KR20190024810A - Photosensitive composition, method for forming cured product, cured product, panel for display device, and display device - Google Patents

Abstract

The purpose of the present invention is to provide a photosensitive composition which enables a desirable cross-sectional shape of a formed pattern to be compatible with the formation of a pattern that is favorably adhered to a substrate even in a low exposure amount although the photosensitive composition contains a lactam-based pigment; a method of forming a cured product using the photosensitive composition; the cured product of the photosensitive composition; a panel for an image display device, which includes a black matrix or a black column spacer composed of the cured product; and an image display device including the panel for an image display device. The photosensitive composition of the present invention comprises a photopolymerization initiator (A) and a lactam-based pigment-containing coloring agent (C), wherein the photopolymerization initiator (A) comprises a combination of two or more oxime ester compounds which have peaks in a wavelength range of 320 nm or more to less than 400 nm in an absorption spectrum, and in which maximum wavelengths of the peaks are different from each other, but does not comprise a compound which exhibits a gram absorption coefficient of 10 or more at one wavelength in a wavelength range of 400 nm or more.

Description

[0001] The present invention relates to a photosensitive composition, a method for forming a cured product, a cured product, a panel for an image display device, and an image display device.

The present invention relates to a photosensitive composition, a cured product forming method using the photosensitive composition, a cured product formed using the photosensitive composition, a panel for an image display device having a black matrix or a black column spacer made of the cured product, And an image display apparatus having a panel for an apparatus.

In a panel for a display device such as a liquid crystal display, a material such as an insulating film or a spacer needs to efficiently transmit light generated from a light source such as a backlight. For this reason, in order to form a pattern of an insulating film or a spacer, a photosensitive composition which gives a transparent cured film by exposure is used. By selectively exposing such a photosensitive composition, a pattern of a transparent cured film can be formed.

In addition, in the panel for a display device, a patterned light shielding film such as a black matrix or a black column spacer is often formed. Various photosensitive compositions containing a light-shielding agent and a photopolymerization initiator, which are used for forming a light-shielding film in such applications, have also been proposed.

In addition, in such applications, a lactam-based pigment may be incorporated in the photosensitive composition in that the light-shielding property of visible light and the transparency of near-infrared light are excellent.

By virtue of the above-mentioned advantages of the lactam-based pigment, the photosensitive composition containing the lactam-based pigment can be used not only for forming a patterned light-shielding film such as a black matrix or a black column spacer, And the like.

For example, as the photosensitive composition containing a lactam-based pigment, it is possible to use a pigment comprising (A) a pigment containing a lactam pigment, (B) a resin having an alkaline group, an alkali-soluble group and an ethylenic unsaturated group, (C) , And (D) an organic dye having a sulfonic acid group or an organic dye having a sulfonic acid group (see Patent Document 1).

Japanese Patent Laid-Open Publication No. 2016-109763

However, when a photosensitive composition comprising a compound having a lactam-based pigment and an ethylenically unsaturated group and a photopolymerization initiator is patterned by photolithography, it is possible to form a pattern well adhering to the substrate at a low exposure dose, There is a problem that compatibility is difficult.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a photosensitive composition capable of satisfactorily adhering closely to a substrate at a low exposure dose and a favorable cross- A method of forming a cured product using the photosensitive composition, a cured product of the photosensitive composition, and a black matrix or black column spacer made of the cured product, and a panel for the image display device And a method for adhering an object to be adhered using the photosensitive composition described above to a photosensitive adhesive composition comprising the photosensitive composition described above.

The present inventors have found that, in a photosensitive composition comprising a photopolymerization initiator (A) and a colorant (C) containing a lactam-based pigment, a peak in a wavelength range of 320 nm or more and less than 400 nm in a light absorption spectrum as a photopolymerization initiator (A) (A) a compound which exhibits an extinction coefficient of 10 or more at any one wavelength in a wavelength region of 400 nm or more, is used as the photopolymerization initiator The above problems can be solved and the present invention has been accomplished.

A first aspect of the present invention is a photosensitive composition comprising a photopolymerization initiator (A) and a colorant (C)

The photopolymerization initiator (A) contains two or more oxime ester compounds having a peak in a wavelength region of 320 nm or more and less than 400 nm in a light absorption spectrum,

Wherein the photopolymerization initiator (A) does not contain a compound exhibiting a gravimetric extinction coefficient of 10 or more at any one wavelength in a wavelength region of 400 nm or more,

The maximum wavelengths of the peaks with respect to two or more kinds of oxime ester compounds are different from each other,

The colorant (C) is a photosensitive composition containing a lactam pigment.

According to a second aspect of the present invention,

A method of forming a coating film using the photosensitive composition according to the first aspect,

Exposure to a coating film

Of the cured product.

A third aspect of the present invention is a cured product of the photosensitive composition according to the first aspect.

A fourth aspect of the present invention is a black matrix or black column spacer made of the cured product according to the third aspect.

A fifth aspect of the present invention is a panel for an image display apparatus comprising a black matrix or a black column spacer according to the fourth aspect.

A sixth aspect of the present invention is the image display device having the image display panel according to the fifth aspect.

A seventh aspect of the present invention is a photosensitive adhesive comprising the photosensitive composition according to the first aspect.

According to an eighth aspect of the present invention,

As a method for bonding an adherend surface,

An adhesive layer made of a photosensitive adhesive according to the seventh aspect is formed on one or both sides of the opposing adhered surfaces,

And curing the adhesive layer by exposure.

According to the present invention, it is possible to provide a photosensitive composition capable of satisfactorily forming a pattern closely adhering closely to a substrate at a low exposure dose and a favorable cross-sectional shape of a formed pattern in spite of containing a lactam-based pigment, A panel for an image display apparatus comprising a cured product forming method, a cured product of the photosensitive composition, and a black matrix or a black column spacer made of the cured product, an image display apparatus including the image display panel, It is possible to provide a method of bonding a photosensitive adhesive made of a photosensitive composition and an object to be adhered using the above photosensitive composition.

Fig. 1 is a schematic view showing a cross-sectional shape in the width direction of a pattern formed using a photosensitive composition, Fig. 1 (a) is a cross-sectional view of a typical pattern, Fig.

&Quot; Photosensitive composition &

The photosensitive composition according to the present invention comprises a photopolymerization initiator (A) and a colorant (C) containing a lactam-based pigment.

The photopolymerization initiator (A) includes two or more kinds of oxime ester compounds having peaks in the wavelength range of 320 nm or more and less than 400 nm in the light absorption spectrum.

However, the maximum wavelength of the peak is different for two or more oxime ester compounds.

Therefore, when the photosensitive composition is subjected to exposure, it is easy to sufficiently utilize the exposure light, so that the photosensitive composition is excellent in sensitivity. As a result, even if the photosensitive composition contains the lactam-based pigment, it is considered that the formation of the pattern closely adhering to the substrate at a low exposure dose and the preferable cross-sectional shape of the formed pattern are easy to be compatible with each other.

In the case where λ _max-r is the maximum wavelength at the longest wavelength side and λ _max-b is the maximum wavelength at the shortest wavelength side among the maximum wavelengths of the above peaks for two or more oxime ester compounds, λ _max-r And? _Max-b is 20 nm or more. The upper limit is, for example, 70 nm or less, preferably 50 nm or less.

It is also preferable that? _Max-r is in a range of 350 nm or more and 400 nm or less, and? _Max-b is in a range of 320 nm or more and 360 nm or less.

In this case, even when the wavelength range of the exposure light used for exposure of the photosensitive composition is wide, the energy of the exposure light is easily used for curing efficiently, and good sensitivity can be easily achieved regardless of the type of the light source.

The photopolymerization initiator (A) does not contain a compound exhibiting a gravimetric extinction coefficient of 10 or more at any one of the wavelength regions of 400 nm or more. It is preferable that the photopolymerization initiator does not contain a compound exhibiting a gravimetric extinction coefficient of 5 or more at any one of the wavelength regions of 400 nm or more and more preferably does not contain a compound exhibiting a gravimetric extinction coefficient of 1 or more.

When the photopolymerization initiator (A) contains a compound exhibiting a gravimetric extinction coefficient of 10 or more at any one of the wavelength regions of 400 nm or more, the light transmittance of the photosensitive composition tends to be low.

For this reason, the sensitivity as a photosensitive composition may be lowered, or it may be difficult to form a pattern having a desired height by halftone exposure.

However, the above-mentioned photosensitive composition is excellent in light transmittance because it does not contain a compound exhibiting a light absorption coefficient of 10 or more at any wavelength out of a wavelength range of 400 nm or more as a photopolymerization initiator (A). As a result, it is easy to sufficiently utilize the exposure light, and it is easy to form a pattern having a desired height by the halftone exposure.

Further, when the photosensitive composition is used as a photosensitive adhesive, the photosensitive adhesive is often applied in a large thickness. However, since the photosensitive adhesive composed of the photosensitive composition containing the photopolymerization initiator (A) has excellent light transmittance as described above, the photosensitive adhesive is cured well even when it is thickly coated.

When a pattern is formed by halftone exposure using the photosensitive composition described above, a sufficient height difference between the FT-exposed portion and the halftone exposed portion can easily be obtained in the formed pattern.

When a black column spacer is formed on a display panel, a TFT or the like may be disposed on the surface on which the black column spacer is formed. In this case, considering the height of the TFT, it is preferable to perform halftone exposure using a mask having a full tone part and a half tone part, and to form the black column spacer having different heights by one exposure.

For this reason, the photosensitive composition is suitably used for forming black column spacers differing in height by halftone exposure.

As described above, the photopolymerization initiator (A) includes a combination of two or more photopolymerization initiators. However, as described above, the photopolymerization initiator (A) essentially comprises two or more oxime ester compounds. The content of each photopolymerization initiator contained in the photopolymerization initiator (A) is not particularly limited within the range not hindering the object of the present invention.

The ratio of the content of each photopolymerization initiator to the mass of the photopolymerization initiator (A) is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 20% Do.

The ratio of the content of each photopolymerization initiator to the mass of the photopolymerization initiator (A) is preferably 99 mass% or less, more preferably 95 mass% or less, even more preferably 90 mass% or less, and 80 mass% Particularly preferred.

The ratio of the content of the oxime ester compound having? _Max-r to the mass of the photopolymerization initiator (A) is preferably 1% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 95% , More preferably 10 mass% or more and 90 mass% or less, and particularly preferably 15 mass% or more and 80 mass% or less.

The ratio of the content of the oxime ester compound having? _Max-b to the mass of the photopolymerization initiator (A) is preferably from 1% by mass to 99% by mass, more preferably from 5% by mass to 95% by mass, More preferably not less than 90% by mass, and particularly preferably not less than 20% by mass and not more than 85% by mass.

The ratio of the content of other oxime ester initiators having a maximum wavelength not greater than? _Max-r and? _Max-b in the range of from 320 nm to less than 400 nm with respect to the mass of the photopolymerization initiator (A) is 0 mass% More preferably 0 mass% or more and 90 mass% or less, still more preferably 0 mass% or more and 80 mass% or less, and particularly preferably 0 mass% or more and 65 mass% or less.

When the photopolymerization initiator (A) is composed of the first oxime ester compound and the second oxime ester compound, the ratio M1 / M2 of the mass M1 of the first oxime ester compound and the mass M2 of the second oxime ester compound is 1/9 or more More preferably not less than 9/1, more preferably not less than 2/8 and not more than 8/2, and particularly preferably not less than 3/7 and not more than 7/3.

Hereinafter, each component contained in the photosensitive composition will be described.

≪ Photopolymerization initiator (A) >

As described above, the photopolymerization initiator (A) contains two or more kinds of oxime ester compounds having a peak in the wavelength range of 320 nm or more and less than 400 nm in the absorption spectrum.

The photopolymerization initiator (A) does not contain a compound exhibiting a gravimetric extinction coefficient of 10 or more at any one of the wavelength regions of 400 nm or more.

The photopolymerization initiator (A) may contain other photopolymerization initiators other than oxime ester compounds. The amount of the oxime ester compound in the photopolymerization initiator (A) is preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, further preferably 90 mass% or more, Or more, particularly preferably 100% by mass or more.

When the photopolymerization initiator (A) contains other photopolymerization initiators other than oxime ester compounds, the photopolymerization initiator (A) may contain two or more kinds of other photopolymerization initiators.

