KR20050072439A - Hexaarylbiimidazole compounds and photopolymerization initiator compositions containing the same - Google Patents

Abstract

The present invention provides a novel hexaarylbiimidazole compound of the following formula (1): wherein each R1 represents a halogen, and each R2 represents an optionally substituted C1-4 alkyl group. The hexaarylbiimidazole compound of the present invention is useful as photoradical generators in photopolymerizable compositions used as resists and is characterized by low sublimating thermal decomposition products. The photopolymerizable compositions may be suitably used as resists or as color filters for color liquid crystal display elements, cameras and the like.

Description

Hexaarylbiimidazole compound and the photoinitiator composition containing these {HEXAARYLBIIMIDAZOLE COMPOUNDS AND PHOTOPOLYMERIZATION INITIATOR COMPOSITIONS CONTAINING THE SAME}

The present invention relates to novel hexaarylbiimidazole compounds. More preferably, it is useful as an optical radical initiator contained in the photopolymerizable composition used for various resists, and the photopolymerizable containing a hexaaryl biimidazole compound and an optical radical generating agent whose thermal decomposition product is low sublimation. An initiator composition and the photopolymerizable composition using these are related. The photopolymerizable composition of the present invention may be suitably used as a color filter used for a resist or a color liquid crystal display element, a camera, or the like.

Photopolymerizable compositions (photosensitive compositions) are widely used in various fields including various resists (photoresist, solder resist, etching resist, and the like).

Recently, in particular, color filters used in color liquid crystal displays, color video cameras, and the like have been required for photopolymerizable compositions as color filter resists that satisfy excellent performances such as high sensitivity, time-lapse stability, high resolution, high heat resistance, and high light resistance.

A color filter is usually manufactured by forming a black matrix on the surface of a transparent substrate such as glass, and then forming a string or mosaic pattern of three or more different colors such as red, green, and blue with a precision of several microns.

One typical method of preparing color filters is pigment dispersion using a coloring composition prepared by dispersing the pigment in the photosensitive composition. The pigment dispersion method is widely used because it has high precision such as position and film thickness of color filter pixels, excellent durability such as light resistance and heat resistance, and no defects such as pinholes.

In the pigment dispersion method, a pigment containing a photosensitive composition is applied onto a substrate and subjected to photolithography to form various colored layers in a predetermined pattern formation. Specifically, one color filter photosensitive composition is applied onto a transparent substrate such as glass and subjected to pattern exposure, and the unexposed portion is developed and removed with a solvent or an alkaline aqueous solution to form a first colored pattern. By repeating the above process to the entire filter color to prepare a color filter. The photosensitive composition is generally considered negative in terms of physical properties as a color filter and abundance of materials, and is developed without using an organic solvent in order to avoid environmental problems. That is, most developments are alkaline developments using alkaline solutions. to be.

In a manufacturing process, baking is generally performed after a developing process (post-baking). That is, after the development treatment, a transparent substrate having a patterned cured photosensitive layer (known as a colored layer, a pixel element layer or a resist layer) is heated for about 10 to 120 minutes at, for example, about 160 to 250 ° C (baking). Is done. Post-baking imparts chemical and physical durability to the colored layer.

However, photosensitive compositions conventionally used in resists often result in sublimation upon post-baking after development. These sublimates adhere to the exhaust duct and the like, and once adhered, problems such as falling on the resist layer occur. This requires the development of a photosensitive composition that suppresses the generation of a sublimation even during the baking process, and in particular, the development of a photosensitive composition using a low-sublimation photopolymerization initiator at high sensitivity.

The hexaarylbiimidazole-based compound is known as a component of the photopolymerization initiator composition to the photosensitive composition (see Patent Document 1 below), and is represented by, for example, 2,2'-bis (shown in Formula (4) described below). Photosensitive compositions of color filters using 2-chlorophenyl) -4,4'-5,5'-tetraphenyl-1,2'-biimidazole (HABI) are described in Japanese Patent Application Laid-Open No. 6-75372 (see Patent Document 2). And Japanese Patent Laid-Open No. 2000-249822 (see Patent Document 3). However, these documents have not dealt with the problem of sublimation at the time of post-baking, and naturally no hexaarylbiimidazole compound having a substituent of the present invention is proposed to them.

[Patent Document 1]

Japanese Patent Application Laid-Open No. 45-37277

[Patent Document 2]

Japanese Patent Application Laid-Open No. 06-075373

[Patent Document 3]

Japanese Patent Application Laid-Open No. 2000-249822

An object of the present invention is to provide a photopolymerizable composition at high sensitivity and low sublimation, a photopolymerization initiator composition using the same, and a photopolymerizable composition which is particularly suitable for a color filter with little sublimation even in a baking process.

As a result of earnestly examining the above-mentioned problems, the present inventors found that the thermal decomposition products of hexaarylbiimidazole-based compounds in which a sublimate adhered to the exhaust duct at the time of post-baking were used as the photopolymerization initiator contained in the photopolymerization composition in the photosensitive composition. The problem described above was solved by the photoinitiator composition which uses the novel hexaaryl biimidazole compound which is the crystal | crystallization of a, and a photopolymerizable composition containing this as a photoradical generator, and reached this invention.

1 is a ¹ H-NMR spectrum of MHABI.

2 is a ¹³ C-NMR spectrum of MHABI.

3 is a ¹³ C-NMR spectrum of (enlarged) MHABI.

4 is the mass spectrum of MHABI.

5 is a photograph of the heated stainless steel of Example 1. FIG.

6 is a photograph of the heated stainless steel of Comparative Example 1. FIG.

That is, the present invention provides a hexaarylbiimidazole compound according to the following [1] to [8], an optical radical generator including the same, a photopolymerization initiator composition using the same, and a photopolymerizable composition containing the same.

[1] Hexaarylbiimidazole compound defined by the following formula (1):

Wherein each R ₁ is a halogen atom and each R ₂ is an optionally substituted alkyl group having 1 to 4 carbon atoms

[2] Hexaarylbiimidazole compound defined by the following formula (2):

[3] The method for using hexaarylbiimidazole according to [1] or [2], which is used as an optical radical generating agent.

[4] The photoinitiator composition according to [1], which contains a hexaarylbiimidazole compound.

[5] The photoinitiator composition according to [4], wherein the photopolymerization initiator composition comprises at least one compound selected from the group consisting of a benzophenone compound, a thioxanthone compound and a ketocomarin compound.

[6] The photopolymerization initiator composition according to [4], which contains a thiol compound and / or a dicarbonyl compound defined by the following formula (3) as a hydrogen donor for the hexaarylbiimidazole compound:

Wherein R ₃ and R ₄ are each independently optionally substituted alkyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted aralkyl, optionally substituted aryl, optionally substituted aryloxy or polymerization It may be an organic group having a unsaturated unsaturated group or a polymer compound residue, or R ₃ and R ₄ may be bonded together to form a ring. R ₅ is a hydrogen atom, optionally substituted alkyl, optionally substituted aralkyl or optionally substituted aryl.

[7] A photopolymerizable composition comprising at least the following components:

(A) The photoinitiator composition in any one of [4]-[6].

(B) Compound of ethylenically unsaturated group

[8] a photopolymerizable composition for color filter resists comprising at least the following components:

(A) The photoinitiator composition in any one of [4]-[6]; And

(B) Compound of ethylenically unsaturated group

Hexaarylbiimidazole compound commonly used as a component of the photoinitiator composition of the photosensitive composition, 2,2'-bis (2-chlorophenyl) -4,4'-5,5'-tetraphenyl-1,2'- Biimidazole (formula (4), abbreviated as HABI) is thermally decomposed during post-baking with the compound represented by the following formula (5). The compound is highly sublimable and easily adheres to the exhaust duct.

