a fluorine atom), the number of aryl groups having a halogen atom is 1 to 3, preferably 2 to 3, particularly 3 It may be.

Ar ¹ , Ar ² and Ar ³ may be the same or different. For example, when all of Ar ¹ , Ar ^2, and Ar ³ are aryl groups having a fluorine atom, they may all be aryl groups having the same fluorine atom (for example, a pentafluorophenyl group), and different fluorine atoms A combination of aryl groups having atoms may also be used.

In the formula (1), M is an n-valent metal. And the number of borate anions (Ar ¹ Ar ² Ar ³ B (OH) ⁻ ) also corresponds to the valence n of this metal.

  In the formula (1), the valence n of the metal M may be monovalent, but is preferably divalent or higher (for example, 2 to 6, preferably 2 to 4, more preferably divalent or 3). Valence, especially divalent).

  Specific examples of the metal M include, for example, a periodic table group 1 metal (eg, lithium, potassium, cesium, etc.), a periodic table group 2 metal (eg, magnesium, calcium, barium, etc.), a transition metal [eg, periodic Table Group 3 metals (or rare earths such as scandium, yttrium, lanthanoids (eg, lanthanum, cerium, etc.)), periodic Group 4 metals (eg, titanium, zirconium, hafnium, etc.), periodic Group 5 metals (eg, , Niobium, tantalum, etc.), periodic table group 6 metal (eg, tungsten), periodic table group 7 metal (eg, manganese), periodic table group 8-10 metal (eg, iron, cobalt, nickel, etc.) ), Periodic Table Group 11 metals (eg, copper, silver, etc.)], Periodic Table Group 12 metals (eg, zinc, etc.), Periodic Table Group 13 gold (E.g., aluminum, indium, etc.), periodic table Group 14 metals (e.g., germanium, tin, etc.) and the like.

  Among these metals, in particular, Group 2 metals (or alkaline earth metals, magnesium, etc.) of the periodic table, Group 13 metals (eg, aluminum, etc.) of the periodic table, etc. are preferable, and magnesium is particularly preferable. Magnesium may be usually divalent (n = 2).

  The compound of the present invention may have any anion X. In other words, the compound of the present invention or the compound represented by the formula (1) is a compound (an electrically neutral compound) having at least an n-valent metal M and an anion represented by the following formula (1A). And a compound having only an anion represented by the following formula (1A) (in formula (1), n = k) may be used. The compound (electrically neutral compound) which has an anion represented by a following formula and arbitrary anions (anion which is not following formula (1A)) may be sufficient.

(In the formula, Ar ¹ , Ar ² and Ar ³ are the same as described above.)

More specifically, in the formula (1), X ^m− is an m-valent arbitrary anion, and the ratio contained in the formula (1) is represented by (n−k) / m. (N−k) / m or (n−k) may be 0, indicating that no X ^m- anion is included.

  Specific combinations (ratio) of n, k, and m are not particularly limited, and examples thereof include combinations shown in the following table.

X ^m− is not particularly limited. For example, halogen ion (eg, fluoride ion, chloride ion, bromide ion, iodide ion, etc.), polyatomic ion (eg, nitrate ion, carbonate ion, acetate ion, sulfate ion) Etc.), complex ions (eg tetrahydroxyaluminate ion, tetrahydroxyzinc (II) acid ion etc.), boron anions {eg quaternary boron anions [eg tetrakis (pentafluorophenyl) borate etc.] etc. A boron anion which does not belong to the category of (1A)}.

A typical compound represented by the formula (1) includes a compound in which at least one of Ar ¹ , Ar ² and Ar ³ is an aryl group having a fluorine atom, and M is magnesium, such as bis [hydroxy- Tris (pentafluorophenyl) borate] magnesium and the like.