Other photopolymerization initiators other than the oxime ester compound are known photopolymerization initiators, and compounds having a light absorption coefficient of 10 or more at any one of the wavelength regions of 400 nm or more can be used.

Specific examples of well-known photopolymerization initiators other than the oxime ester compound include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl- beta -methoxyethyl acetal, benzyldimethyl Ketoxylic acid, ketal, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethyl anthraquinone, octamethylanthraquinone, , 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o- (O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- , 5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (that is, Ton), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, Benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethyl Acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, p-tert- butyltrichloroacetophenone, p- Dichloroacetophenone,?,? -Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- Propane, p-methoxy Triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloro (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl- - (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis- trichloromethyl-6- , 2,4-bis-trichloromethane 6 and the like (2-bromo-4-methoxy) styryl phenyl -s- triazine.

Other photopolymerization initiators can be selected from these groups of compounds after measuring the gram extinction coefficient in the wavelength region of 400 nm or more.

The combination of a plurality of oxime ester compounds in the photopolymerization initiator (A) is not particularly limited as long as the above-mentioned conditions for the photopolymerization initiator (A) are satisfied.

A preferred combination of the oxime ester compound is a combination of the oxime ester compound (A1) represented by the formula (a1) described below and the oxime ester compound (A2) represented by the formula (a2) described later.

The photopolymerization initiator (A) may contain one or more oxime ester compounds (A1) and one or more oxime ester compounds (A2).

Hereinafter, the oxime ester compound (A1) and the oxime ester compound (A2) will be described.

[Oxime ester compound (A1)]

The oxime ester compound (A1) is represented by the following formula (a1):

However,

(In the formula (a1), R ¹ is a monovalent organic group, R ² is a hydrocarbon group which may have a substituent, or a heterocyclyl group which may have a substituent, R ³ is a monovalent organic group, and R ⁴ R ⁵ and R ⁶ are each independently a benzene ring which may have a substituent or a naphthalene ring which may have a substituent and m 1, m 2 and m 3 are each 0 or 1.)

(1) to (3):

(1) R ¹ includes a group represented by -OR ⁷ , and R ⁷ is a halogenoalkyl group.

(2) m2 is 1, R ⁴ comprises a group represented by -OR ⁷ , and R ⁷ is a halogenoalkyl group.

(3) R ³ is a branched chain alkyl group which may have a substituent.

≪ / RTI >

In formula (a1), R ⁵ and R ⁶ are a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.

The ring containing the nitrogen atom bonded to R ³ in the formula (a1), the benzene ring or the naphthalene ring is condensed by sharing any carbon-carbon bond in the benzene ring or the naphthalene ring.

Therefore, in the formula (a1), the ring containing the nitrogen atom bound to R ³ is a ring-constituting atom in which a nitrogen atom, two carbon atoms derived from R ⁵ , and two carbon atoms derived from R ⁶ Five-membered ring.

That is, the compound represented by the formula (a1) has R ⁵ and R ⁶ and a triple to five-membered condensed ring composed of the above-mentioned 5-membered rings as a central skeleton.

When R ⁵ and / or R ⁶ is a naphthalene ring, the form of the condensation of the naphthalene ring with the above-mentioned 5-membered ring containing a nitrogen atom bonded to R ³ is not particularly limited.

When at least one of R ⁵ and R ⁶ is a naphthalene ring, the condensed ring composed of the above-mentioned 5-membered ring containing R ⁵ and R ⁶ and a nitrogen atom bonded to R ³ may be any of the following.

[Figure 2]

When the benzene ring or naphthalene ring as R ⁵ and R ^{6 has} a substituent, the kind and number of the substituent are not particularly limited as long as they do not impair the object of the present invention.

Suitable examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, A saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group of 1 to 6 carbon atoms, a dialkylamino group having an alkyl group of 1 to 6 carbon atoms, a morpholin-1-yl group , A piperazin-1-yl group, a halogen atom and a cyano group.

When the benzene ring or naphthalene ring as R ⁵ and R ^{6 has} a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, and is preferably 1 or more and 4 or less. When plural substituents are present, plural substituents may be the same or different.

When R ⁵ has a substituent, the substituent of R ⁵ may be combined with R ¹ or R ³ to form a ring.

When R ⁶ has a substituent, the substituent of R ⁶ may be combined with R ³ to form a ring.

The substituent of R ⁵ and the ring formed by combining R ¹ may be a hydrocarbon ring or a heterocyclic ring. The hetero atom contained in the heterocyclic ring is not particularly limited. Preferred heteroatoms include N, O, S, and the like.

The ring formed by combining the substituent group of R ⁵ and / or R ⁶ with R ³ may contain other heteroatoms in addition to the nitrogen atom bonded to R ³ . The hetero atom contained in the heterocyclic ring is not particularly limited. Preferred heteroatoms include N, O, S, and the like.

And the substituent or substituents R ⁶ is R ⁵ having having, R ³ form a ring if this bond, a compound represented by the formula (a1), the formula (a1-1-a) ~ (a1-1- h):

[Figure 3]

(Formula (a1-1-a) ~ (h in-a1-1), R ^1, R ^2, R ^4, m1, m2 and m3 are the same, and the formula (a1), R ⁸ is an alkyl group.)

Are preferred.

The alkyl group as R ⁸ may be straight chain or branched chain. The number of carbon atoms of the alkyl group as R ⁷ is not particularly limited and is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less.

When a substituent of R ⁵ is bonded to R ¹ to form a ring, m ¹ is preferably 0 in formula (a1). In this case, the compound represented by the formula (a1) is a compound represented by the following formulas (a1-1-i) to (a1-1-l)

[Figure 4]

(Wherein R ² , R ³ , R ⁴ , m 2 and m 3 are the same as in formula (a1), and R ⁸ is an alkylene group having 1 to 20 carbon atoms Lt; / RTI >

Are preferred. The alkyl group as R ⁸ may be straight chain or branched chain.

By considering the above described preferred combination of R ⁵ and R ^6, the compound represented by the formula (a1) is of formula (I-a1) ~ (IV-a1):

[Figure 5]

(Wherein (a1-I) ~ (from ^{a1-IV), R 1,} R 2, R 3, R 4, m1, m2 and m3 is the same as the formula (a1).)

Is more preferably a compound represented by formula (a1-II) or a compound represented by formula (a1-III), and particularly preferably a compound represented by formula (a1-III).

The compounds represented by the above formulas (a1-I) to (a1-IV) are preferably compounds represented by the following formulas (a1-Ia) to (a1-IV- ) Or a compound represented by the formula (a1-III-a) is more preferable, and a compound represented by the formula (a1-III-a) is particularly preferable.

[6]

The compounds represented by the above formulas (a1-Ia) to (a1-IV-a) are preferably compounds represented by the following formulas (a1-Ib) to (a1-IV- -b), or a compound represented by the formula (a1-III-b) is more preferable, and a compound represented by the formula (a1-III-b) is particularly preferable.

[Figure 7]

Examples of suitable monovalent organic groups suitable as R ¹ include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyl group which may have a substituent A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, A heterocyclylcarbonyl group which may have a substituent, an amino group substituted by an organic group of 1 or 2, a morpholin-1-yl group and a piperazin-1- Diary, and the like.

When R ¹ is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ¹ is an alkyl group, it may be a straight chain or a branched chain. Specific examples of when R ¹ is an alkyl group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- N-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-hexyl, - decyl group and isodecyl group. When R ¹ is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ¹ is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. When R ¹ is an alkoxy group, a straight chain or branched chain may be used. Specific examples of when R ¹ is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group and isodecyloxy group. When R ¹ is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group and a methoxy Propyloxy group and the like.

When R ¹ is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples of the case where R ¹ is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Specific examples of when R ¹ is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ¹ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. Specific examples of when R ¹ is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, - pentadecanoyl group, and n-hexadecanoyl group. Specific examples of when R ¹ is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2- Hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group and n-hexadecanoyloxy group.

When R ¹ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples of when R ¹ is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec- An n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group and an isodecyloxycarbonyl group.

When R ¹ is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. When R ¹ is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples of when R ¹ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group and a 4-phenylbutyl group. Specific examples of when R ¹ is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group and a 2- (β-naphthyl) ethyl group. When R ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl group or the naphthyl group.

When R ¹ is a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing 1 or more N, S or O, or a heterocyclyl group formed by condensation of such monocyclic ring and benzene ring. And when the heterocyclyl group is a condensed ring, the number of rings is 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Benzimidazole, benzothiazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, quinazoline, quinazoline, quinazoline, quinazoline, Thallazine, cinnoline and quinoxaline. When R ¹ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ¹ is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as the case where R ¹ is a heterocyclyl group.

When R ¹ is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 2 to 21 carbon atoms A saturated aliphatic acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, A tolyl group, a naphthylalkyl group having from 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Examples of these suitable organic groups are the same as R < ¹ >. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n- An amino group, an amino group, an n-pentylamino group, an n-hexylamino group, an n-heptylamino group, an n-octylamino group, N-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, .

Examples of the substituent group in the case where the phenyl group, naphthyl group and heterocyclyl group have further substituents included in R ¹ include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, A dialkylamino group having an alkyl group of 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group and a cyano group. When the phenyl group, the naphthyl group and the heterocyclyl group contained in R ¹ further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, and is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group and heterocyclyl group contained in R ¹ have a plurality of substituents, the plurality of substituents may be the same or different.

R ¹ is preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in R ¹ may have.

Of the monovalent organic groups, R ¹ is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group or a phenylthioalkyl group which may have a substituent on an aromatic ring. The alkyl group is preferably an alkyl group of 1 to 20 carbon atoms, more preferably an alkyl group of 1 to 8 carbon atoms, particularly preferably an alkyl group of 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, the 2- (4-chlorophenylthio) ethyl group is preferred.

As described above, the compound represented by the formula (a1) is a compound represented by the following formula (1) to (3):

(1) R ¹ includes a group represented by -OR ⁷ , and R ⁷ is a halogenoalkyl group.

(2) m2 is 1, R ⁴ comprises a group represented by -OR ⁷ , and R ⁷ is a halogenoalkyl group.

(3) R ³ is a branched chain alkyl group which may have a substituent.

It is necessary to satisfy at least one of the conditions.

Therefore, it is preferable that R ¹ is substituted with a substituent represented by -OR ⁷ . R ⁷ is a halogenoalkyl group. When R ¹ is substituted by a group represented by -OR ^7, the number of the groups represented by -OR ⁷ contained in the R ¹ is not particularly limited. When R ¹ is substituted by a group represented by -OR ^7, the number of the groups represented by -OR ⁷ contained in the R ¹ is 1 or 2 are preferred, and more preferably 1.

The number of the group represented by -OR ⁷ of the compound represented by the formula (a1) is preferably 1 or 2, more preferably 1.

Examples of the halogen atom contained in the halogenoalkyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halogenoalkyl group may contain one halogen atom or two or more halogen atoms in combination.

The number of halogen atoms of the halogenoalkyl group is not particularly limited within a range not hindering the object of the present invention. The number of halogen atoms of the halogenoalkyl group is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more. The upper limit of the number of halogen atoms of the halogenoalkyl group is preferably 7 or less, more preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of good compatibility with the other components in the photosensitive composition of the compound represented by formula (a1) Or less is particularly preferable.

The number of halogen atoms contained in the compound represented by formula (a1) is preferably at least 1, more preferably at least 2, particularly preferably at least 3, even more preferably at most 7, even more preferably at most 6, 5 or less is particularly preferable.

The number of carbon atoms of the halogenoalkyl group is not particularly limited within the range not hindering the object of the present invention. The number of carbon atoms of the halogenoalkyl group is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more. The upper limit of the number of carbon atoms of the halogenoalkyl group is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less.

As the halogenoalkyl group, a fluorinated alkyl group is particularly preferable. Specific preferred examples of the halogenoalkyl group include 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3- 3,3,3-pentafluoropropyl group, and 2,2,3,3,4,4,5,5-octafluoropentyl group. Of these, the 2,2,3,3-tetrafluoropropyl group is preferable because of the ease of preparation of the compound represented by the formula (a1).

As the group substituted with a halogenoalkyl group as R ¹ , a phenyl group substituted with one or two halogenoalkyl groups is preferable. Specifically, the group substituted with a halogenoalkyl group as R ¹ is a group represented by the following formula (a1-01):

[Figure 8]

(Had formula (a1-01) of, R ⁷ are same as the above, R ⁹ is a substituent which may have a phenyl group as R ^1, and m4 is 1 or 2, m4 + m5 is an integer of 1 to 5.)