The hexaarylbiimidazole compound represented by formula (1) of the present invention was first discovered in the present invention. The decomposition products of these compounds represented by the formula (1) are low sublimability, unlike HABI, and are characterized by crystallization on the exhaust duct during post-baking. In the present invention, a novel hexaarylbiimidazole compound is used as a photoradical generator in a photosensitive composition for the first time that crystals do not adhere to the exhaust duct at the time of post-baking, thereby preventing problems caused by the crystals. It was.

Embodiments of the present invention will be described in detail.

1. Hexaarylbiimidazole compounds

The hexaarylbiimidazole compound of the present invention is represented by the following formula (1):

Wherein each R ₁ is halogen and each R ₂ is an optionally substituted alkyl group having 1 to 4 carbon atoms.

In formula (1), a chlorine atom is preferable as the halogen atom of R ₁ . Each R ₂ is an optionally substituted alkyl group having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group or an isopropyl group, and more preferably a methyl group. As the substituent for R ₂ , a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group or the like may be used.

Among the hexaarylbiimidazole compounds represented by formula (1), particularly preferred compounds are 2,2'-bis (2-chlorophenyl) -4,4'-5,5'-tetrakis represented by the following formula (2): 4-methylphenyl) -1,2'-biimidazole (MHABI) may be sufficient.

The hexaarylbiimidazole compound of the present invention may be suitably used as an optical radical generating agent in the photosensitive composition of a high sensitivity color filter.

2.Photoinitiator composition

2- (1) hexaarylbiimidazole compound

The photoinitiator composition of this invention is characterized by including the hexaaryl biimidazole represented by said Formula (1). Although the compounding ratio of a hexaaryl biimidazole compound in the said photoinitiator composition is not specifically limited, 20 to 60 weight% is preferable, More preferably, it is 30 to 50 weight%. When the ratio of the hexaarylbiimidazole compound is too low, the amount of radicals is reduced, so that the photosensitivity may be deteriorated or the curing of the photopolymerizable composition may be insufficient. If the amount is too large, the amount of addition of the sensitizer or hydrogen donor is reduced and the photosensitivity is lowered, which is not preferable.

If the photoinitiator composition of the present invention contains the specific hexaarylbiimidazole compound described above as an essential component, other components (hydrogen donor, sensitizer, other photoinitiator) usually used in the photopolymerization initiator composition are also used without particular limitation. . Although these components may combine the said component so that it may show the function of a photoinitiator as a whole, it is preferable to add the following compound.

At least one compound selected from the group consisting of 2- (2) benzophenone compound, thioxanthone compound and ketocomarin compound

In the photoinitiator composition of this invention, in order to improve a sensitivity, it is preferable to use at least 1 sort (s) of compound chosen from the group which comprises a benzophenone type compound, a thioxanthone type compound, and a ketocomarin type compound as a sensitizer.

Examples of the benzophenone compounds include benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4,4'-bis (dimethylamino) benzophenone And 4,4'-bis (diethylamino) benzophenone.

As an example of a thioxanthone type compound, 2-methyl thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, isopropyl thioxatone, 2, 4- diisopropyl thioxanthone, 2-chlorothioxanthone, etc. are mentioned.

Examples of ketomarin-based compounds include 3-acetylcoumarin, 3-acetyl-7-diethylaminocomarin, 3-benzoylcomarin, 3-benzoyl-7-diethylaminocomarin, 3-benzoyl-7-meth Toxickoumarin, 3,3'-carbonylbiscomarin, 3,3'-carbonylbis (7-methoxycoumarin) and 3,3'-carbonylbis (5,7-dimethoxycoumarin) And the like.

Although the mixing ratio of a sensitizer to a photoinitiator composition is not specifically limited, 5-40 weight% is preferable in all the photoinitiator compositions, More preferably, it is 10-30 weight%. When these compounding ratios are too low, a sensitivity will fall, and when said ratio is too high, sufficient light will not reach | attain a resist lower layer part, and hardening of the part will become inadequate.

2- (3) thiol compound and / or carbonyl compound

In the photopolymerization initiator composition of the present invention, a thiol compound and / or a carbonyl compound may be used as the hydrogen donor of the hexaarylbiimidazole compound described above.

[1] thiol compounds

The thiol compound used in the present invention is not particularly limited as long as it is a compound having a thiol group in the molecule, and any of those conventionally used as a photopolymerization initiator composition may be optionally selected and used.

Examples of the thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 5-chloro-2-mercaptobenzothiazole, 2-mercapto-5-methoxy Benzothiazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 5-mercapto-1-methyltetrazole, 3-mercapto-4-methyl-4H-1,2,4- Triazole, 2-mercapto-1-methylimidazole, 2-mercaptothiazoline, octanethiol, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, 1,4-butanediol bis (3- Mercaptopropionate), 1,4-butanediol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (mercaptoacetate), trimethylolpropane tris (3-mercapto Propionate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (mercaptoacetate).

From the viewpoint of the holding stability of the photopolymerizable composition, the thiol compound of the present invention is particularly preferably a thiol compound having a structure branched to carbon at the α- and / or β-position of the thiol group, or the α- and / of the thiol group. Or a thiol compound having a branched structure, that is, bonded to carbon at the β-position with at least 3 atoms other than hydrogen, for example, at least one of substituents other than the main chain at the α- and / or β-position relative to the thiol group Listed are compounds in which the dog is an alkyl group. Here, the main chain shows the structure of the longest main chain which consists of atoms other than hydrogen containing a thiol group.

Especially, the thiol compound in which a thiol group containing structure part is represented by following formula (6) is preferable.

-(CH ₂ ) _m C (R ₆ ) (R ₇ ) (CH ₂ ) _n SH (6)

(Wherein R ₆ and R ₇ each independently represent a hydrogen or alkyl group, R ₆ and R ₇ do not become hydrogen atoms at the same time, m is an integer of 0 to 2, and n represents an integer of 0 or 1 .)

Here, it is preferable that an alkyl group (R <_6> and R <_7> in Formula (6)) is a C1-C3 linear or branched alkyl group. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, etc. are mentioned, More preferably, they are a methyl group or an ethyl group.

The thiol compound used in the present invention is more preferably a polyfunctional thiol compound having two or more mercapto groups from the viewpoint of increasing the photosensitivity, and in order to satisfy both the photosensitivity and the storage stability of the photosensitive composition, the formula of the present invention ( Particularly preferred is a polyfunctional thiol compound having the structure shown in 6). Specifically, the following compounds are listed.

Examples of hydrocarbon dithiols include 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis (1-mercaptoethyl) benzene and the like.

Compounds containing ester linkages include phthalic bis (1-mercaptoethyl ester), phthalic bis (2-mercaptopropyl ester), phthalic bis (3-mercaptobutyl ester), phthalic bis (3-mercaptoisobutyl Ester), ethylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), 1,4-butanediol bis (3-mercaptobutyrate) , 1,3-butanediol bis (3-mercaptobutyrate), 1,2-butanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercapto Butyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoiso Butyrate), 1,4-butanedi Bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), Ethylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoisobutyrate), 1,4-butanediol bis (3-mercaptoisobutyrate) Butyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate), and the like.

You may use these thiol compounds individually or in combination of 2 or more types.