Since the boron compound of the present invention has a skeleton corresponding to a Lewis acid such as tris (pentafluorophenyl) borane, it generates a Lewis acid by heat, and this Lewis acid exhibits catalytic activity. It is thought that. Therefore, the boron compound of the present invention can also be referred to as a thermal Lewis acid generator, and can also be applied to various uses [for example, chemically amplified resists] in which a Lewis acid can be used.
That is, the compound of the present invention (the compound represented by the formula (1)) exhibits a catalytic function by heat, and in particular can generate a Lewis acid. Such a Lewis acid is a compound represented by the following formula (2) [for example, tris (pentafluorophenyl) borane (a compound in which Ar ¹ , Ar ² and Ar ³ are all pentafluorophenyl groups)]. May be.

(In the formula, Ar ¹ , Ar ² and Ar ³ are the same as described above.)

As described above, the compound of the present invention seems to be able to generate a Lewis acid derived from an anion moiety having boron as a central atom. In particular, the compound of the present invention can be easily and efficiently simply selected and heated ( Can generate strong Lewis acids [eg, fluoroarylboranes such as tris (pentafluorophenyl) borane].
In addition, the compound of the present invention is composed of boron as the central atom of the anion portion and does not need to contain a metal such as antimony. Therefore, the compound of the present invention is excellent in safety and extremely useful.

The temperature at which the compound of the present invention exhibits a catalytic function (or generates a Lewis acid) is not particularly limited, but is, for example, 20 ° C. or higher (eg, 25 ° C. or higher), preferably 40 ° C. or higher (eg, 50 ° C. or higher). More preferably, it may be 60 ° C. or higher (for example, 70 ° C. or higher). In particular, the compound of the present invention exhibits a catalytic function even in a low temperature region of 140 ° C. or lower, preferably 110 ° C. or lower.
As described above, the boron compound [or agent (thermal Lewis acid generator, thermal latent polymerization initiator)] of the present invention can exhibit catalytic activity even at low temperatures, but the refrigerated storage temperature [for example, 0 ° C. or less (for example, −20 ° C. to 0 ° C.)] and room temperature (for example, 30 ° C. or lower, 25 ° C. or lower, 20 ° C. or lower, etc.). In other words, Lewis acid is not generated or does not exhibit catalytic activity at refrigerated storage temperature or room temperature.

The method for producing the compound of the present invention is not particularly limited. For example, the anion moiety [borate anion represented by the formula (1A) (Ar ¹ Ar ² Ar ³ B (OH) ⁻ )] or a salt thereof and a cation You may manufacture by making a part ( ^{Mn +} ) or its salt react at least. In addition, in the formula (1), the compound in which nk / m is a finite value (n ≠ k) coexists or mixes an anion represented by X ^m− or a salt thereof as an anion portion or a salt thereof. It may be manufactured.

  In particular, the compound of the present invention can be produced by reacting at least the compound represented by the formula (2), a salt of the metal M, and water. Such a method is preferable because a boron compound can be easily obtained in an aqueous system.

  Examples of the salt of the metal M include halides (for example, chloride, bromide, iodide, etc.), inorganic acid salts (for example, carbonate, hydrogencarbonate, sulfate, nitrate, etc.), carboxylates (for example, , Acetate salts, etc.), amine salts, ammonium salts, sulfonium salts and the like.

Among these, salts of inorganic acids (for example, carbonates such as magnesium carbonate (MgCO ₃ )) are preferable.

  In addition, when magnesium carbonate is used as the salt of the metal M, the reaction for obtaining a compound where n = k in the formula (1) is considered to follow the following reaction formula.

(In the formula, Ar ¹ , Ar ² and Ar ³ are the same as described above.)
In the formula (1), a compound in which n−k / m is a finite value (n ≠ k) is a salt represented by M ^{n +} X ^m− _{n / m} in the salt obtained by the above reaction. May be further reacted or mixed.

  In addition, the compound represented by Formula (2), the salt of an anion part, and the salt of a cation part can also be manufactured by a conventional method, and you may use a commercial item about what exists in a commercial item.