Is preferable.

R ⁹ is preferably an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group and an ethyl group, Particularly preferred.

m5 is preferably 1.

R ¹ is a group represented by the following formula (a1-02):

[Figure 9]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m 1, m 2 and m 3 are the same as in formula (a1) and R ¹⁰ is a divalent organic group. )

.

The divalent organic group as R < ¹⁰ > is not particularly limited within the scope of not impairing the object of the present invention. Suitable examples of the divalent organic group as R ¹⁰ include an alkanediyl group having 1 to 10 carbon atoms (e.g., a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, A 1,4-diyl group and the like) and an arylene group (p-phenylene group, m-phenylene group, o-phenylene group, 1,1'-biphenyl-4,4'-diyl group and the like).

Specific examples of the compound represented by the formula (a1) when R ¹ is a group represented by the formula (a1-02) include compounds represented by the following formulas.

[10]

Among the R ^{1 s} described above, a group represented by the following formula is preferable.

[Figure 11]

In formula (a1), R ² is a hydrocarbon group which may have a substituent or a heterocyclyl group which may have a substituent. The hydrocarbon group which may have a substituent is preferably an alkyl group having from 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As the aryl group, a phenyl group and a naphthyl group are preferable, and a phenyl group is preferable. As the substituent which R ² may be taken as an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. The substituent which may be taken when R ² is an aryl group is preferably an alkyl group, an alkoxy group or a halogen atom having 1 to 5 carbon atoms.

When R ² is a heterocyclyl group, the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. When R ² is a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing one or more N, S or O, or a heterocyclyl group in which these monocyclic rings and condensed benzene rings are condensed. And when the heterocyclyl group is a condensed ring, the number of rings is 3. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Benzimidazole, benzothiazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, quinazoline, quinazoline, quinazoline, quinazoline, Thallazine, cinnolin, quinoxaline, piperidine, piperazine, morpholine, tetrahydropyran and tetrahydrofuran.

When R ² is a heterocyclyl group, examples of the substituent which the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, and a nitro group.

As R ^{2, a} methyl group, a phenyl group and a thienyl group are preferable, and a methyl group is more preferable.

In formula (a1), R ³ is a monovalent organic group. R ³ may be selected from a variety of organic groups within the scope of not impairing the object of the present invention. Suitable examples of R ³ include an alkyl group which may have a substituent having 1 to 20 carbon atoms and a cycloalkyl group which may have a substituent having 3 to 20 carbon atoms and may have a substituent having 2 to 20 carbon atoms A saturated aliphatic acyl group, an alkoxycarbonyl group which may have a substituent of 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, A naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthocarbonyl group which may have a substituent, a number of carbon atoms of not less than 11 but not more than 20 A naphthylalkyl group, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

R ³ is preferably an alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched. From the viewpoint of good solubility in the photosensitive composition of the compound represented by the formula (a1), the number of carbon atoms of the alkyl group as R ³ is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. The number of carbon atoms of the alkyl group as R ³ is preferably 15 or less, more preferably 10 or less, from the viewpoint of good compatibility of the compound represented by formula (a1) with other components in the photosensitive composition.

When R ³ has a substituent, suitable examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, A phenoxy group, a benzoyl group, a benzoyloxy group, a group represented by -PO (OR) ₂ (R is an alkyl group having 1 to 6 carbon atoms), a halogen atom, a cyano group Anthracene group, and heterocyclyl group. A suitable example of a heterocyclyl group as a substituent is the same as a suitable example of a heterocyclyl group as R ² .

As described above, the compound represented by the formula (a1) is a compound represented by the following formula (1) to (3):

(1) R ¹ includes a group represented by -OR ⁷ , and R ⁷ is a halogenoalkyl group.

(2) m2 is 1, R ⁴ comprises a group represented by -OR ⁷ , and R ⁷ is a halogenoalkyl group.

(3) R ³ is a branched chain alkyl group which may have a substituent.

It is necessary to satisfy at least one of the conditions.

Therefore, it is preferable that R ³ is a branched chain alkyl group which may have a substituent.

As R ³ , the following formula (a1-03):

[Figure 12]

(Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , m 1, m 2 and m 3 are the same as in formula (a1) and R ¹¹ is a divalent organic group.

The divalent organic group as R < ¹¹ > is not particularly limited within the range not hindering the object of the present invention. Suitable examples of the divalent organic group as R ¹¹ include an alkanediyl group having 1 to 10 carbon atoms (e.g., a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, A heptane-1,7-diyl group, an octane-1,8-diyl group, etc.), an arylene group (p-phenyl Phenylene group, o-phenylene group, 1,1'-biphenyl-4,4'-diyl group and the like).

It is also preferable as a divalent organic group as the following R ¹¹ . In the formula, R ¹² is an alkylene group having 1 to 20 carbon atoms. Examples of the alkylene group as R ¹² include methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane- Diyl group, a heptane-1,7-diyl group and an octane-1,8-diyl group.

[Figure 13]

Specific examples of the compound represented by the formula (a1) when R ³ is a group represented by the formula (a1-03) include compounds represented by the following formulas.

[14]

Suitable specific examples of R ³ as described above include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- Pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group.

As the above-mentioned alkyl groups, it is preferable to use a branched alkyl group as R ³ as described above, so that the alkyl group is preferably an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, -Hexyl group, sec-pentyl group, tert-pentyl group and 2-ethylhexyl group are preferable.

From the viewpoint of good solubility of the compound represented by the formula (a1) in the photosensitive composition, an n-octyl group and a 2-ethylhexyl group are preferable, and a 2-ethylhexyl group is more preferable.

R ⁴ in the formula (a1) is a monovalent organic group. Examples of the monovalent organic group as R ⁴ include the same groups as the monovalent organic group as R ¹ .

R ⁴ is a group represented by R ⁴ - (CO) _{m 3} - and bonds to the main skeleton of the compound represented by formula (a1). Suitable specific examples of the group represented by R ⁴ - (CO) _{m 3} - include the groups represented by the following formulas. In the following formula, m3 is the same as in formula (a1) and is 1 or 0.

[Figure 15]

[16]

[Figure 17]

Among the suitable examples of the group represented by R ⁴ - (CO) _{m 3} -, the 1,3,5-trimethylbenzoyl group is particularly preferable.

As described above, the compound represented by the formula (a1) is a compound represented by the following formula (1) to (3):

(1) R ¹ includes a group represented by -OR ⁷ , and R ⁷ is a halogenoalkyl group.

(2) m2 is 1, R ⁴ comprises a group represented by -OR ⁷ , and R ⁷ is a halogenoalkyl group.

(3) R ³ is a branched chain alkyl group which may have a substituent.

It is necessary to satisfy at least one of the conditions.

Therefore, it is preferable that R ⁴ is substituted with a substituent represented by -OR ⁷ . R ⁷ is a halogenoalkyl group. R ⁷ is as described above.

As the group substituted with a halogenoalkyl group as R ⁴ , a phenyl group substituted with one or two halogenoalkyl groups is preferable. Specifically, a group represented by the above-mentioned formula (a1-01) is preferable, similarly to a group substituted with a halogenoalkyl group as R ¹ .

As R ⁴ , the following formula (a1-04):

[Figure 18]

(In formula (a1-04), R ¹ , R ³ , R ⁵ , R ⁶ , m 1, m 2 and m 3 are the same as in formula (a1) and R ¹³ is a divalent organic group.

As shown in FIG.

The divalent organic group represented by R < ¹³ > is not particularly limited within the scope of not impairing the object of the present invention. Suitable examples of the divalent organic group as R ¹³ include an alkanediyl group having 1 to 10 carbon atoms (e.g., a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, A heptane-1,7-diyl group, an octane-1,8-diyl group, etc.), an arylene group (p-phenyl Phenylene group, o-phenylene group, 1,1'-biphenyl-4,4'-diyl group and the like).

It is also preferable as a divalent organic group as the following ring R ¹³ . In the formula, R ¹³ is an alkylene group having 1 to 20 carbon atoms which may be substituted with a halogen atom. Examples of the alkylene group as R ¹⁴ include methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane- Diyl group, a heptane-1,7-diyl group and an octane-1,8-diyl group.

Further, all the hydrogen atoms in these alkylene groups are preferable as the airway R ¹⁴ substituted with a halogen atom, particularly a fluorine atom.

[19]

In the formula (a1), m1, m2 and m3 are all 0 or 1. 0 is preferable as m1. m2 is preferably 1, and m3 is preferably 1.

Specific examples of the compound represented by the formula (a1) described above include the following compounds.

[20]

[Figure 21]

[22]

[23]

[24]

[25]

[26]

[Oxime ester compound (A2)]

The oxime ester compound (A2) has the following formula (a2):

[Figure 27]

(In the formula (a2), CR represents a group represented by the following formula (a2a) or the following formula (a2b):

[28]

, R ^a1 is a hydrogen atom, a nitro group or a monovalent organic group, R ^a2 and R ^a3 each represent a straight chain alkyl group which may have a substituent, a straight chain alkoxy group which may have a substituent, Or a hydrogen atom, R ^a2 and R ^a3 may combine with each other to form a ring, R ^a4 is a monovalent organic group, and R ^a5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent An aliphatic hydrocarbon group or an aryl group which may have a substituent, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.)

≪ / RTI >

From the fact that the oxime ester compound represented by the formula (a2) can be easily adjusted and the characteristics of the oxime ester compound can be easily adjusted by selecting R ^a2 and R ^a3, the CR in the formula (a2) a2a) is preferable.

In the group represented by formula (a2a) or formula (a2b) represented by the formula (a2), R ^a1 is a hydrogen atom, a nitro group or a monovalent organic group. R ^a1 is bonded to a 6-membered aromatic ring different from the aromatic ring bonded to the group represented by - (CO) _{n 2} - on the condensed ring in the formula (a2a) or the formula (a2b). The bonding position of R ^{a1 in} the formula (a2a) or the formula (a2b) is not particularly limited. Expression when having the (a2) compound is at least one R ^a1 represented by the formula (a2), from a point such as a synthetic ease of compound represented by one of the one or more R ^a1 formula (a2a-1) and the equation (a2b-1):

[29]

Is bonded at a position represented by * in the structure represented by *. When R ^a1 is a plurality, the plurality of R may be the same or different is ^a1.

When R ^a1 is an organic group, R ^a1 is not particularly limited as long as it does not impair the object of the present invention, and is suitably selected from various organic groups. Suitable examples of R ^a1 being an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, , A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, , An amino group substituted with an organic group of 1 or 2, a morpholin-1-yl group and a piperazin-1- Diary, and the like.

When R ^a1 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ^a1 is an alkyl group, it may be linear or branched. Specific examples of the case where R ^a1 is an alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- N-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-hexyl, - decyl group and isodecyl group. When R ^a1 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^a1 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. When R ^a1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of when R ^a1 is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group and isodecyloxy group. When R ^a1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group and a methoxy Propyloxy group and the like.

When R ^a1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Concrete examples of the case where R ^a1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Concrete examples of the case where R ^a1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group and a cyclooctyloxy group.

When R ^a1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. Specific examples of when R ^a1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, - pentadecanoyl group, and n-hexadecanoyl group. Specific examples of the case where R ^a1 is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2- Hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group and n-hexadecanoyloxy group.

When R ^a1 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples of when R ^a1 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec- An n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group and an isodecyloxycarbonyl group.

When R ^a1 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. When R ^a1 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples of when R ^a1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group and a 4-phenylbutyl group. Specific examples of the case where R ^a1 is a naphthylalkyl group include? -Naphthylmethyl group,? -Naphthylmethyl group, 2- (? -Naphthyl) ethyl group and 2- (? -Naphthyl) ethyl group. When R ^a1 is a phenylalkyl group or a naphthylalkyl group, R ^a1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^a1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing 1 or more N, S or O, or a heterocyclyl group in which the monocyclic ring is condensed with a benzene ring. And when the heterocyclyl group is a condensed ring, the number of rings is 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Benzimidazole, benzothiazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, quinazoline, quinazoline, quinazoline, quinazoline, Thallazine, cinnolin, quinoxaline, piperidine, piperazine, morpholine, tetrahydropyran and tetrahydrofuran. When R ^a1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^a1 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as the case where R ^a1 is a heterocyclyl group.