In the case of using the thiol compound, the mixing ratio of the thiol compound to the photopolymerization initiator composition is not particularly limited, but is preferably 20 to 70% by weight, more preferably 30 to 60% by weight relative to the total photopolymerization initiator composition. If the ratio of the thiol compound is too low, the surface curability of the resist is lowered, and if it is too high, the chain transfer of the mercapto group may lower the crosslinking degree of the cured product.

[2] carbonyl compounds

Preferred carbonyl compounds used as hydrogen donors in the present invention are those represented by the following formula (3):

Wherein R ₃ and R ₄ are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted amino group, an optionally substituted aralkyl group, an optionally substituted aryl group, an optionally substituted aryl An organic group having an oxy group or a photopolymerizable unsaturated group or a polymer compound residue may be represented, and R ₃ and R ₄ may be bonded to each other to form a ring. R ₅ represents hydrogen, an optionally substituted alkyl group, an optionally substituted aralkyl group or an optionally substituted aryl group.

As an alkyl group of R <_3> and R <_4> of Formula (3), C1-C8, More preferably, a C1-C6 linear or branched alkyl group etc. are mentioned. Specific examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group and 2-ethyl And hexyl groups. These may be further substituted with an alkoxy group, halogen or the like.

As an alkoxy group of R <_3> and R <_4> of Formula (3), C1-C8, More preferably, a C1-C6 linear or branched alkoxy group etc. are mentioned. Specific examples include methoxy group, ethoxy group, propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group and 2-ethylhex It includes a siloxy group. These may be further substituted with an alkoxy group, halogen or the like.

The amino group of R <_3> and R <_4> of Formula (3) may have these hydrogen atoms substituted by hydrocarbon groups, such as an alkyl group, an aralkyl group, or an aryl group. As an alkyl group substituted by the hydrogen atom of an amino group, it is preferable to list C1-C4 things, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, or t-butyl group. Alicyclic hydrocarbon groups, such as cyclohexyl and cyclopentyl, may be enumerated.

As an aralkyl group substituted by the hydrogen atom of an amino group, benzyl, phenethyl, etc. may be mentioned. Examples of the aryl group substituted in the hydrogen atom of the amino group include a phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, ananiyl group and naphthyl group. A heterocyclic amino group having a nitrogen atom in the ring is also suitable, and examples of the amino group include morpholino, piperidino, and pyrrolidino.

Examples of the aralkyl group represented by R ₃ and R ₄ in formula (3) include benzyl and phenethyl groups. It may be substituted with an alkyl group, an alkoxy group, an aryl group, a halogen or the like.

As an aryl group of R <_3> and R <_4> in Formula (3), a phenyl group, a tolyl group, a xylyl group, cumenyl group, a mesityl group, an anylyl group, a naphthyl group, etc. can be mentioned. Examples of the aryloxy group include phenoxy group and naphthoxy group. These may be substituted with alkyl groups, alkoxy groups, aryl groups, halogens and the like.

As an organic group which has a polymerizable unsaturated group in R <_3> and R <_4> in Formula (3), a vinyl group, a vinylidene group, an acryl oil group, a methacryl oil group, etc. can be mentioned.

As an organic group which has a polymer compound residue in R <_3> and R <_4> in Formula (3), it has a polymer compound group which the various repeating unit couple | bonded by superposition | polymerization or polycondensation. For example, the thing which superposed | polymerized in the said polymerizable unsaturated group and formed the polymer compound can be mentioned. According to the above-mentioned separately, a polymer compound can be formed by copolymerizing a compound with R <_3> and R <_4> of Formula (3).

Specifically, as monomers having a carbonyl group at the 1,3-position, 2-acetoacetoxyethyl methacrylate, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl crotonate and the like or methacrylic acid or methyl methacrylate The copolymer of unsaturated group containing monomers, such as a rate, can be mentioned. The weight average molecular weight of the polymer compound residue is not particularly limited, but is preferably 1,000 to 1,000,000.

R <_3> and R <_4> may combine with each other in Formula (3), and may form a ring structure, and in that case, the compound of the 5- to 7-membered ring structure is preferable.

R ₅ in formula (3) represents hydrogen, an optionally substituted alkyl group, an optionally substituted aralkyl group or an optionally substituted aryl group.

As an alkyl group, Preferably, C1-C8, More preferably, a C1-C4 linear or branched alkyl group etc. are mentioned, A specific example is a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, and 2-ethylhexyl group. Examples of the aralkyl group include benzyl group and phenethyl group. These may be further substituted with alkyl groups, aryl groups, alkoxy groups, halogens and the like. As an aryl group, a phenyl group, a tolyl group, a xylyl group, cumenyl group, a mesityl group, an anyl group, a naphthyl group, etc. can be mentioned. These may be substituted with alkyl groups, aryl groups, alkoxy groups, halogens and the like.

Dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, diisobutyl malonate, di-n-hexyl malo as compounds of formula (3) Nate, di-n-octyl malonate, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid n-propyl ester, acetoacetic acid isopropyl ester, acetoacetic acid n-butyl ester, acetoacetic acid isobutyl ester, acetoacetic acid n- Hexyl ester, acetoacetic acid n-octyl ester, acetoacetic acid benzyl ester, acetoacetic acid 2-methoxyethyl ester, acetoacetoxyethyl methacrylate, N-methylacetoacetamide, N-ethylacetoacetamide, N, N- Dimethylacetoacetamide, N, N-diethylacetoacetamide, N-acetoacetyl-N-morpholine, aceto Cetoanilide, N-acetoacetyl-2-chloroaniline, N-acetoacetyl-2,5-, dichloroaniline, N-acetoacetyl-p-toluidine, N-acetoacetyl-o-toluidine, 1,3-cyclohexane Diones and dimethones may be enumerated.

When using the compound of Formula (3), although the compounding ratio of the said carbonyl compound in a photoinitiator composition is not specifically limited, Preferably it is 20 to 70 weight%, More preferably, it is 30 to 60 weight%. If the carbonyl compound ratio is too low, the surface curability of the resist is lowered, and if too high, the crosslinking degree of the cured product may be lowered.

2- (4) Other Ingredients

The photoinitiator composition of this invention can contain an organoboron salt compound in addition to the component mentioned above.

The organoborone salt compound used in the present invention can be used as long as it is a general one used in a conventional photopolymerization initiator composition, but preferably those having a structure represented by the following formula (7):

In formula (7), R ₈ , R ₉ , R ₁₀ and R ₁₁ each independently represent an optionally substituted alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, silyl group or heterocycle, and Z ⁺ is Any cation. Examples of groups represented by R ₈ , R ₉ , R ₁₀ and R ₁₁ are listed below.

Specifically as the alkyl group, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl The group, tert- butyl group, n-pentyl group, n-hexyl group, n-octyl group, dodecyl group, cyanomethyl group, 4-chlorobutyl group, 2-ethylaminoethyl group, 2-methoxyethyl group, etc. are mentioned. .

Examples of the aryl group include substituted or unsubstituted phenyl group, tolyl group, xylyl group, mesityl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 4-n-butylphenyl group, 4-tert-butylphenyl group, naphthyl group, 4-methylnaphthyl group, anthryl group, phenanthryl group, 4-nitrophenyl group, 4-trifluoromethylphenyl group, 4-fluorophenyl group, 4-chlorophenyl group, and 4-dimethylaminophenyl group can be mentioned.

Examples of aralkyl groups include substituted or unsubstituted benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, and 4-methoxybenzyl groups.