[Use and composition of compound]
Since the compound of the present invention usually generates a Lewis acid by heat (thermal energy), it can be called a heat Lewis acid generator. Such a compound of the present invention (and a thermal Lewis acid generator) can be used in various applications in which a Lewis acid can be used, for example, a polymerization initiator (thermal polymerization initiator, thermal latent polymerization initiator), a chemically amplified resist material. It can be used as such.

  Such a compound of the present invention (thermal Lewis acid generator) can constitute various compositions depending on applications. That is, the composition of this invention contains the said compound (or agent), and other components can be selected according to a use etc.

The compound (thermal Lewis acid generator) of the present invention can be suitably used as a thermal polymerization initiator or a thermal latent polymerization initiator (preferably a thermal latent cationic polymerization initiator). That is, the thermal latent polymerization initiator of the present invention contains the compound of the present invention.
Therefore, the present invention includes a thermal Lewis acid generator and a thermal latent polymerization initiator composed of the compound represented by the formula (1).
The thermal latent polymerization initiator of the present invention may contain, for example, 10 to 100% by mass of the compound of the present invention. The thermal latent polymerization initiator of the present invention may contain a solvent and an additive described later.

The present invention also includes a composition containing the compound or the agent (thermal Lewis acid generator, thermal latent polymerization initiator).
For example, when the compound is used as a polymerization initiator, the composition of the present invention may contain the compound and a polymerizable compound that can be polymerized with a Lewis acid.

Examples of such polymerizable compounds include cationic polymerizable compounds [for example, cyclic ethers (epoxy compounds, oxetane compounds, etc.), vinyl ethers, nitrogen-containing monomers (for example, N-vinylpyrrolidone, N-vinylcarbazole). Etc.) etc.]. The polymerizable compound may be an oligomer.
The polymerizable compound may typically contain at least one selected from cationically polymerizable compounds such as epoxy compounds and vinyl ethers.
The polymerizable compounds may be used alone or in combination of two or more.
The polymerizable compound may typically contain at least one selected from the above cationic polymerizable compounds.

  The epoxy compound (cationic polymerizable epoxy resin) is not particularly limited, and examples thereof include aliphatic epoxy compounds (for example, polyglycidyl ethers of aliphatic polyols such as hexanediol diglycidyl ether) and alicyclic (alicyclic). ) Epoxy compounds [e.g., epoxycycloalkanes (e.g., cyclohexene oxide, 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate)], aromatic epoxy compounds [e.g., phenols (phenol, bisphenol A) , Glycidyl ether of phenol novolac, etc.], or a combination thereof.

  In the epoxy compound, the epoxy group may be in any form such as a glycidyl ether type, a glycidyl ester type, and an olefin oxidation (alicyclic) type.

  Among these, in particular, an aromatic epoxy compound (or an aromatic epoxy resin) may be preferably used.

  The compound of the present invention has a wide range of applicable polymerizable compounds, and even for specific polymerizable compounds that are difficult to apply the thermal latent polymerization initiator of Patent Document 1 such as an aromatic epoxy resin, Shows good polymerizability. More specifically, the compound of the present invention can efficiently proceed polymerization (curing) to a polymerizable compound such as a bisphenol A type epoxy resin.

  As the aromatic epoxy resin, for example, bisphenol type epoxy resin (bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc.), biphenyl type epoxy resin, novolac type epoxy resin (phenol novolak type epoxy resin, cresol novolak type epoxy resin, etc.) ), A triphenolalkane type epoxy resin, a phenol aralkyl type epoxy resin, a condensed ring aromatic hydrocarbon-modified epoxy resin (such as 1,6-bis (glycidyloxy) naphthalene) and the like.

  Among these aromatic epoxy resins, bisphenol type epoxy resins (for example, bisphenol A type epoxy resins) are preferable.