When R ^a1 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 2 to 21 carbon atoms A saturated aliphatic acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, A tolyl group, a naphthylalkyl group having from 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Specific examples of these suitable organic ^groups are the same as R ^a1 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n- An amino group, an amino group, an n-pentylamino group, an n-hexylamino group, an n-heptylamino group, an n-octylamino group, N-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, .

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^a1 have a further substituent, the substituent includes an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, an alkoxy group of 2 A saturated aliphatic acyl group having 7 or less carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, A dialkylamino group having an alkyl group having at least 1 atom and at most 6 atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group and a cyano group. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^a1 further have a substituent, the number of the substituent is not limited within the range not hindering the object of the present invention, but is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^a1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, it is preferable that R ^a1 is a group represented by a nitro group or R ^a6 -CO- because the sensitivity tends to be improved. R ^a6 is not particularly limited as long as the object of the present invention is not impaired, and R ^a6 can be selected from a variety of organic groups. Examples of the group suitable as R ^a6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. As R ^a6 , among these groups, a 2-methylphenyl group, a thiophen-2-yl group and an a-naphthyl group are particularly preferable.

When R ^a1 is a hydrogen atom, transparency tends to be good, which is preferable. When R ^a1 is a hydrogen atom and R ^a3 is a group represented by the formula (a2-a) or (a2-b) described later, the transparency tends to be better.

In formula (a2a), R ^a2 and R ^a3 are each a straight chain alkyl group which may have a substituent, a straight chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^a2 and R ^a3 may be bonded to each other to form a ring. Among these groups, R ^a2 and R ^a3 are preferably chain alkyl groups which may have a substituent. When R ^a2 and R ^a3 are a straight chain alkyl group which may have a substituent, the straight chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^a2 and R ^a3 are a straight chain alkyl group having no substituent, the number of carbon atoms of the straight chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. Specific examples of the case where R ^a2 and R ^a3 are chain alkyl groups include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- N-hexyl group, n-hexyl group, n-hexyl group, isohexyl group, iso-pentyl group, sec-pentyl group, tert- Nonyl group, n-decyl group and isodecyl group. When R ^a2 and R ^a3 are alkyl groups, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^a2 and R ^a3 are a straight chain alkyl group having a substituent, the number of carbon atoms of the straight chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The straight chain alkyl group having a substituent is preferably a straight chain.

The substituent that the alkyl group may have is not particularly limited within the scope of not impairing the object of the present invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a fluorine atom, a chlorine atom and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as those in the case where R ^a1 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Concrete examples of the heterocyclyl group are the same as those in the case where R ^a1 is a heterocyclyl group. When R ^a1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear, branched or straight-chain. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When the straight chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When R ^a2 and R ^a3 are a straight chain alkoxy group having no substituent, the number of carbon atoms of the chain alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. Specific examples of the case where R ^a2 and R ^a3 are chain alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- N-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group and isodecyloxy group. When R ^a2 and R ^a3 are alkoxy groups, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group and a methoxy Propyloxy group and the like.

When R ^a2 and R ^a3 are a straight chain alkoxy group having a substituent, the substituent that the alkoxy group may have is the same as the case where R ^a2 and R ^a3 are straight chain alkyl groups.

When R ^a2 and R ^a3 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^a2 and R ^a3 are cyclic organic groups, the substituent that the cyclic organic group may have is the same as the case where R ^a2 and R ^a3 are chain alkyl groups.

When R ^a2 and R ^a3 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, or a group in which a plurality of benzene rings are bonded through a carbon-carbon bond, or a group in which a plurality of benzene rings are condensed to form. In the case where the aromatic hydrocarbon group is a phenyl group or a group in which a plurality of benzene rings are formed by bonding or condensation, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, preferably 3 or less, more preferably 2 or less, Do. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ^a2 and R ^a3 are aliphatic cyclic hydrocarbon groups, aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobonyl group, a tricyclodecyl group , Tetracyclododecyl group, and an adamantyl group.

When R ^a2 and R ^a3 are a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing 1 or more N, S, O, or a monocyclic or bicyclic monocyclic ring containing one or more of these monocyclic rings, . And when the heterocyclyl group is a condensed ring, the number of rings is 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Benzimidazole, benzothiazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, quinazoline, quinazoline, quinazoline, quinazoline, Thallazine, cinnolin, quinoxaline, piperidine, piperazine, morpholine, tetrahydropyran and tetrahydrofuran.

R ^a2 and R ^a3 may be bonded to each other to form a ring. The group formed by the ring formed by R ^a2 and R ^a3 is preferably a cycloalkylidene group. When R ^a2 and R ^a3 are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered to 6-membered ring, more preferably a 5-membered ring.

When the group formed by combining R ^a2 and R ^a3 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring which may be condensed with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, A pyrazine ring and a pyrimidine ring.

Examples of suitable groups among R ^a2 and R ^a3 described above include groups represented by the formula -A ¹ -A ² . Wherein A ¹ is a straight chain alkylene group and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group or an alkoxycarbonyl group.

The number of carbon atoms of the straight chain alkylene group of A ¹ is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is an alkoxy group, the alkoxy group may be linear or branched or straight-chain. The number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom. The halogenated alkyl group may be straight chain or branched chain, and straight chain is preferable. When A ² is a cyclic organic group, examples of cyclic organic groups are the same as cyclic organic groups having R ^a2 and R ^a3 as substituents. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group having R ^a2 and R ^a3 as a substituent.

Suitable examples of R ^a2 and R ^a3 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group and n-octyl group; Methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, Alkoxyalkyl groups such as a t-butyl group, a 6-ethoxy-n-hexyl group, a 7-ethoxy-n-heptyl group and an 8-ethoxy-n-octyl group; N-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano- a cyanoalkyl group such as an n-heptyl group and an 8-cyano-n-octyl group; Phenyl-n-pentyl group, a 6-phenyl-n-hexyl group, a 7-phenyl-n-heptyl group and a 3-phenyl- A phenylalkyl group such as an 8-phenyl-n-octyl group; Cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl n-hexyl group, 7-cyclohexyl cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, Cycloalkylalkyl groups such as a t-butyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group and an 8-cyclopentyl-n-octyl group; Methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl- Ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, An alkoxycarbonylalkyl group such as an ethoxycarbonyl-n-octyl group; Chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro- n-heptyl group, Propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5 Heptafluoro-n-pentyl group, and the like.

As suitable groups among R ^a2 and R ^a3 among the above groups, there may be mentioned ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2- methoxyethyl group, A 2-chloroethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group and a 3,3,4,4,5,5,5-heptafluoro-n - pentyl group.

Examples of suitable organic groups of R ^a4 are R ^a1 in the same manner, an alkyl group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a substituent A phenoxy group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, A naphthoyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoylcarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, A heterocyclylcarbonyl group which may have a substituent, an amino group substituted by an organic group of 1 or 2, a morpholin-1-yl group and / Blow binary may be mentioned 1-yl group and the like. Specific examples of these groups are the same as those described for R ^a1 . R ^a4 is preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in R ^a1 may have.

Among the organic groups, R ^a4 is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group or a phenylthioalkyl group which may have a substituent on an aromatic ring. The alkyl group is preferably an alkyl group of 1 to 20 carbon atoms, more preferably an alkyl group of 1 to 8 carbon atoms, particularly preferably an alkyl group of 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, the 2- (4-chlorophenylthio) ethyl group is preferred.

The group represented by R ^a4 is preferably -A ³ -CO-OA ⁴ . A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and is preferably an alkylene group. A ⁴ is a monovalent organic group and is preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched or straight-chain. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, particularly preferably 1 or more and 4 or less.

Suitable examples of A ⁴ include an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, a cycloalkyl alkyl group of 4 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, And an aromatic hydrocarbon group having 6 to 20 carbon atoms. Suitable examples of A ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, Phenyl group, naphthyl group, benzyl group, phenethyl group,? -Naphthylmethyl group and? -Naphthylmethyl group.

Specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n- N-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-pentyloxycarbonylethyl group, Propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycar N-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group and 3-phenoxycarbonyl- .

Above has been described for the R ^a4, R ^a4 is preferably a group represented by the following formula (a2-a) or (a2-b) roneun.

[T]

(In the formulas (a2-a) and (a2-b), R ^a7 and R ^a8 are each an organic group, n3 is an integer of 0 or more and 4 or less, and R ^a7 and R ^a8 are present at adjacent positions on the benzene ring when, R ^a7 and R ^a8 is bonded to form a ring, n4 is an integer in a range from 1 8, n5 is an integer of at least 1 5, n6 is an integer of not less than 0 (n5 + 3), R ^a9 is an organic group.)

Examples of organic ^groups for R ^a7 and R ^a8 in formula (c2-a) are the same as R ^a1 . R ^a7 is preferably an alkyl group or a phenyl group. When R ^a7 is an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, most preferably 1. In other words, R ^a7 is most preferably a methyl group. When R ^a7 and R ^a8 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (c2-a) in which R ^a7 and R ^a8 form a ring include a naphthalene-1-yl group, a 1,2,3,4-tetrahydronaphthalen- . In the formula (c2-a), n3 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the formula (a2-b), R ^a9 is an organic group. The organic group includes the same group as the organic group described for R ^a1 . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less. R ^a9 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and among these, a methyl group is more preferable.

In the formula (a2-b), n5 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the formula (a2-b), n6 is an integer of 0 or more and (n5 + 3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, In the formula (a2-b), n4 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.

In formula (a2), R ^a5 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, or an aryl group which may have a substituent. When R ^a5 is an aliphatic hydrocarbon group, preferred examples of the substituent include phenyl group and naphthyl group. The substituent which may be introduced when R ^a1 is an aryl group is preferably an alkyl group, an alkoxy group or a halogen atom having 1 to 5 carbon atoms.

In formula (a2), R ^a5 is preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group, a cyclohexylmethyl group, , A methylphenyl group, a naphthyl group and the like are preferably exemplified, and among these, a methyl group or a phenyl group is more preferable.

Suitable specific examples of the compound represented by the formula (a2) include the following compounds.

However,

[0035]

[0035]

[0035]

[35]

The content of the photopolymerization initiator (A) in the photosensitive composition is not particularly limited within the range not hindering the object of the present invention. The content of the photopolymerization initiator (A) is preferably from 0.1% by mass to 50% by mass, more preferably from 0.3% by mass to 30% by mass, more preferably from 0.5% by mass to 20% by mass, based on the mass of the solid content of the photosensitive composition Particularly preferred. By using the positive photopolymerization initiator (A) in such a range, it is easy to obtain a desired effect by using the photopolymerization initiator (A) without harming the mechanical properties, solvent resistance, chemical resistance and the like of the cured product.

≪ Polymerizable base component (B) >

The photosensitive composition may further comprise a polymerizable base component (B). The polymerizable base component (B) (hereinafter also referred to as " component (B) ") is a component that imparts photopolymerization and film-forming ability to the photosensitive composition. The polymerizable base component (B) is not particularly limited as long as it contains a component capable of being polymerized by the photopolymerization initiator (A) and is a component capable of preparing a film-forming photosensitive composition. The polymerizable base component (B) may be used alone or in combination of two or more.

The polymerizable base component (B) typically comprises a photopolymerizable compound (B1) or a photopolymerizable compound (B1) and a resin (B2). The photopolymerizable compound (B1) may be a low molecular compound or a high molecular compound. The photopolymerizable compound (B1) and the resin (B2) may be used alone or in combination of two or more.

The photopolymerizable compound (B1) and the resin (B2) are, for example, polymers of one kind or two or more kinds of monomer compounds, wherein a polymer having a weight average molecular weight of 1000 or more is used as the resin (B2) Can be distinguished by using a compound having a photopolymerizable functional group as the photopolymerizable compound (B1).

From the viewpoint of photopolymerization, the polymerizable base component (B) preferably contains a combination of a low molecular weight photopolymerizable compound (B1), which is not a polymer, and a crosslinkable group-containing resin which is the resin (B2).

When the polymerizable base component (B) contains the resin (B2), from the viewpoint of developability, it is preferable that the resin (B2) comprises an alkali-soluble resin. The alkali-soluble resin may contain a crosslinkable group. The alkali-soluble resin containing a crosslinkable group (including a crosslinkable group as a substituent in the constituent unit) is preferable from the viewpoints of both the photopolymerization and the alkali developability.

Hereinafter, the photopolymerizable compound (B1) and the resin (B2) will be described in order.