Examples of alkenyl groups include substituted or unsubstituted vinyl groups, propenyl groups, butenyl groups, and octenyl groups.

Examples of the heterocyclic group include substituted or unsubstituted pyridyl group, 4-methylpyridyl group, quinolyl group and indolyl group.

Examples of the alicyclic group include substituted or unsubstituted cyclohexyl, 4-methylcyclohexyl, cyclopentyl, cycloheptyl and the like.

In formula (7), R ₈ is preferably a methyl group, an ethyl group, n-propyl group or n-butyl group, and R ₉ -R ₁₁ are each a phenyl group, tolyl group, 4-t-butyl group, naphthyl group or 4-methylnaph; Til group is preferred.

Z ⁺ is preferably an ammonium cation, sulfonium cation, oxosulfonium cation, pyridinium cation, phosphonium cation, oxonium cation or iodonium cation.

Specific examples of the ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetra-n-propyl ammonium cation, tetra-n-butyl ammonium cation, n-butyltriphenyl ammonium cation, tetraphenyl ammonium cation and benzyltriphenyl ammonium cation. Can be enumerated.

Specific examples of the sulfonium cation include triphenylsulfonium cation, tri (4-tolyl) sulfonium cation and 4-tert-butylphenyldiphenylsulfonium cation.

Specific examples of the oxosulfonium cation include triphenyloxosulfonium cation, tri (4-tolyl) oxosulfonium cation and 4-tert-butylphenyldiphenyl oxosulfonium cation.

Specific examples of pyridinium cations include N-methylpyridinium cations and N-n-butylpyridinium cations.

Specific examples of the phosphonium cation include tetramethylphosphonium cation, tetra-n-butyl phosphonium cation, tetra n-octylphosphonium cation, tetraphenyl phosphonium cation and benzyltriphenylphosphonium cation.

Specific examples of the oxonium cation include triphenyl oxonium cation, tri (4-tolyl) oxonium cation and 4-tert-butylphenyldiphenyl oxonium cation.

Specific examples of the iodonium cation include diphenyl iodonium cation, di (4-methylphenyl) iodonium cation and di (4-tert-butylphenyl) iodonium cation.

Examples of the organoboron salt compound represented by formula (7) include tetramethylammonium n-butyltriphenylborate, tetraethylammonium isobutyltriphenylborate, tetra-n-butylammonium n-butyltri (4-tert-butylphenyl) borate , Tetra-n-butylammonium n-butyltrinaphthylborate, tetra-n-butylammonium methyltri (4-methylnaphthyl) borate, triphenylsulfonium n-butyltriphenylborate, triphenyloxosulfonium n- Butyltriphenylborate, triphenylphenylononium n-butyltriphenylborate, N-methylpyridinium n-butyltriphenylborate, tetraphenylphosphonium n-butyltriphenylborate and diphenyliodonium n-butyltriphenylborate Can be enumerated.

Since the organic boron salt compound represented by the formula (7) cannot absorb light having a wavelength of 300 nm or more, the light source of a conventional ultraviolet lamp has little sensitivity when used alone, but in combination with a sensitizer, very high sensitivity Can be obtained.

When the organoboron salt compound is used in combination with the hexaarylbiimidol compound of the present invention, the total of the hexaarylbiimidazole compound and the organoboron salt compound in the photopolymerizable composition is preferably 20 to 60% by weight in total, more preferably. Preferably it is 30-50 weight%. Too low a ratio of the hexaarylbiimidazole compound and the organoboron salt compound has a disadvantage in that the amount of radicals is insufficient, resulting in deterioration of light sensitivity or insufficient curing, and too high a decrease in the amount of sensitizer or hydrogen donor added. There is a disadvantage that the photosensitivity is lowered.

3. Photopolymerizable Composition

The photopolymerizable composition of the present invention is characterized by comprising (A) the above-described photopolymerization initiator composition of the present invention and (B) a compound having an ethylenically unsaturated group. You may also contain binder resin and a coloring pigment.

3- (1) Compound having an ethylenically unsaturated group

The compound which has an ethylenically unsaturated group in the photopolymerizable composition of this invention is a compound superposed | polymerized and bridge | crosslinked by the radical which generate | occur | produced by the photoradical photoinitiator by irradiating light, and a monomer or a polymer may be any.

3- (1)-[1] monomer

(Meth) acrylic acid ester is preferable as a monomer. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert- Butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) Alkyl (meth) acrylates such as) acrylate and stearyl (meth) acrylate;

Alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate;

Benzyl (meth) acrylate, phenyl (meth) acrylate, phenylcarbitol (meth) acrylate, nonylphenyl (meth) acrylate, nonylphenylcarbitol (meth) acrylate, and nonylphenoxy (meth) acrylate Aromatic (meth) acrylates such as;

2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, butanediol mono (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylic Hydroxyl group-containing (meth) acrylates such as acrylate and glycerol di (meth) acrylate;

Amino group-containing (meth) acrylates such as 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate and 2-tert-butylaminoethyl (meth) acrylate;

Phosphorus-containing methacrylates such as methacryloxyethyl phosphate, bismethacryloxyethyl phosphate and methacryloxyethylphenyl acid phosphate (phenyl P);

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, Diacrylates such as neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and bisglycidyl (meth) acrylate;

Polyacrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; 4 mole addition diacrylate of ethylene oxide of bisphenol S, 4 mole addition diacrylate of ethylene oxide of bisphenol A, fatty acid modified pentaerythritol diacrylate, 3 mole addition triacrylate of trimethylolpropane and trimethylolpropane propylene oxide Modified polyol polyacrylates such as 6 mol addition triacrylate;

Polyacrylates containing isocyanuric acid skeletons such as bis (acryloyloxyethyl) monohydroxyethyl isocyanate, tris (acryloyloxyethyl) isocyanate and ε-caprolactone addition tris (acryloyloxyethyl) isocyanate; polyester acrylates such as α, ω-diacrylic oil (bisethylene glycol) phthalate and α, ω-tetraacrylic oil (bistrimethylolpropane) tetrahydrophthalate;

Glycidyl (meth) acrylate, allyl (meth) acrylate; ω-hydroxyhexanoyloxyethyl (meth) acrylate; Polycaprolactone (meth) acrylates; (Meth) acryloyloxyethyl phthalate; (Meth) acryloyloxyethyl ethyl succinate; 2-hydroxy-3-phenoxypropyl acrylate; Phenoxyethyl acrylate and the like.

N-vinyl compounds, such as n-vinylpyrrolidone, n-vinylformamide, and n-vinylacetamide, may be suitably used as a monomer.

Among these, preferred compounds for enhancing the light sensitivity may include polyacrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythrol hexa (meth) acrylate.

3- (1)-[2] polymer

Examples of the polymer include epoxy (meth) acrylates, urethane (meth) acrylates and ethylenically unsaturated group-containing acrylic acid copolymers. However, when used in resists and color filter applications, development is carried out in an aqueous alkali solution. Carboxyl group-containing polymers are preferred. Herein, "polymer" includes "prepolymer" and "oligomer" having a low molecular weight.

<Carboxyl group-containing epoxy (meth) acrylate (EA)>

It does not restrict | limit especially to the carboxyl group-containing epoxy (meth) acrylate of this invention, Epoxy (meth) acrylate obtained by making the reaction material of an epoxy compound and an unsaturated group containing monocarboxylic acid react with an acid anhydride is suitable.

Although not particularly limited to epoxy compounds, bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, phenol-novolac epoxy compounds, cresol novolac epoxy compounds and fatty acid epoxy compounds may be listed. These can be used individually or in combination of 2 or more types.

Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, 2- (meth) acrylic oiloxyethyl succinic acid, 2- (meth) acrylic oiloxyethyl phthalic acid, (meth) acrylic oiloxyethyl hexahydrophthalic acid, (meth) acrylic acid dimer , β-furfuryl acrylic acid, β-styryl acrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like. In addition, anti-ester compounds which are reaction products of hydroxyl group-containing acrylates and saturated or unsaturated dibasic anhydrides, and anti-ester compounds which are reaction products of unsaturated group-containing monoglycidyl ethers and saturated or unsaturated dibasic anhydrides can be listed. . These unsaturated group containing monocarboxylic acids can be used individually or in combination of 2 or more types.

Examples of the acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and methylene domethylene tetrahydrophthalic anhydride Aromatic polyhydric carboxylic acid anhydrides such as dibasic acid anhydrides such as acid anhydride and methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride, or 5- (2,5-di Oxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride and endobicyclo- [2,2,1] -hept-5-ene-2,3-dicar Polyhydric carboxylic acid anhydride derivatives such as acid anhydride and the like. These can be used individually or in combination of 2 or more types.

The molecular weight of the carboxyl group-containing epoxy (meth) acrylate obtained in the above method is not particularly limited, but the weight average molecular weight is preferably 1000-40,000, more preferably 2000-5000, based on polystyrene by GPC.

The acid value of the above-mentioned epoxy (meth) acrylate compound (solid acid value measured by JIS K0070, hereinafter equal) is preferably at least 10 mgKOH / g, more preferably in the range of 45-160 mgKOH / g, and alkaline developability ( The range of 50-140 mgKOH / g is more preferable in order to satisfy the balance of alkali solubility) and the alkali resistance of a cured film. If the acid value is less than 10 mgKOH / g, the alkaline solubility is lowered. If the acid value is too high, the alkali resistance or other performance of the cured film is lowered depending on the combination of components of the curable resin composition for resist.

<Carboxyl group-containing urethane (meth) acrylate (UA)>

Since the carboxyl group-containing urethane (meth) acrylate compound used in the present invention can be provided as an acrylic acid copolymer or an epoxy (meth) acrylate flexible binder resin, it is suitable for applications requiring flexibility and flex resistance.

The carboxyl group-containing urethane (meth) acrylate compound is a compound containing a hydroxyl group-containing (meth) acrylate derived unit, a polyol derived unit, and a polyisocyanate derived unit as structural units. More specifically, the sock end is composed of a hydroxyl group-containing (meth) acrylate derived unit, and the sock end is made of a polyol derived unit and a polyisocyanate derived unit of a urethane bond linkage, and a carboxyl group is included in the repeating unit. exist.

That is, the carboxyl group-containing urethane (meth) acrylate compound is-(OR _b O-OCNHR _c NHCO) _n- (where OR _b O is a dehydrogenated moiety of the polyol and R _c is a deisocyanated moiety of the polyisocyanate) ).

The carboxyl group-containing urethane (meth) acrylate compound can be prepared by reacting at least the hydroxyl group-containing (meth) acrylate (a) with a polyol (b) and a polyisocyanate (c), but the carboxyl group-containing compound is contained in a polyol or polyisocyanate. It is necessary to use with which. Using a carboxyl group-containing compound as the polyol and / or polyisocyanate, a urethane (meth) acrylate compound having a carboxyl group in R _b or R _c can be produced. In the formula, n is preferably 1 to 200, more preferably 2 to 30. If the value of n exists in these ranges, the flexibility of a cured film will become more excellent.

When at least one of a polyol and a polyisocyanate uses 2 or more types, although a repeating unit shows a some kind, the regularity of the some unit can be suitably selected according to the objective, such as a perfect random, a block, a local part, etc.

As a hydroxyl group containing (meth) acrylate (a) of 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the above-mentioned (meth) acrylate Caprolactone or alkylene oxide adducts, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, glycidyl methacrylate-acrylic acid adduct, trimethylolpropane mono (meth) acrylate, trimethylol di ( Meta) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethololpropane-alkylene oxide adduct-di (meth) acrylate, and the like.

These hydroxyl group containing (meth) acrylates (a) can be used individually or in combination of 2 or more types. Among these, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable. Using 2-hydroxyethyl (meth) acrylate facilitates the synthesis of the carboxyl group-containing urethane (meth) acrylate compound (UA).

The polyol (b) used in the present invention may be a polymer polyol and / or a dihydroxy compound. Examples of the polymer polyol include units derived from polyether diols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polyester diols obtained from esters of polyhydric alcohols and polybasic acids, hexamethylene carbonate, pentamethylene carbonate, and the like. And polylactone diols such as polycarbonate diol and polycaprolactone diol and polybutyrolactone diol.

When using a carboxyl group-containing polymer diol, a compound synthesized such that a carboxyl group remains by adding a trivalent or polybasic acid such as trimellitic acid (or anhydride), for example, in synthesizing the polymer polyol.

Polymer polyols can be used alone or in combination of two or more thereof. As a polymer polyol, when the number average molecular weight uses 200-2,000, the flexibility of a cured film will become more excellent.

The dihydroxy compound uses a straight chain or branched compound having two alcoholic hydroxyl groups, but carboxyl group-containing dihydroxy aliphatic carboxylic acid is particularly preferred. Dimethylolpropionic acid and dimethylolbutanoic acid may be cited as the dihydroxy compound. A carboxyl group-containing dihydroxy aliphatic carboxylic acid can be used to easily include a carboxyl group in the urethane (meth) acrylate compound.

A dihydroxy compound can be used 1 type or in combination of 2 or more types, and can be used together with a polymer polyol selectively.

When using a carboxyl group-containing polymer polyol in combination, or when using the carboxyl group-containing compound mentioned later as a polyisocyanate, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5 Dihydroxy compounds which do not have a carboxyl group such as -pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol or 1,4-cyclohexane dimethanol can be used.

Polyisocyanates used in the present invention are specifically 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, (o, p or p)- Xylene diisocyanate, methylenebis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate and 1,5-naphthalene diisocyanate The diisocyanate of can be mentioned. These polyisocyanates can be used individually or in combination of 2 or more types. Carboxyl group-containing polyisocyanates can also be used.

Although the molecular weight of the carboxyl group-containing urethane (meth) acrylate used for this invention is not restrict | limited, Preferably the weight average molecular weight is 1000-40,000 based on polystyrene by GPC, More preferably, it is 8000-30,000. The acid value of the carboxyl group-containing urethane (meth) acrylate compound (UA) is preferably 5 to 150 mgKOH / g, more preferably 30 to 120 mgKOH / g.

If the weight average molecular weight of the carboxyl group-containing urethane (meth) acrylate compound (UA) is less than 1000, the elongation and strength of the cured film may be inhibited, and when larger than 40,000, the film may become more cured and less flexible. If the acid value is less than 5 mgKOH / g, the alkaline solubility (dissolving property) of the curable resin composition for resist may be inhibited. If the acid value is greater than 150 mgKOH / g, the alkali resistance of the cured film may be inhibited.