In the composition, the ratio of the compound (or agent) is not particularly limited, but is, for example, 0.001 to 10% by mass, preferably 0.005 to 5% by mass, and more preferably 0.01 to 3% by mass ( For example, it may be about 0.05 to 2.5% by mass), particularly about 0.1 to 2% by mass (for example, 0.3 to 1.5% by mass).
Further, in the composition, the ratio of the polymerizable compound is not particularly limited, but is, for example, 0.1% by mass or more (for example, 0.5 to 99.99% by mass), preferably 1% by mass or more (for example, 3 ˜99.9 mass%), more preferably about 5 mass% or more (for example, 10 to 99.5 mass%).
In the composition, the ratio of the compound (or agent) is, for example, 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass, and more preferably 0 to 100 parts by mass of the polymerizable compound. It may be about 1 to 5 parts by mass.

  The composition may be mixed with a solvent [for example, conventional solvents such as carbonates (for example, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.)], additives (for example, Pigments, fillers, antistatic agents, flame retardants, antifoaming agents, stabilizers, antioxidants, etc.).

  You may use a solvent and an additive individually or in combination of 2 or more types.

  When the composition contains a solvent, the ratio of the non-solvent component in the composition may be any value, but may be, for example, about 0.01 to 70% by mass, preferably about 0.1 to 50% by mass. .

  In addition, if necessary, the composition may contain an acid generator or a polymerization initiator that does not belong to the category of the compound of the present invention (thermal Lewis acid generator) [for example, the thermal latent polymerization initiator of Patent Document 1]. May be included.

  As described above, the compound of the present invention exhibits catalytic activity by heat (generally generates a Lewis acid). Therefore, the present invention also includes a method in which the composition (the compound or agent) is heated (irradiated with heat rays) to exert catalytic activity (generate a Lewis acid).

In such a method, when the composition contains a polymerizable compound, the polymerization of the polymerizable compound proceeds by the catalytic function (or Lewis acid), and a polymer of the polymerizable compound can be produced. Depending on the type of the polymerizable compound, the polymer forms a cured product.
Therefore, the present invention includes a method of heating the composition and producing a polymer (cured product) of a polymerizable compound.

  The heating temperature can be appropriately selected according to the type of the compound of the present invention and the polymerizable compound, and is, for example, 20 ° C. or higher (eg, 25 ° C. or higher), preferably 40 ° C. or higher (eg, 50 ° C. or higher), More preferably, it may be 60 ° C. or higher (for example, 70 ° C. or higher). In particular, the compound of the present invention exhibits a catalytic function even in a low temperature range where the heating temperature is 140 ° C. or lower, preferably 110 ° C. or lower.

  The heating time can be appropriately selected according to the compound, the polymerizable compound and the like, and is not particularly limited.

  Applications of the composition of the present invention include, for example, paints, coating agents, various coating materials (hard coats, antifouling coating materials, antifogging coating materials, touchproof coating materials, optical fibers, etc.), backside treatment agents for adhesive tapes, Release coating material for adhesive label release sheet (release paper, release plastic film, release metal foil, etc.), printing plate, dental material (dental compound, dental composite) ink, inkjet ink, positive resist (circuit board) , CSP, MEMS device and other electronic component manufacturing connection terminals, wiring pattern formation, etc.), resist film, liquid resist, negative resist (surface protection film such as semiconductor device, interlayer insulation film, planarization film, etc. permanent film materials Etc.), MEMS resists, positive photosensitive materials, negative photosensitive materials, various adhesives (various electronic component temporary fixing agents, HDD adhesives, CUP lens adhesive, FPD functional film (deflection plate, antireflection film, etc.), holographic resin, FPD material (color filter, black matrix, partition material, photo spacer, rib, liquid crystal alignment Membranes, FPD sealants, etc.), optical members, molding materials (for building materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, sealing materials, optical semiconductors ( LED) sealing material, optical waveguide material, nanoimprint material, photofabrication material, and micro stereolithography material.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. The embodiments of the present invention can also be obtained by appropriately combining technical means disclosed in different embodiments. Included in the range.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention.