[Photopolymerizable compound (B1)]

As the photopolymerizable compound (B1) contained in the photosensitive composition, a compound having an ethylenically unsaturated double bond can be preferably used. Suitable examples of the compound having an ethylenically unsaturated double bond include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy Acrylates such as methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate, isobutyl acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl , 2-phenoxy-2-hydroxypropyl (meth) acrylate (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N, N-dimethylaminoethyl (Meth) acrylate of 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate and phthalic acid derivatives, And the like. These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, tricyclodecanedimethanol di (Meth) acrylate, dipentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxylated neopentyl glycol di (Ethylene-propylene) glycol di (meth) acrylate, poly Acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (Meth) acrylate, diethyleneglycol di (meth) acrylate, tetraethyleneglycol di (meth) acrylate, propyleneglycol di (meth) acrylate, polypropyleneglycol di Acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol di Acrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, 2,2-bis (Meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy- (Meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacryl (Meth) acrylate (e.g., tolylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and the like, and 2-hydroxyethyl (meth) acrylate such as glycerin polyglycidyl ether poly Acrylate, a condensation product of a polyhydric alcohol and N-methylol (meth) acrylamide, a triacryloformate, a 2,4,6-trimethylolpropane tri (meth) acrylate, Trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol triacrylate and 2,4,6-trioxohexahydro-1,3,5-triazine- 5-trisethanol diacrylate, and the like. These polyfunctional monomers may be used alone or in combination of two or more.

Among these compounds having an ethylenically unsaturated double bond, a multifunctional monomer having three or more functional groups is preferable from the viewpoint of obtaining a photosensitive composition which gives a cured product having excellent strength and adhesion to a substrate.

From the viewpoint of controlling the glass transition point (Tg), a monofunctional monomer or a bifunctional monomer may be used in combination with a polyfunctional monomer having three or more functional groups. Among these, 1,6-hexanediol di (meth) acrylate is preferable.

The content of the photopolymerizable compound (B1) is preferably 5% by mass or more and 97% by mass or less, more preferably 10% by mass or more and 95% by mass or less, based on the solid content of the photosensitive composition. By setting the content of the photopolymerizable compound (B1) in the photosensitive composition within the above range, the curability is good. In addition, when the amount is 60% by mass or less (preferably 5% by mass or more and 40% by mass or less) with respect to the solid content of the photosensitive composition, there is a tendency to balance the sensitivity, developability and resolution of the photosensitive composition.

[Resin (B2)]

The photosensitive composition preferably contains the resin (B2) together with the photopolymerizable compound (B1) as the polymerizable base component (b). The resin (B2) is not particularly limited as long as it does not impair the object of the present invention, and resin components conventionally blended with various photosensitive compositions can be used.

Preferable examples of the resin (B2) will be described below.

(Crosslinkable group-containing resin)

When the photosensitive composition contains a crosslinkable group-containing resin as the resin (B2), the formation of a cured product using the photosensitive composition tends to be facilitated. The crosslinkable group-containing resin is a resin having a crosslinkable group and preferably contains a unit derived from a (meth) acrylic acid ester having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a functional group capable of crosslinking the crosslinkable group-containing resin mainly by heating, and is preferably an epoxy group or an ethylenically unsaturated double bond. The crosslinkable group can be introduced into the crosslinkable group-containing resin by including, for example, at least one member selected from the group consisting of a unit derived from a (meth) acrylic acid ester having an epoxy group and a unit having an ethylenically unsaturated double bond .

As the crosslinkable group-containing resin, a resin containing a unit derived from a (meth) acrylic acid ester having an epoxy group is preferable. By having such a unit, adhesion and mechanical strength to the base material of the cured film formed using the photosensitive composition can be improved.

The (meth) acrylic acid ester having an epoxy group may be a (meth) acrylic acid ester having a chain aliphatic epoxy group or a (meth) acrylic acid ester having an alicyclic epoxy group as described later.

The (meth) acrylic acid ester having an epoxy group may have an aromatic group. In the present specification, an aromatic group is a group having an aromatic ring. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of the (meth) acrylic acid ester having an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, 2-glycidyloxyphenyl (Meth) acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate and 2-glycidyloxyphenylmethyl have.

When the film formed using the photosensitive composition is required to have transparency, it is preferable that the (meth) acrylic acid having an epoxy group does not have an aromatic group.

Examples of the (meth) acrylate ester having a chain aliphatic epoxy group include an ester group (-O-CO-) such as an epoxy alkyl (meth) acrylate and an epoxyalkyloxyalkyl (meth) (Meth) acrylic acid ester to which a chain aliphatic epoxy group is bonded. Such a chain aliphatic epoxy group of the (meth) acrylic acid ester may contain one or more oxy groups (-O-) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited and is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, particularly preferably 3 or more and 10 or less.

Specific examples of the (meth) acrylic acid esters having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) Epoxy alkyl (meth) acrylates such as 7-epoxyheptyl (meth) acrylate; (Meth) acrylate, 3-glycidyloxyethyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3- glycidyloxy- (Meth) acrylate such as oxy-n-hexyl (meth) acrylate and 6-glycidyloxy-n-hexyl (meth) acrylate.

Specific examples of the (meth) acrylic acid ester having an alicyclic epoxy group include, for example, the compounds represented by the following formulas (d2-1) to (d2-16). Among them, the compounds represented by the following formulas (d2-1) to (d2-6) are preferable and the compounds represented by the following formulas (d2-1) to (d2-4) are preferred in order to make the developability of the photosensitive composition suitable. Compounds are more preferable.

With respect to each of these compounds, the bonding site of the oxygen atom of the ester group to the alicyclic group is not limited to those shown here, and may include some position isomers.

[36]

Wherein R ^d4 represents a hydrogen atom or a methyl group, R ^d5 represents a divalent aliphatic saturated hydrocarbon group having 1 to ⁶ carbon atoms, R ^d6 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 0 or more and 10 or less. R ^d5 is preferably a linear or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, or hexamethylene. Examples of R ^d6 include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH ₂ -Ph-CH ₂ - (Ph represents a phenylene group).

When the (meth) acrylic acid ester having an epoxy group is a (meta) acrylic acid ester having an alicyclic epoxy group as described above, the (meth) acrylic acid ester containing a unit derived from the (meth) acrylic acid ester The storage stability of the crosslinkable group-containing resin, and furthermore the photosensitive composition is excellent, and the range of the temperature (prebake temperature margin) that can be prebaked at the time of forming the cured film is widened.

The crosslinkable group-containing resin may also be a resin containing a unit having an ethylenically unsaturated double bond as a crosslinkable group (sometimes referred to as a " resin having an ethylenically unsaturated double bond " in the present specification). The ethylenically unsaturated double bond is preferably a part constituting the (meth) acryloyloxy group.

Examples of the resin having an ethylenically unsaturated double bond include a resin having a (meth) acryloyloxy group.

The resin having a (meth) acryloyloxy group can be obtained, for example, by reacting at least a part of a carboxyl group contained in a polymer containing a unit derived from an unsaturated carboxylic acid and at least part of a carboxyl group contained in the (meth) acryloyloxy group having the alicyclic epoxy group and / (Meth) acrylic acid ester having an aliphatic epoxy group.

When the crosslinkable group-containing resin is a resin having an ethylenically unsaturated double bond, it may be one having photopolymerization. By containing the photopolymerizable resin having such an ethylenically unsaturated double bond as the resin (B2) in the photosensitive composition, the curing property of the photosensitive composition is improved and pattern formation can be facilitated.

In the crosslinkable group-containing resin, the amount of the unit derived from the (meth) acrylic acid ester having a crosslinkable group is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% , More preferably from 33 mass% to 65 mass%.

In the crosslinkable group-containing resin, the amount of the unit derived from the (meth) acrylic acid ester having an epoxy group with respect to the mass of the resin is preferably 10% by mass or more and 90% by mass or less, more preferably 15% by mass or more and 80% , And still more preferably 20 mass% or more and 70 mass% or less.

In the crosslinkable group-containing resin, the amount of the unit having an ethylenically unsaturated double bond with respect to the mass of the resin is preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 35% by mass or less.

As the crosslinkable group-containing resin, a polymer of at least one monomer selected from (meth) acrylic acid and (meth) acrylic acid ester is preferable, and even in the case of the above polymer, the (meth) acrylic acid ester having a crosslinkable group The content of the derived unit is the same as the above with respect to the mass of the resin.

The crosslinkable group-containing resin may contain both a unit derived from a (meth) acrylic acid ester having an epoxy group and a unit having an ethylenically unsaturated double bond, but may be a unit derived from a (meth) acrylic acid ester having an epoxy group, Unsaturated double bonds. The crosslinkable group preferably includes a unit derived from a (meth) acrylic acid ester having an epoxy group.

The crosslinkable group-containing resin is preferably a resin having a crosslinkable group and an alkali-soluble resin. By blending such an alkali-soluble resin, the photosensitive composition can impart alkali developability to the photosensitive composition.

In this specification, a resin having a film thickness of 1 mu m is formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass% in the present invention, and the alkali soluble resin is dissolved in a KOH aqueous solution having a concentration of 0.05 mass% Means that the film thickness is 0.01 占 퐉 or more when the film is immersed for 1 minute.

When the crosslinkable group-containing resin is also an alkali-soluble resin, it usually has an alkali-soluble group. The alkali-soluble group is not particularly limited as long as it is a functional group that imparts solubility to the alkali in the crosslinkable group-containing resin, and a carboxyl group or a group that deprotects the carboxyl group to form a carboxyl group is preferable. For example, a unit derived from an unsaturated carboxylic acid (Meth) acrylic acid ester, which is capable of imparting an alkali-soluble group, to the crosslinkable group-containing resin. In the present specification, the (meth) acrylic acid ester which imparts an alkali-soluble group does not include the (meth) acrylic acid ester having the above-mentioned crosslinkable group.

When the crosslinkable group-containing resin is also an alkali-soluble resin, a functional group (hereinafter referred to as " alkali dissolution inhibiting group " or " dissolution inhibiting group ") for suppressing or inhibiting the solubility of the crosslinkable group- ), But a resin having an alkali-soluble group and a dissolution inhibitor is preferable. The dissolution inhibitor may also be referred to as an alkali-insoluble group in that it has a function of lowering the solubility of the crosslinkable group-containing resin in alkali. The crosslinkable group-containing resin has an alkali-soluble group and a dissolution inhibitor, whereby the solubility in alkali can be adjusted, thereby adjusting the alkali developing property of the photosensitive composition. Examples of the dissolution inhibiting agent include styrene or styrene derivatives described later; Unsaturated imides; (Meth) acrylic esters having an alicyclic skeleton (except those having an epoxy group); (Meth) acrylate having an aromatic group such as benzyl (meth) acrylate. In the present specification, the (meth) acrylic acid ester which imparts the dissolution inhibitor does not include the (meth) acrylic acid ester having the above-mentioned crosslinkable group.

Among the crosslinkable group-containing resins, a polymer of a monomer having an ethylenically unsaturated double bond is preferable from the standpoint of excellent film formability and easy adjustment of characteristics of the resin by selection of the monomer. Examples of the monomer having an ethylenically unsaturated double bond include (meth) acrylic acid; (Meth) acrylic acid esters; (Meth) acrylic acid amide; Crotonic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these dicarboxylic acids; Allyl compounds such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate and allyloxyethanol; Ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, Vinyl ethers such as vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; Vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, Vinyl esters such as acetate, vinyl lactate, vinyl-beta-phenylbutylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate; Examples of the monomer include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy There may be mentioned styrenes such as methylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Styrene or styrene derivatives such as styrene, mystyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene and 4-fluoro-3-trifluoromethylstyrene; Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl- 1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, Olefins such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; And unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide.

When the crosslinkable group-containing resin is a polymer of a monomer having an ethylenically unsaturated double bond, it usually contains a unit derived from an unsaturated carboxylic acid. Examples of the unsaturated carboxylic acid include (meth) acrylic acid; (Meth) acrylic acid amide; Crotonic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids. The amount of the unit derived from the unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has the desired alkali solubility. The amount of the unit derived from the unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably from 5 mass% to 25 mass%, more preferably from 8 mass% to 16 mass% with respect to the mass of the resin, Containing resin has a dissolution inhibiting agent to be described later, these amounts are particularly preferable. When the crosslinkable group-containing resin has no dissolution inhibiting group to be described later, the amount of the unit derived from the unsaturated carboxylic acid in the resin is preferably from 50 mass% to 80 mass%, more preferably from 60 mass% to 70 mass% % Or less is more preferable.