<Carboxyl group and ethylenically unsaturated group-containing acrylic acid copolymer (AP-A)>

The carboxyl group- and ethylenically unsaturated group-containing acrylic acid copolymer is obtained by copolymerizing an a) carboxyl group-containing ethylenically unsaturated monomer and b) an ethylenically unsaturated monomer other than the above a), and then copolymerizing the monomer. To some carboxyl groups in the side chain of B), an epoxy group of a compound having an epoxy group and an ethylenically unsaturated group is reacted with each molecule such as glycidyl (meth) acrylate or allyl glycidyl ether, or the whole of the acrylic acid copolymer With respect to the hydroxyl group, an isocyanate group of a compound having an isocyanate group and an ethylenically unsaturated group is reacted with each molecule such as 2-methacryloyloxyethyl isocyanate to introduce an ethylenically unsaturated group into the side chain.

The carboxyl group-containing ethylenically unsaturated monomer a) is used for the purpose of imparting alkaline developability to the acrylic acid copolymer. Specific examples of the carboxyl group-containing ethylenically unsaturated monomers include (meth) acrylic acid, 2- (meth) acrylic oiloxyethyl succinic acid, 2- (meth) acrylic oiloxyethyl phthalic acid, (meth) acrylic oiloxyethyl hexahydrophthalic acid, (meth) ) Acrylic acid dimer, maleic acid, crotonic acid, itaconic acid, fumaric acid, and the like.

In addition to the above a), the ethylenically unsaturated monomer b) is used for the purpose of controlling the application (resist, color filter) of strength and pigment dispersibility. Specific examples include vinyl compounds such as styrene, α-methylstyrene, (o, m, p-) hydroxystyrene and vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylic Latex, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylic Latex, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, allylglycidyl Ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, trifluoroethyl acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylic Yate and perfluorooctylethyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl (meth) acrylamide And amino such as N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactone and N- (meth) acryloyl morpholine. .

The copolymerization ratio of a) and b) is preferably 5:95 to 40:60 by weight, and more preferably 10:90 to 35:65. If the copolymerization ratio of a) is less than 5, alkali developability will fall and it will become difficult to form a pattern. When the copolymerization ratio of a) is larger than 40, the alkaline phenomenon of the photocured portion is easily promoted, and it is difficult to keep the line width constant.

The preferred molecular weight of the carboxyl group and the ethylenically unsaturated group-containing acrylic acid copolymer is preferably in the range of 1000 to 500,000, more preferably 3000 to 200,000, based on gel permeation chromatography (GPC) with respect to the weight average molecular weight on the basis of polystyrene. At less than 1000, the film strength is significantly lowered. When it exceeds 500,000, alkaline solubility (developability) falls remarkably.

The ethylenically unsaturated group containing monomer and polymer mentioned above can be used in combination of 2 or more different form.

3- (2) binder resin

The photopolymerizable composition of the present invention comprises a binder resin having no ethylenically unsaturated group. Although the said epoxy resin, polyester resin, and urethane resin can be mentioned as said binder resin, In a resist use, a carboxyl group-containing acrylic acid copolymer is especially preferable. As said acrylic acid copolymer, the said carboxyl group-containing acrylic acid copolymer (AP-B) can be enumerated, As a preferable AP-B copolymer, the thing before reacting the compound which has ethylenically unsaturated group to the side chain of said AP-A can be enumerated. have.

3- (3) coloring pigment

When the photopolymerizable composition of the present invention is used as a color filter, it contains a colored pigment. As the color of the color filter, a red, green, and blue mixed color mixture system, a cyan, magenta, and black navy blue color mixture system used in the yellow matrix portion are mainly used. When a dye and a pigment are used as a coloring agent, it is preferable to use a pigment from a viewpoint of heat resistance, light resistance, etc. Obtain an appropriate spectrum and use a combination of two or more pigments, for example, a suitable spectrum can be obtained by combining cyan pigment and violet pigment to obtain blue color, combining green pigment and yellow pigment to obtain green color, red pigment and yellow or The orange pigment is combined to give a red pigment.

The following can be enumerated as the coloring pigments used in the present invention, and are represented by color index numbers. CIPigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, 168, CIPigemtnt Orange 36, 43, 51, 55, 59, 61, CIPigemtnt Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228 , 240, CIPigemtnt Violet 19, 23, 29, 30, 37, 40, 50, CIPigemtnt Blue 15, 15: 1, 15: 4, 15: 6, 22, 60, 64, CIPigemtnt Green 7, 36, CIPigemtnt Brown 23, 25, 26

Examples of the black pigment include carbon black, titanium black, and the like, and specific examples of the carbon black include Black 4, Special Black 100, Special Black 250, Special Black 350 Special Black 550, Colombia Carbon Raven 1040, and Raven 1060 made by Degussa. , Raven 1080 and Raven 1255, manufactured by Mitsubishi Chemical, MA7, MA8, MA11, MA100, MA220, and MA230.

3- (4) Other Ingredients

In the photopolymerizable composition of the present invention, in order to provide applicability, it is preferable to adjust the viscosity by using a solvent. Examples of the solvent include methanol, ethanol, toluene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, xylene, ethylbenzene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, isoamyl acetate, ethyl lactate, methyl ethyl ketone, acetone, cyclohexane and the like. Or two or more types can be used in combination.

Preparation of 3- (5) Photopolymerizable Composition

When the photopolymerizable composition of the present invention contains a pigment, the above-mentioned components are mixed using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, an attritor, a ball mill, a kneader, a paint shaker, and the like. Can be prepared. In order to suppress gelation by the polymerization reaction at the time of dispersion, a polymerization initiator may be added, or a monomer or a photoinitiator may be added after pigment dispersion. Appropriate dispersing aids may be added to satisfy the dispersion of the pigment. Dispersion aids facilitate the dispersion of the pigment and have the effect of inhibiting reagglomeration after dispersion.

The present invention will be described by way of examples, but the present invention is not limited by these examples.

Synthesis Example

Synthesis of Biimidazole Compounds

Synthesis Example 1 2,2'-bis (2-chlorophenyl) -4,4'-5,5'-tetrakis (4-methylphenyl) -1,2'-biimidazole (abbreviated as MHABI)

4,4'-dimethylbenzyl (product of Tokyo Kasei Kogyo Co., Ltd.) 27.50 g (115 mmol), o-chlorobenzaldehyde (product of Tokyo Kasei Kogyo Co., Ltd.) 16.25 g (116 mmol), ammonium acetate ( A mixture of 69.45 g (901 mmol) of acetic acid (product of Junsei Chemicals Co., Ltd.) and 450 g of acetic acid (product of Junsei Chemicals Co., Ltd.) was charged to a 1 L volumetric flask, and the mixture was stirred at 117 ° C. for 5 hours. . After cooling the reaction mixture, 2-chlorophenyl-4,5-bis (4-methylphenyl) imidazole was precipitated while slowly adding 2 L of stirred deionized water. 2-chlorophenyl-4,5-bis (4-methylphenyl) imidazole was filtered and washed, dissolved in 500 g of methylene chloride (manufactured by Junsei Chemicals Co., Ltd.), and the solution in a 2 L volume four-necked flask. Was added and cooled to 5-10 ° C. Stir a mixture of 117.6 g (357 mmol) of potassium ferricyanide (product of Junsei Chemicals Co., Ltd.), 44.7 g of sodium hydroxide (product of Junsei Chemicals Co., Ltd.) and 600 g of deionized water over 1 hour. It added while making it react at room temperature for 18 hours. The reaction mixture was washed with three times deionized water, and then dehydrated with about 50 g of anhydrous magnesium sulfate (product of Junsei Chemicals Co., Ltd.), and methylene chloride was distilled off under reduced pressure to obtain MHABI crystals. MABHI was recrystallized from ethanol (product of Junsei Chemicals Co., Ltd.), filtered and dried to give 36.5 g (yield 88.7%) of pale yellow crystals.