Example 1 Preparation of bis [hydroxy-tris (pentafluorophenyl) borate] magnesium Tris (pentafluorophenyl) borane (1.21 g, 2.37 mmol), magnesium carbonate (0.50 g, 1.21 mmol), water (5.0 g) was mixed and stirred for 30 minutes. The reaction proceeded while generating carbon dioxide, and bis [hydroxy-tris (pentafluorophenyl) borate] magnesium was obtained. Excess magnesium carbonate was removed by filtration, and water was removed by an evaporator, whereby bis [hydroxy-tris (pentafluorophenyl) borate] magnesium (1.40 g, water content 21.9 mass) was removed. %, A compound of the following formula):

[Curing test 1]
99 parts of a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828) was mixed with 1 part by mass of an aqueous solution (concentration: 78.1% by mass) of the compound obtained in Example 1. The obtained solution (5 mg) was subjected to differential scanning calorimetry at a measurement temperature range of 20 to 300 ° C. and a temperature increase rate of 10 ° C./min. As a result, heat generation started at 69.9 ° C., and an exothermic peak was reached at 109.1 ° C. The total calorific value was 446 mJ / mg. After the measurement, the resin was completely cured.

[Curing test 2]
99 parts of an alicyclic epoxy resin (Celoxide 2021P, manufactured by Daicel Corporation) was mixed with 1 part by mass of an aqueous solution (concentration: 78.1% by mass) of the compound obtained in Example 1. The obtained solution (5 mg) was subjected to differential scanning calorimetry at a measurement temperature range of 20 to 300 ° C. and a temperature increase rate of 10 ° C./min. As a result, heat generation started at 38.4 ° C., and an exothermic peak was reached at 78.8 ° C. The total calorific value was 616 mJ / mg. After the measurement, the resin was completely cured.

[Curing test 3]
1 part by mass of an aqueous solution (concentration 78.1% by mass) of the compound obtained in Example 1 was mixed with 99 parts by hydrogenated bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER YX8000). The obtained solution (5 mg) was subjected to differential scanning calorimetry at a measurement temperature range of 20 to 300 ° C. and a temperature increase rate of 10 ° C./min. As a result, the exotherm started at 36.0 ° C. and reached an exothermic peak at 96.8 ° C. The total calorific value was 319 mJ / mg. After the measurement, the resin was completely cured.

  According to the compound of the present invention, a catalytic function can be exhibited (or a Lewis acid can be generated) by heat. Therefore, the compound of the present invention can be applied to various uses utilizing a catalytic action (Lewis acid), such as a polymerization initiator and a resist.

Claims (8)

A compound represented by the following formula (1).
(Wherein Ar ¹ , Ar ² and Ar ³ are the same or different aryl groups which may have a substituent, M is an n-valent metal, X is an anion, k and m are numbers greater than 0. Where n is a number of 2 or more.) The compound according to claim 1, wherein in formula (1), at least one of Ar ¹ , Ar ² and Ar ³ is an aryl group having at least one halogen atom.   The compound according to claim 1 or 2, wherein in the formula (1), M is a divalent or trivalent metal. The method to manufacture the compound in any one of Claims 1-3 by making the compound represented by following formula (2), the salt of the metal M, and water react at least.
(In the formula, Ar ¹ , Ar ² and Ar ³ are the same as those in the formula (1).)   The thermal latent polymerization initiator comprised with the compound in any one of Claims 1-3.   The composition containing the compound or agent in any one of Claims 1-3 and 5.   The composition according to claim 6, further comprising a polymerizable compound polymerizable by a Lewis acid.   A method for producing a polymer of a polymerizable compound by heating the composition according to claim 7.