Among the polymers of monomers having an ethylenically unsaturated double bond, which are polymers of at least one monomer selected from monomers exemplified above, polymers of at least one monomer selected from (meth) acrylic acid and (meth) acrylic acid ester are preferable. Hereinafter, polymers of at least one monomer selected from (meth) acrylic acid and (meth) acrylic acid ester will be described.

The (meth) acrylic acid ester used in the preparation of the polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester is not particularly limited in the range not hindering the object of the present invention, ) Acrylic acid esters.

Suitable examples of the (meth) acrylic acid esters include linear or branched (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate and t- Branched alkyl (meth) acrylates; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ; (Meth) acrylic acid esters having an aromatic group such as benzyl (meth) acrylate; (Meth) acrylate ester having an alicyclic skeleton. Details of the (meth) acrylate ester having a cycloaliphatic skeleton will be described later.

Among the polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, it is preferable to use a photosensitive composition derived from a (meth) acrylic acid ester having an alicyclic skeleton from the viewpoint of forming an insulating film having a high transmittance Is also preferable. In the present specification, the (meth) acrylic acid ester having an alicyclic skeleton does not include the (meth) acrylic acid ester having the above-mentioned crosslinkable group.

In the (meth) acrylate ester having an alicyclic skeleton, the group having an alicyclic skeleton is preferably a group having an alicyclic hydrocarbon group. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobonyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Examples of the (meth) acrylic acid ester having an alicyclic hydrocarbon group among the (meth) acrylic acid esters having an alicyclic skeleton include compounds represented by the following formulas (d1-1) to (d1-8). Among these, compounds represented by the following formulas (d1-3) to (d1-8) are preferable, and compounds represented by the following formula (d1-3) or (d1-4) are more preferable.

[37]

R ^d1 represents a hydrogen atom or a methyl group, R ^d2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms and R ^d3 represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms Alkyl group. R ^d2 is preferably a single bond, a straight chain or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene or hexamethylene. R ^d3 is preferably a methyl group or an ethyl group.

The crosslinkable group-containing resin is preferably a resin containing a unit derived from at least one monomer selected from (meth) acrylic acid and (meth) acrylic acid ester and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group . Such a resin may further contain a unit derived from a (meth) acrylic acid ester having an alicyclic skeleton. In this case, the amount of the unit derived from the (meth) acrylic acid ester having an alicyclic skeleton in the resin is preferably 10% Or more and 35 mass% or less, 15 mass% or more and 30 mass% or less, and 20 mass% or more and 25 mass% or less.

Among the polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters including units derived from (meth) acrylic acid esters having alicyclic skeletons, units derived from (meth) acrylic acid and , And a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group. The film formed using the photosensitive composition containing such a crosslinkable group-containing resin is excellent in adhesion to a substrate. When such a resin is used, it is possible to cause a self-reaction between the carboxyl group contained in the resin and the alicyclic epoxy group. For this reason, when a photosensitive composition containing such a resin is used, mechanical properties such as hardness of a film to be formed can be improved by causing a magnetic reaction between a carboxyl group and an alicyclic epoxy group using a method of heating the film or the like.

(Former) (meth) acrylic acid in the resin in a resin containing units derived from (meth) acrylic acid (excluding those having a crosslinkable group) and units derived from a (meth) acrylic acid ester having an alicyclic epoxy group, The amount of the derived unit is preferably 1% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 70% by mass or less. In the resin comprising a unit derived from the (meth) acrylic acid and a unit derived from a (meth) acrylic ester having an alicyclic epoxy group, the amount of the unit derived from the (meth) acrylic acid ester having an alicyclic epoxy group in the resin is 1 By mass or more and 95% by mass or less, and more preferably 10% by mass or more and 50% by mass or less.

(Meth) acrylic acid and (meth) acrylic acid ester containing a unit derived from a (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group (Meth) acrylic acid ester having a cycloaliphatic epoxy group, a unit derived from a (meta) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group and a unit derived from a (meth) acrylic ester having an alicyclic epoxy group.

(Meth) acrylic acid ester having a unit derived from a (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group and a (meth) acrylic ester having an alicyclic epoxy group, ) Acrylic acid is preferably 1% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 50% by mass or less. (Meth) acrylic acid ester having a cycloaliphatic epoxy group, a unit derived from a (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group and a unit derived from a The amount of the unit derived from the (meth) acrylic acid ester having a hydrocarbon group is preferably 1% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 70% by mass or less. (Meth) acrylic acid ester having a cycloaliphatic epoxy group, a unit derived from a (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group and a unit derived from a The amount of the unit derived from the (meth) acrylic acid ester having an epoxy group is preferably 1% by mass or more and 95% by mass or less, and more preferably 30% by mass or more and 80% by mass or less.

The mass average molecular weight (Mw: measurement value in terms of polystyrene conversion of gel permeation chromatography (GPC) of the crosslinkable group-containing resin is preferably 2000 or more and 200000 or less, more preferably 2000 or more and 18000 or less. Within the above range, there is a tendency that the film forming ability of the photosensitive composition and the balance of developability after exposure tends to be easily obtained.

(Resin having cardo structure)

A resin having a cardo structure described below (hereinafter also referred to as " cardo resin ") can also be suitably used as the resin B2.

As the cardo resin, a resin having a cardo skeleton in its structure and having a predetermined alkali solubility can be used. The cardo skeleton refers to a skeleton in which a second cyclic structure and a third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. The second annular structure and the third annular structure may have the same structure or different structures.

A typical example of the cardo skeleton is a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to the 9th carbon atom of the fluorene ring.

The resin having a cardo structure is not particularly limited, and conventionally known resins can be used. Among them, the resin represented by the following formula (b-1) is preferable.

The resin represented by the following formula (b-1) fulfills its role as an alkali-soluble resin having a crosslinkable group because it has a carboxyl group and an ethylenically unsaturated double bond in its structure.

[38]

In the formula (b-1), X ^b represents a group represented by the following formula (b-2). t1 represents an integer of 0 to 20 inclusive.

[39]

R ^b11 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R ^b12 each independently represents a hydrogen atom or a methyl group, R ^b13 represents a hydrogen atom or a methyl group, T2 represents 0 or 1, and W ^b represents a group represented by the following formula (b-3).

[40]

In formula (b-2), R ^b13 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms And most preferred are ethane-1,2-diyl group, propane-1,2-diyl group and propane 1,3-diyl group.

The ring A ^b in the formula (b-3) represents an aliphatic ring which may be condensed with an aromatic ring or may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocycle.

Examples of the aliphatic ring include monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane.

Specific examples thereof include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and adanthan, norbornane, isoborane, tricyclodecane and tetracyclododecane.

The aromatic ring which may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle, preferably an aromatic hydrocarbon ring. Specifically, benzene ring and naphthalene ring are preferable.

Suitable examples of divalent groups represented by formula (b-3) include the following groups.

[41]

The divalent X ^b in the formula (b-1) is introduced into the cardo resin by reacting the tetracarboxylic dianhydride giving the residue Z ^b with the diol compound represented by the following formula (b-2a).

[42]

In formula (b-2a), R ^b11 , R ^b12 , R ^b13 and t2 are as described for formula (b-2). The ring A ^b in the formula (b-2a) is as described for the formula (b-3).

The diol compound represented by the formula (b-2a) can be produced, for example, by the following method.

First, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (b-2b) is replaced with a group represented by -R ^b13 -OH according to a usual method, if necessary, and then epichlorohydrin To obtain an epoxy compound represented by the following formula (b-2c).

Next, the diol compound represented by the formula (b-2a) is obtained by reacting the epoxy compound represented by the formula (b-2c) with acrylic acid or methacrylic acid.

R ^b11 , R ^b13 and t2 in the formulas (b-2b) and (b-2c) are as described for the formula (b-2). The ring A ^b in the formula (b-2b) and the formula (b-2c) is as described for the formula (b-3).

The production method of the diol compound represented by the formula (b-2a) is not limited to the above-mentioned method.

[43]

Suitable examples of the diol compound represented by the formula (b-2b) include the following diol compounds.

[44]

In the above formula (b-1), R ^b0 is a hydrogen atom or a group represented by -CO-Y ^b -COOH. Here, Y ^b represents a residue excluding an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-undo-methylene tetrahydrophthalic anhydride, anhydrous chloridic acid, methyltetrahydrophthalic anhydride , And anhydrous glutaric acid.

In the above formula (b-1), Z ^b represents a residue other than the two acid anhydride groups from the tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like represented by the following formula (b-4) .

In the above formula (b-1), t1 represents an integer of 0 or more and 20 or less.

[45]

(B-4), R ^b14 , R ^b15 and R ^b16 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, t3 is 0 or more Represents an integer of 12 or less.)

The alkyl group which may be selected as R ^b14 in the formula (b-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms contained in the alkyl group within this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R ^b14 is an alkyl group, the number of carbon atoms thereof is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, still more preferably 1 or more and 4 or less, from the viewpoint of easily obtaining a cardo resin having excellent heat resistance. More preferably 1 or more and 3 or less.

When R ^b14 is an alkyl group, the alkyl group may be linear or branched.

As R ^b14 in the formula (b-4), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more preferable, independently from each other, because a carboxyl resin having excellent heat resistance is easily obtained. R ^b14 in the formula (b-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.

It is preferable that a plurality of R ^b14 in the formula (b-4) is the same group because the preparation of the high purity tetracarboxylic acid dianhydride is easy.

T3 in the formula (b-4) represents an integer of 0 or more and 12 or less. By setting the value of t3 to 12 or less, purification of the tetracarboxylic dianhydride can be facilitated.

From the viewpoint that the tetracarboxylic acid dianhydride can be easily purified, the upper limit of t3 is preferably 5, more preferably 3.

From the viewpoint of the chemical stability of the tetracarboxylic acid dianhydride, the lower limit of t3 is preferably 1, more preferably 2.

T3 in the formula (b-4) is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms which can be selected as R ^b15 and R ^b16 in the formula (b-4) is the same as the alkyl group having 1 to 10 carbon atoms which can be selected as R ^b14 .

R ^b15 and R ^b16 are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, still more preferably 5 or less, Is preferably an alkyl group of 1 or more and 4 or less, particularly preferably 1 or more and 3 or less, particularly preferably a hydrogen atom or a methyl group.

Examples of the tetracarboxylic acid dianhydride represented by the formula (b-4) include norbornane-2-spiro-a-cyclopentanone-a'-spiro-2'-norbornane- ', 6,6' '- tetracarboxylic dianhydride (also called "norbornane-2-spiro-2'-cyclopentanone-5'-spiro- , 6 "-tetracarboxylic dianhydride"), methyl norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 '' - (methylnorbornane) -5,5 " , 6 " -tetracarboxylic dianhydride, norbornane-2-spiro- [alpha] -cyclohexanone- [alpha] -spiro-2 " -norbornane-5,5 ", 6,6 & (Also referred to as " norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2 '' -norbornane-5,5 '', 6,6 '' -tetracarboxylic acid dianhydride Spiro-a-cyclohexanone-a'-spiro-2 '' - (methylnorbornane) -5,5 '', 6,6 "-tetracarboxylic acid dianhydride , Norbornane-2-spiro-a-cyclopropanone-a'-spiro- 2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro-a-cyclobutanone-a'-spiro- 5,5 '', 6,6 '' -tetracarboxylic dianhydride, norbornane-2-spiro-a-cycloheptanone-a'-spiro- ', 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro-a-cyclooctanone-a'-spiro- -Tetracarboxylic dianhydride, norbornane-2-spiro- [alpha] -cyclononanone- [alpha] -spiro-2 " -norbornane-5,5 ", 6,6 " -tetracarboxylic acid dianhydride , Norbornane-2-spiro-a-cyclodecanone-a'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane- -Spiro-a-cyclodecanone-a'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane- Spore-2 " -norbornane-5,5 ", 6,6 " -tetracarboxylic acid 2 & Water, norbornane-2-spiro- [alpha] -cyclotridecanone-a'-spiro-2 " -norbornane-5,5 ", 6,6 " -tetracarboxylic dianhydride, Spiro-a-cyclotetradecanone-a'-spiro-2''-norbornane-5,5 '', 6,6'-tetracarboxylic dianhydride, norbornane- -cyclopentadecanol-a'-spiro-2''-norbornane-5,5 '', 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro- Pentane) -α'-spiro-2''-norbornane-5,5 '', 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro-α- (methylcyclohexanone) -α'-spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic dianhydride, and the like.