The chemical formula of MHABI obtained is C ₄₆ H ₃₆ N ₄ C ₂ , and molecular weight is 715.70.

Structural analysis

(1) ¹ H-NMR

¹ H-NMR of MHABI is shown in FIG. ¹ H-NMR was measured in heavy chloroform using JNM-AL400 manufactured by JEOL.

(2) ¹³ C-NMR

¹³ C-NMR of MHABI is shown in Figs. ¹³ C-NMR was measured in heavy chloroform using AMX400 from Bruker. Characteristic chemical shifts are assigned.

21.0, 21.2, 21.5, 21.6 ppm: Carbon atom of methyl group at 24, 25, 24 ', 25'

110.7 ppm: Carbon atom at 2 '

(3) mass spectrometry

Mass spectrometry of MHABI was measured using JEOL's JMS-SX102A. The chart is shown in FIG. The molecular weight of MHABI was 715.69 and the molecular ion peak was detected at 714. This value was consistent with the molecular weight of MHABI when it did not contain isotopes of each atom of each atom.

(4) melting point

The melting point was measured by Buchi using a Model 510 melting point measuring apparatus. The MHABI had a melting point of 211 ° C.

Synthesis of Binder Resin

Synthesis Example 2: Carboxyl group-containing acrylic acid copolymer (AP-B), AP-1: 25% by weight solution of carboxyl group-containing acrylic acid copolymer (solvent: propylene glycol methyl ether acetate, abbreviated as PGMEA, Tokyo Kasei Kogyo Co., Ltd Product of.)

11.25 parts by weight of methacrylic acid (hereinafter abbreviated as MAA, product of Kyoeisha Chemical Co., Ltd.) to a four-necked flask equipped with a dropping funnel, thermometer, cooling tube, stirrer and nitrogen introduction tube, and methyl methacrylate (hereinafter MMA) Furnace abbreviation, produced by Kyoeisha Chemical Co., Ltd.) 15.00 parts, n-butyl methacrylate (hereinafter abbreviated as BMA) 41.25 parts by weight, 2-hydroxyethyl methacrylate (hereinafter abbreviated as HMEA, Kyoeisha Chemical Co. 7.50 parts by weight and 210.0 parts by weight of PGMEA were added and nitrogen-substituted in the four-necked flask for 1 hour. After heating to 90 ° C., 11.25 parts by weight of MAA, 15.00 parts by weight of MMA, 41.25 parts by weight of BMA, 7.50 parts by weight of HEMA (0.0776 moles), 210.0 parts by weight of PGMEA and 2,2′-azobisisobutyronitrile (by AIBN) Abbreviation, product of Pure Chemical Industries, Ltd.) 3.20 parts by weight was added dropwise over 1 hour. After polymerization for 3 hours, the mixture was heated to 100 ° C, a mixture of 1.0 parts by weight of AIBN and 30.0 parts by weight of PGMEA was added, and polymerization was performed for 1.5 hours to obtain a carboxyl group-containing acrylic acid copolymer (AP-1). The weight average molecular weight (measurement of GPC, polystyrene basis) of AP-1 was 26,000.

Synthesis of ethylenically unsaturated group-containing compound

Synthesis Example 3 Acrylic Acid Copolymer (AP-A) Containing Carboxyl Group and Ethylenically Unsaturated Group,

AP-2: 26 wt% solution of carboxyl group- and ethylenically unsaturated group-containing acrylic acid copolymer (solvent: PGMEA)

600 parts by weight of the carboxyl group-containing acrylic acid copolymer AP-1, 8.8 g of 2-methacryloyloxyoxyethyl isocyanate (Karenz MOI, product of Showa Denko KK) in a four-necked flask equipped with a thermometer, a cooling tube, a stirrer, and a nitrogen introduction tube; 0.36 g of dibutyltin dilaurate (product of Tokyo Kasei Kogyo Co., Ltd.) was added and the reaction was carried out at 60 ° C. for 3 hours while bubbling air, and then the reaction mixture was cooled to obtain AP-2.

Synthesis Example 4 60% by weight solution of carboxyl group-containing epoxy acrylate (EA) and EA-1: carboxyl group-containing epoxy acrylate (solvent: diethylene glycol monoethyl ether acetate)

Cresol- novolac epoxy resin (EPOTOTO YDCN-704, epoxy equivalent: 210, softening point 90 ° C, products of Toto Chemical Co., Ltd.) 210 parts by weight, acrylic acid (product of Tokyo Kasei Kogyo Co., Ltd.) 72 weights Part, 0.28 parts by weight of hydroquinone (product of Tokyo Kasei Kogyo Co., Ltd.), 232.6 parts by weight of diethylene glycol monoethyl ether acetate (product of Tokyo Kasei Kogyo Co., Ltd.), and then the mixture was After heating to make sure that the mixture was dissolved uniformly, 1.4 parts by weight of triphenylphosphine (product of Tokyo Kasei Kogyo Co., Ltd.) was added thereto, and the mixture was heated to 100 ° C. and reacted for approximately 30 hours to give an acid value. A reaction mixture of 0.5 mg KOH / g was obtained. 66.9 parts by weight of tetrahydrophthalic anhydride was added to the mixture, and the mixture was heated to 90 ° C and reacted for approximately 6 hours to confirm the loss of absorption of acid anhydride in IR (infrared absorption spectrum), and the acid value of 70 mgKOH / g, solid content concentration. 60.0% of carboxyl group-containing epoxy acrylate resin EA-1 was obtained.

Evaluation of Photopolymerizable Compositions

Reagents

Ethylenically unsaturated group-containing compound (monomer)

Dipentaerythritol hexaacrylate: Product of Toa Gosei Co., Ltd.

Photopolymerization Initiator

1) EMK (4,4'-bis (N, N-diethylamino) benzophenone: product of Hodogaya Chemical Co., Ltd.)

2) HABI (2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole: product of Hodogaya Chemical Co., Ltd.)

3) MN3M (tetra-n-butylammonium methyltris (4-methylnaphthyl) borate): synthesized by the process described in Japanese Unexamined Patent Publication HEI No.11-222489

4) TPMP (trimethylolpropane tris (3-mercaptopropionate)): Product of Yodo Kagaku Co., Ltd.

5) Dimedone: Product of Tokyo Kasei Kogyo Co.Ltd.

Pigment

1) Carbon Black: Special Black 4, product of Degussa

Other ingredients

1) PGMEA (propylene glycol monomethyl ether acetate): product of Tokyo Kasei Kogyo Co., Ltd.

2) cyclohexane: product of Wako Pure Chemical Industries, Ltd.

3) FLOWLEN DOPA-33: dispersant, amino group-containing acrylic acid copolymer, solid content concentration: 30% by weight, main solvent: cyclohexanone, product of Kyoeisha Chemical Co., Ltd.

Preparation of Photopolymerizable Composition

Example 1

Acrylic copolymer AP-1 (49.0 parts by weight of solids, 147 parts by weight of solvent), 65.0 parts by weight of Special Black 4, FLOWLEN DOPA-33 (dispersant: product of Kyoeisha Chemical Co., Ltd.) 21.7 parts by weight (6.5 parts by weight of solids) Part (15.2 parts by weight of solvent) and 200.0 parts by weight of cyclohexanone were mixed and dispersed for 3 hours using a paint conditioner (manufactured by Asada Iron Works Co., Ltd.).