The weight average molecular weight of the cardo resin is preferably from 1,000 to 40,000, more preferably from 1,500 to 30,000, and still more preferably from 2,000 to 10,000. Within the above range, sufficient heat resistance and film strength can be obtained while satisfactory developability is obtained.

(Novolac resin)

A novolac resin may be used as the resin (B2). The novolac resin corresponds to an alkali-soluble resin. When the photosensitive composition contains a novolak resin as the resin (B2), excessive heat flow of the cured film can be easily suppressed when post-baking is performed on the cured film when the cured film is formed using the photosensitive composition.

Therefore, in the case of forming a black column spacer using a photosensitive composition, if the photosensitive composition contains a novolac resin, it is easy to form a black column spacer having a desired shape.

As the novolac resin, various novolac resins conventionally blended with the photosensitive composition can be used. The novolak resin is preferably obtained by subjecting an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as " phenol ") and an aldehyde to an addition condensation under an acid catalyst.

· Phenols

Examples of the phenol used in the preparation of the novolak resin include phenol; cresols such as o-cresol, m-cresol and p-cresol; Such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Sileenol; ethyl phenols such as o-ethyl phenol, m-ethyl phenol and p-ethyl phenol; Alkyl phenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol and p-tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol and fluoroglycinol; Alkyl-substituted phenols such as alkyl resorcin, alkyl catechol and alkyl hydroquinone (all alkyl groups having 1 to 4 carbon atoms); alpha -naphthol; ? -naphthol; Hydroxydiphenyl; And bisphenol A. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various properties such as heat resistance of the cured film formed using the photosensitive composition can be controlled by adjusting the blending ratio of both.

The mixing ratio of m-cresol and p-cresol is not particularly limited, but is preferably 3/7 to 8/2 by mole in terms of the molar ratio of m-cresol / p-cresol. By using m-cresol and p-cresol in this range, it is easy to obtain a photosensitive composition capable of forming a cured film having excellent heat resistance.

A novolak resin prepared by using m-cresol and 2,3,5-trimethylphenol in combination is also preferable. When such a novolak resin is used, a photosensitive composition capable of forming a cured film which is difficult to flow excessively by heating during post-baking is particularly easy to obtain.

The blending ratio of m-cresol and 2,3,5-trimethyl phenol is not particularly limited, but is preferably 70/30 or more and 95/5 or less in molar ratio of m-cresol / 2,3,5-trimethylphenol.

· Aldehydes

Examples of the aldehyde used in the preparation of the novolak resin include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde and acetaldehyde. These aldehydes may be used alone, or two or more aldehydes may be used in combination.

· Acid catalyst

Examples of the acid catalyst used for preparing the novolak resin include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and phosphorous acid; Organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid and para-toluenesulfonic acid; And metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

·Molecular Weight

The weight average molecular weight (Mw) of the novolak resin in terms of polystyrene (hereinafter simply referred to as " weight average molecular weight ") is preferably from 2,000 to 1,000,000 as a lower limit value from the viewpoint of resistance to flow by heating the cured film formed using the photosensitive composition More preferably 5000, particularly preferably 10000, more preferably 15000, most preferably 20000, the upper limit is preferably 50000, more preferably 45000, still more preferably 40000 and most preferably 35000 Do.

As the novolak resin, at least two kinds of resins having different weight average molecular weights in terms of polystyrene may be used in combination. A balance between the developability of the photosensitive composition and the heat resistance of the cured film formed using the photosensitive composition can be balanced by using a combination of large and small ones having different weight average molecular weights.

(Modified epoxy resin)

The photosensitive composition contains the epoxy compound (b-3a) and the unsaturated group-containing carboxylic acid (b-3a) as the resin (B2) from the viewpoint of easily imparting higher flow resistance and high water resistance to the cured film formed by using the photosensitive composition, (b-3c) of the reaction product of the polyfunctional epoxy resin (b-3b).

Since the modified epoxy resin has a carboxyl group and an ethylenically unsaturated double bond in its structure, it plays a role as an alkali-soluble resin having a crosslinkable group.

In the specification and claims of the present application, as the compound corresponding to the above definition, a compound not corresponding to the resin having the above-mentioned cardo structure is referred to as a modified epoxy resin.

The epoxy compound (b-3a), the unsaturated group-containing carboxylic acid (b-3b) and the polybasic acid anhydride (b-3c) will be described below.

Epoxy compound (b-3a)

The epoxy compound (b-3a) is not particularly limited as long as it is a compound having an epoxy group, and may be an aromatic epoxy compound having an aromatic group, an aliphatic epoxy compound not containing an aromatic group, or an aromatic epoxy compound having an aromatic group.

The epoxy compound (b-3a) may be a monofunctional epoxy compound or a bifunctional or more polyfunctional epoxy compound, preferably a polyfunctional epoxy compound.

Specific examples of the epoxy compound (b-3a) include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin and biphenyl type epoxy resin Epoxy resin; Glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; Glycidylamine-type epoxy resins such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmethacrylylenediamine and tetraglycidylbisaminomycyclohexane; Heterocyclic epoxy resins such as triglycidyl isocyanurate; Trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-epoxypropoxy) propyl) glycidyl ether, Phenyl] propane and 1,3-bis [4- [1- [4- (2, 3-dipropoxyphenyl) -1,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- methylethyl] phenyl] ethyl] phenoxy] -2-propanol Trifunctional epoxy resin; Tetrafunctional epoxy resins such as tetrahydroxyphenyl ethane tetraglycidyl ether, tetraglycidyl benzophenone, bis-resorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl.

The epoxy compound (b-3a) is preferably an epoxy compound having a biphenyl skeleton.

The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (b-3a-1) in its main chain.

The epoxy compound having a biphenyl skeleton is preferably a polyfunctional epoxy compound having two or more epoxy groups.

By using an epoxy compound having a biphenyl skeleton, it is easy to obtain a photosensitive composition capable of forming a cured film excellent in balance of sensitivity and developability and excellent in adhesion to a substrate.

[46]

(B-3a-1), R ^b17 is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent, and j is an integer of 1 to 4 to be.)

When R ^b17 is an alkyl group having 1 to 12 carbon atoms, specific examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, Butyl group, n-pentyl group, iso-pentyl group, sec-pentyl group, tert-pentyl group, n- n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-undecyl group and n-dodecyl group.

When R ^b17 is a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

When R ^b17 is a phenyl group which may have a substituent, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 or more and 5 or less, and 0 or 1 is preferable.

Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aliphatic acyl group having 2 to 4 carbon atoms, a halogen atom, a cyano group and a nitro group.

The epoxy compound (b-3a) having a biphenyl skeleton represented by the above formula (b-3a-1) is not particularly restricted but includes, for example, epoxy compounds represented by the following formula (b- .

[47]

(B-3a-2), R ^b17 and j are the same as in the formula (b-3a-1), and k is the average number of repeating units in the parentheses is 0 or more and 10 or less.

Among the epoxy compounds represented by the formula (b-3a-2), the compounds represented by the following formula (b-3a-3) are preferable from the viewpoint of easily obtaining a photosensitive composition excellent in balance of sensitivity and developability.

[48]

(In the formula (b-3a-3), k is the same as in the formula (b-3a-2).)

(Unsaturated group-containing carboxylic acid (b-3b))

In preparing the modified epoxy compound (b-3), an epoxy compound (b-3a) is reacted with an unsaturated carboxylic acid (b-3b).

As the unsaturated group-containing carboxylic acid (b-3b), a monocarboxylic acid containing a reactive unsaturated double bond such as an acrylic group or a methacrylic group in the molecule is preferable. Examples of such unsaturated carboxylic acids include acrylic acid, methacrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid,? -Cyanosinic acid and cinnamic acid. The unsaturated group-containing carboxylic acid (b-3b) may be used singly or in combination of two or more.

The epoxy compound (b-3a) and the unsaturated group-containing carboxylic acid (b-3b) can be reacted by a known method. Examples of the preferable reaction method include a method in which an epoxy compound (b-3a) and an unsaturated group-containing carboxylic acid (b-3b) are reacted with a tertiary amine such as triethylamine, benzylethylamine, dodecyltrimethylammonium chloride, A quaternary ammonium salt such as chloride, tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine or triphenylphosphine as a catalyst, and the reaction is carried out in an organic solvent at a reaction temperature of 50 ° C. or higher and 150 ° C. or lower for several hours to several hours Method.

The ratio of the amount of the epoxy compound (b-3a) to the amount of the unsaturated group-containing carboxylic acid (b-3b) used in the reaction is not particularly limited as long as the epoxy equivalent of the epoxy compound (b- Equivalent ratio is usually 1: 0.5 to 1: 2, more preferably 1: 0.8 to 1: 1.25, and particularly preferably 1: 0.9 to 1: 1.1.

When the ratio of the amount of the epoxy compound (b-3a) to the amount of the unsaturated group-containing carboxylic acid (b-3b) is 1: 0.5 to 1: 2 in terms of the equivalent ratio described above, the crosslinking efficiency tends to be improved.

(Polybasic acid anhydride (b-3c))

The polybasic acid anhydride (b-3c) is an anhydride of a carboxylic acid having two or more carboxyl groups.

Examples of the polybasic acid anhydride (b-3c) include, but are not limited to, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, There may be mentioned phthalic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydro- (B-3c-1), represented by the following formula (b-3c-1), can be prepared by reacting a compound represented by the following formula (b-3c-1) with an acid anhydride , And a compound represented by the following formula (b-3c-2). The polybasic acid anhydrides (b-3c) may be used alone or in combination of two or more.

[49]

(In the formula (b-3c-2), R ^b18 represents an alkylene group which may have a substituent having 1 to 10 carbon atoms.)

The polybasic acid anhydride (b-3c) is preferably a compound having two or more benzene rings from the viewpoint of easily obtaining a photosensitive composition having excellent balance of sensitivity and developability. It is more preferable that the polybasic acid anhydride (b-3c) contains at least one of the compound represented by the formula (b-3c-1) and the compound represented by the formula (b-3c-2)

The method of reacting the epoxy compound (b-3a) with the unsaturated group-containing carboxylic acid (b-3b) and then reacting the polybasic acid anhydride (b-3c) can be appropriately selected from known methods.

The ratio of the amount to be used is usually 1: 1, preferably 1: 1, more preferably 1: 1, more preferably 1: 1, more preferably 1: 1 to 1: 0.1, preferably 1: 0.8 to 1: 0.2. Within the above range, it is easy to obtain a photosensitive composition having good developing properties.

The acid value of the modified epoxy resin (b-3) is preferably from 10 mgKOH / g to 150 mgKOH / g, more preferably from 70 mgKOH / g to 110 mgKOH / g, When the acid value of the resin is 10 mgKOH / g or more, sufficient solubility to the developer is obtained. When the acid value is 150 mgKOH / g or less, sufficient curability can be obtained and the surface property can be improved.

The weight average molecular weight of the modified epoxy resin (b-3) is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. When the weight average molecular weight is 1000 or more, it is easy to form a black column spacer having excellent heat resistance and strength. When it is 40,000 or less, it is easy to obtain a photosensitive composition exhibiting sufficient solubility in a developing solution.

(A polymer containing a constituent unit having a cyclic structure in its main chain)

Provided that the polymer containing a constituent unit having a cyclic structure in the main chain is a resin having a predetermined cyclic structure and having a predetermined alkali solubility. (Hereinafter also referred to as " polymer (A2) ") as a suitable example of a polymer containing a constituent unit having a ring structure in its main chain (Hereinafter also referred to as " polymer (A1) "), and a structural unit represented by the following formula (A-1)

The maleimide-derived structural unit (A2a) of the polymer (A2) is not particularly limited as long as it is obtained by polymerizing a monomer having maleimide skeleton. Examples of the monomer having a maleimide skeleton include N-benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

In particular, the photosensitive composition comprising the polymer (A1) containing the constituent unit (A1a) having a ring structure in the main chain has good solubility in a developing solution.