35.0 weight part of ethylenically unsaturated group containing compound EA-1 (solid content 21.0 weight part, solvent content 14.0 weight part), dipentaerythritol hexaacrylate, and 38.5 weight part of 4,4'-bis (N, N-) to the said dispersion liquid 5.0 parts by weight of diethylamino) benzophenone (hereinafter abbreviated as "EMK"), 15.0 parts by weight of MHABI, 15.0 parts by weight of TPMP and 600.0 parts by weight of cyclohexanone were added and dissolved. The composition was filtered with a 0.8 μm pore filter (Kiriyama filter paper for GFP) to obtain a photopolymerizable composition of the present invention. The physical properties of the obtained photopolymerizable composition were evaluated by the following method. The results are shown in Table 1.

Example 2, Comparative Examples 1,2

Example 2 and Comparative Examples 1 and 2 were carried out in the same manner as in Example 1 except as listed in Table 1. The physical properties of the obtained photopolymerizable property were evaluated in Example 1. The results are shown in Table 1.

Assessment Methods

(1) Remnant sensitivity

The obtained photopolymerizable composition was spin-coated on a glass substrate (100 x 100 mm) so as to have a dry film thickness of about 1.5 mu m, dried at room temperature for 30 minutes, and then vacuum dried at room temperature for 10 minutes. Accurately measure the film thickness of the film after dry coating with a film thickness meter (SURFCOM130A, manufactured by Tokyo Seimitsu Co., Ltd.), and then use an ultra-high pressure mercury lamp ("Multilight ML-251A / B", manufactured by Ushio, Inc.). The exposure amount was changed through a quartz photomask, and the photopolymerizable composition was irradiated with light to photocure. The exposure amount was measured using an ultraviolet integrating photometer (brand name "UIT-150", light receiving part "UVD-S365", manufactured by Ushio Inc.). A5, 10, 30, 50, 70, 100 µm line / space patterns were formed on the quartz photomask used. The gap between the photomask and application was adjusted to 100 μm. The exposed film was alkali developed for a predetermined time with 0.1% sodium carbonate solution (25 ° C.). The development time was adjusted to 1.5 times the time: tD in which the film before exposure completely dissolved the film by alkali development. In addition, as time tD, the experiment which observes the extent of melt | dissolution of a film by changing alkali developing time was repeated, and time until the film melt | dissolved completely was determined as tD. After the alkali development, the glass substrate was washed and dried by air dispersion, the film thickness of the remaining film (resist soup) was measured, and the residual film ratio was calculated. The remaining film ratio was calculated by the following formula.

Residual film ratio (%) = 100 × (film thickness after alkali development) / (film thickness before alkali development)

The exposure amount was changed to perform the same photocuring operation, the relationship between the exposure amount and the residual film rate was plotted on a graph, and the exposure amount (mJ / cm ² ) at which the residual film rate reached saturation was obtained, which was defined as the residual film sensitivity. Smaller values indicate higher sensitivity.

(2) Sublimation at the time of the post baking

The obtained photopolymerizable composition was spin-coated on a glass substrate (100 x 100 x 1 mm) so as to have a dry film thickness of about 1.5 mu m, dried at room temperature for 30 minutes, and then vacuum dried at room temperature for 10 minutes. Further, using the exposure apparatus, light was cured by irradiating light of 100 mJ / cm ² . The obtained board | substrate was put into the dish, the dish was put on the hotplate, and it heated. A stainless steel substrate (200 × 200 × 1 mm) was placed on the dish, and a moisture-containing dish was placed thereon to cool the stainless steel substrate. After heating the glass substrate at 230 ° C. for 30 minutes on a hot plate, the sublimation induced on the cured film deposited on the stainless steel substrate was observed under an optical microscope (VH-Z250, manufactured by Keyence Corporation), and the presence or absence of crystallization Was judged visually. The results are shown in Fig. 5 (Example 1) and Fig. 6 (Comparative Example 1). When HABI is used, it shows that crystals (birds in the shape of birds in Fig. 6) are formed, but when MHABI is used, no crystals are observed.

Table 1

* 1: Methacrylic acid / methyl methacrylate / n-butyl methacrylate / 2-hydroxyethyl methacrylate = 15/20/55/10 (weight ratio) copolymer Mw = 26,000 solid content concentration 25 weight% solvent PGMEA

* 2: Acrylic acid copolymer solid content concentration 26weight% solvent PGMEA which added 2-isocyanate ethyl methacrylate to AP-1

* 3: Carboxyl group-containing cresol novolac epoxy acrylate, solid content concentration: 60% by weight, acid value: 70 mgKOH / g

* 4: FLOWLEN DOPA-33 ^{* 4} : Dispersant, amino-group-containing acrylic acid copolymer, solid content concentration: 30 weight%, main solvent: cyclohexanone

* 5: Special Black 4

* 6: 4,4'-bis (N, N-diethylamino) benzophenone

* 7: 2,2'-bis (2-cyclophenyl) -4,4'-5,5'-tetrakis (4-methylphenyl) -1,2'-biimidazole

* 8: 2,2'-bis (2-cyclophenyl) -4,4'-5,5'-tetrakis-1,2'-biimidazole

* 9: tetra-n-butylammonium methyltris (4-methylnaphthyl) borate

* 10: trimethylolpropane tris (3-mercaptopropionate)

The novel hexaarylbiimidazole compounds of the present invention have low thermal sublimation properties, and when used as a component of a photoinitiator composition in a photosensitive composition, a sublimation product can be obtained during post-baking in a resist manufacturing process such as a color filter. Does not occur. Therefore, problems such as adhesion of the sublimate generated in the exhaust duct and dropping of the deposit on the resist, which frequently occur when a photosensitive composition containing a conventional photopolymerization initiator is used, can be suppressed.

The photoinitiator composition of the present invention using the above-described hexaarylbiimidazole compound is used in the production of photopolymerizable compositions used as various resists such as solder resists, etching resists, photoresists, especially color filters used in color liquid crystal display devices, cameras, and the like. It is effective in the photopolymerization composition which is preferably used as the color filter resist used.

Claims (8)

Hexaarylbiimidazole compounds defined by the following formula (1): Here, each R ₁ is a halogen atom, and each R ₂ is an optionally substituted alkyl group having 1 to 4 carbon atoms. Hexaarylbiimidazole compounds defined by the following formula (2): The method of using hexaarylbiimidazole according to claim 1 or 2, which is used as an optical radical generating agent. The photoinitiator composition according to claim 1, which contains a hexaarylbiimidazole compound. The photoinitiator composition according to claim 4, which contains at least one compound selected from the group consisting of benzophenone compounds, thioxanthone compounds and ketocomarin compounds. The photoinitiator composition according to claim 4, which contains a thiol compound and / or a dicarbonyl compound defined by the following formula (3) as a hydrogen donor for the hexaarylbiimidazole compound: Wherein R ₃ and R ₄ are each independently optionally substituted alkyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted aralkyl, optionally substituted aryl, optionally substituted aryloxy or polymerization It may be an organic group having a unsaturated unsaturated group or a polymer compound residue, or R ₃ and R ₄ may be bonded together to form a ring. R ₅ is a hydrogen atom, optionally substituted alkyl, optionally substituted aralkyl or optionally substituted aryl. A photopolymerizable composition comprising at least the following components: (A) The photoinitiator composition of any one of Claims 4-6. (B) Compound of ethylenically unsaturated group A photopolymerizable composition for color filter resists comprising at least the following components: (A) The photoinitiator composition of any one of Claims 4-6; And (B) Compound of ethylenically unsaturated group