[50]

In the formula (A-1), the ring A is a saturated aliphatic cyclic group having 4 or more carbon atoms and having one oxygen atom as a ring-constituting atom. Ring A is preferably a saturated aliphatic cyclic group having 4 or 5 carbon atoms having one oxygen atom as a ring constituent atom, more preferably a tetrahydrofuran ring or tetrahydropyran ring, more preferably a saturated aliphatic ring group having 4 or 5 carbon atoms, (Hereinafter referred to as " structural unit (A1a1) ") in the structural unit represented by the structural unit (A-3) ) &Quot;) is a tetrahydrofuran ring.

[51]

(Polymer (A1)) containing a structural unit represented by the above formula (A-1) in its main chain is usually a polymer containing a plurality of structural units (structural units (A1a)) represented by the above formula (A- do. In the plurality of structural units (A1a), the ring A contained in each structural unit (A1a) may be the same or different in one main chain constituting the polymer (A1). Concretely, one main chain constituting the polymer (A1) is a structural unit represented by the above formula (A-1) contained in the main chain, and examples thereof include a structural unit represented by the above formula (A-3) (A-3) and the structural unit represented by the above formula (A-4). The structural unit represented by the above formula .

In the formulas (A-1), (A-3) and (A-4), R ^b1 and R ^b2 are each independently a hydrogen atom or -COOR ^b3 , and each R ^b3 is independently a hydrogen atom or a substituent And a hydrocarbon group having 1 to 25 carbon atoms. R ^b1 and R ^b2 are preferably -COOR ^b3 . When one main chain constituting the polymer (polymer (A1)) containing the structural unit represented by the above formula (A-1) contains a plurality of rings A, -COOR ^b3 bonded to each ring A is independently And the same or different groups as -COOR ^b3 may be bonded to each Ring A.

The hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent represented by R ^b1 and R ^b2 , is not particularly limited. Specific examples of the hydrocarbon group include a linear or branched group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t- butyl, t- amyl, stearyl, lauryl, An alkyl group; An aryl group such as phenyl; Cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adanthyl, 2-methyl-2-adamantyl and the like; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like.

When R ^b1 and R ^b2 are hydrocarbon groups, the number of carbon atoms in the hydrocarbon group is preferably 8 or less. The hydrocarbon group having 8 or less carbon atoms is preferably a hydrocarbon group bonded to the primary carbon atom or the secondary carbon atom because the terminal end of the hydrocarbon group is free of bonding from the viewpoint of difficulty in desorption by acid or heat. Such a hydrocarbon group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms and is preferably a linear or branched alkyl group having 1 to 5 carbon atoms.

Specific examples of such a hydrocarbon group include methyl, ethyl, cyclohexyl, and benzyl, and a methyl group is preferable.

When a plurality of the structural units (A1a) are contained in one main chain constituting the polymer (polymer (A1)) containing the structural unit (structural unit (A1a)) represented by the above formula (A-1) R ^b1 and R ^b2 bonded to the structural unit (A1a) may be the same or different between the structural units (A1a).

When the same or different ring A is contained in each structural unit (A1a), R ^b1 and R ^b2 are independent of each other regardless of the kind of each ring A to be bonded.

Specifically, when a plurality of the structural units (structural units (A1a1)) represented by the above formula (A-3) are contained in one main chain constituting the polymer (A1), ^Rb1 And ^Rb2 may be the same or different between the respective structural units (A1a1).

When a plurality of the structural units (structural units (A1a2)) represented by the above formula (A-4) are contained in one main chain constituting the polymer (A1), ^Rb1 and ^Rb2 in each structural unit (A1a2) May be the same or different between the respective structural units A1a2.

The constituent unit (constituent unit (A1a1)) represented by the above formula (A-3) and the constituent unit (constituent unit ( when containing the A1a2)), R ^b1 and R ^b2 and R ^b1 and R ^b2 in each of the structural units (A1a2) in each of the structural units (A1a1) is may be the same or different.

The structural unit (structural unit (A1a1)) represented by the above formula (A-3) may be a part of a repeating unit represented by the following formula (A-5) (hereinafter also referred to as "repeating unit (ar1)"). The structural unit (structural unit (A1a2)) represented by the above formula (A-4) may be a part of a repeating unit represented by the following formula (A-6) (hereinafter also referred to as a "repeating unit (ar2)").

[52]

(In the formulas (A-5) and (A-6), R ^b1 and R ^b2 are each independently the same as defined above.)

Examples of the monomer giving each of the repeating units represented by the above formulas (A-5) and (A-6) include 1,6-dienes represented by the following formulas.

[53]

( ^Wherein R < ^b3 > are each independently the same as defined above).

(A1)) in the monomer composition which gives the polymer (polymer (A1)) containing the structural unit (structural unit (A1a)) represented by the above formula (A-1) The content of the monomer (A1ma) that gives the monomer (A1a1) and the structural unit (A1a2)) may be preferably 1% by mass or more and 60% by mass or less relative to the total amount of the monomers in the monomer composition, More preferably 5% by mass or more and 50% by mass or less, and particularly preferably 10% by mass or more and 40% by mass or less.

The polymer (A1) preferably has a repeating unit (A1b) having an acid group in the side chain. When the polymer (A1) has a repeating unit (A1b) having an acid group in the side chain, a photosensitive composition having excellent alkali developability can be obtained. Examples of the monomer (A1mb) constituting the repeating unit (A1b) having an acid group in the side chain include (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, itaconic acid, omega -carboxy-polycaprolactone Monomers having a carboxyl group such as monoacrylate; And monomers having a carboxylic anhydride group such as maleic anhydride and itaconic anhydride. Among them, (meth) acrylic acid is preferable.

The content of the monomer (A1mb) constituting the repeating unit (A1b) having an acid group in the side chain in the monomer composition for imparting the polymer (A1) is preferably 1% by mass or more, Or more and 50 mass% or less, more preferably 5 mass% or more and 40 mass% or less, further preferably 10 mass% or more and 35 mass% or less.

Preferably, the polymer (A1) has a repeating unit (A1c) having a carbon double bond in the side chain. The recurring unit (A1c) having a carbon double bond in the side chain is obtained by adding a compound having a carbon double bond with a part or all (preferably a part) of the acid group of the recurring unit (A1b) having an acid group in the side chain as a reaction point .

When the acid group of the repeating unit (A1b) having an acid group in the side chain is a carboxyl group, a compound having a carbon double bond, a compound having a double bond with an epoxy group, a compound having a double bond with an isocyanate group, and the like can be used. Examples of the compound having an epoxy group and a double bond include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, P-vinylbenzyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, and the like. Examples of the compound having an isocyanate group and a double bond include 2-isocyanatoethyl (meth) acrylate and the like. When the acid group of the repeating unit (A1b) having an acid group in the side chain is a carboxylic acid anhydride group, a compound having a carbon double bond and having a hydroxyl group and a double bond can be used. As the compound having a hydroxyl group and a double bond, for example, 2-hydroxyethyl (meth) acrylate and the like can be given.

The polymer (A1) may further have another recurring unit (A1e) derived from the other monomer (A1me) copolymerizable with the monomer (A1ma), the monomer (A1mb) and / or the monomer (A1mc).

As the other monomer (A1me), for example, a repeating unit having two or more oxyalkylene groups in the side chain may be further added. Examples of the repeating unit having two or more oxyalkylene groups in the side chain include repeating units represented by the following formulas.

[54]

In the formula, R ^b7 , R ^b8 and R ^b9 are each independently a hydrogen atom or a methyl group, preferably a hydrogen atom. R ^b10 is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a hydrogen atom, A straight chain alkyl group having 1 to 20 carbon atoms, a straight chain alkenyl group having 2 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a straight chain group having 1 to 10 carbon atoms A straight chain alkyl group having from 1 to 5 carbon atoms, a phenyl group or a biphenyl group, and particularly preferably a methyl group, a phenyl group or a biphenyl group. The alkyl group, alkenyl group and aromatic hydrocarbon group may have a substituent. AO represents an oxyalkylene group. The number of carbon atoms of the oxyalkylene group represented by AO is 2 or more and 20 or less, preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, still more preferably 2 or less. The repeating unit having two or more oxyalkylene groups in the side chain may contain one or two or more oxyalkylene groups. and x represents an integer of 0 or more and 2 or less. y represents 0 or 1. z represents an average addition mole number of the oxyalkylene group and is 2 or more, preferably 2 or more and 100 or less, more preferably 2 or more and 50 or less, still more preferably 2 or more and 15 or less.

The repeating unit having two or more oxyalkylene groups in the side chain is composed of a monomer having two or more oxyalkylene groups in the side chain. Examples of the monomer include monomers represented by the following formulas.

[55]

^Wherein R ^b7 , R ^b8 , R ^b9 , R ^b10 , AO, x, y and z are as defined above.

Examples of the monomer having two or more oxyalkylene groups in the side chain include ethoxylated o-phenylphenol (meth) acrylate (EO 2 mols), phenoxy diethylene glycol (meth) acrylate, phenoxypolyethylene glycol ) Methacrylate (EO 4 mole), methoxypolyethylene glycol (meth) acrylate (EO 9 mole), methoxypolyethylene glycol (meth) acrylate (EO 13 mole), methoxy triethylene glycol (meth) (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, Acrylate (EO4-17 mole), nonylphenoxypolypropylene glycol (meth) acrylate (PO5 mole), EO-modified cresol (metha) acrylate (EO2 ), And the like. These monomers may be used alone or in combination of two or more. Of these, ethoxylated o-phenylphenol (meth) acrylate (EO 2 mole), methoxypolyethylene glycol (meth) acrylate (EO 9 mole), methoxypolyethylene glycol (meth) )to be. More preferably, ethoxylated o-phenylphenol acrylate (EO 2 mole), methoxypolyethylene glycol acrylate (EO 9 mole), and methoxypolyethylene glycol acrylate (EO 13 mole). In the present specification, the notation such as " EO 2 mols ", " PO 5 moles " and the like indicate the average addition mole number of oxyalkylene groups.

Examples of the other monomer (A1me) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl Acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, 2- (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Decyl (meth) acrylate, di (Meth) acrylate, nonylphenoxyethyleneglycol (meth) acrylate, nonylphenoxypropyleneglycol, benzyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate and the like; (Meth) acryloylmorpholine (morpholino (meth) acrylate), (meth) acrylamide, N-methyl (meth) acrylamide, N- (Meth) acrylamide, N-isopropyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nt- (Meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N- (Meth) acrylic acid amides such as N, N-dimethyl (meth) acrylamide; Aromatic vinyl compounds such as styrene, vinyltoluene, and? -Methylstyrene; Butadiene or substituted butadiene compounds such as butadiene and isoprene; Ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; And vinyl esters such as vinyl acetate. These monomers may be used alone or in combination of two or more.

The content of the monomer (A1me) for imparting the other recurring units (A1e) in the monomer composition giving the polymer (A1) is preferably 0% by mass or more and 55% by mass or less relative to the total amount of the monomers in the monomer composition More preferably 5% by mass or more and 50% by mass or less, and still more preferably 10% by mass or more and 45% by mass or less.

The polymer (A1) may be a random copolymer or a block copolymer. The polymer (A1) may be used alone or in combination of two or more.

The weight average molecular weight of the polymer (A1) is preferably 3,000 or more and 200,000 or less as measured by a gel permeation chromatography method (GPC) using a tetrahydrofuran (THF) solvent, More preferably from 3,500 to 100,000, and still more preferably from 4,000 to 50,000. With such a range, it is possible to obtain a photosensitive composition having heat resistance and having a viscosity suitable for forming a coating film.

The polymer (A1) can be obtained by polymerizing the monomer composition giving the polymer (A1) by any suitable method. As the polymerization method, for example, a solution polymerization method can be mentioned.

The monomer composition conferring the polymer (A1) may comprise any suitable solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol monomethyl ether; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Alcohols such as methanol and ethanol; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; Dimethyl sulfoxide, and the like. These solvents may be used alone or in combination of two or more. The polymerization concentration at the time of polymerizing the monomer composition is preferably 5% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 50% by mass or less, still more preferably 10% to be.

The monomer composition conferring the polymer (A1) may comprise any suitable polymerization initiator. Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t- Organic peroxides such as peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate and the like; Azo compounds such as 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) '-Azobis (2-methylpropionate), and the like. The content of the polymerization initiator is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total monomers in the monomer composition.

The polymerization temperature when the polymer (A1) is polymerized by the solution polymerization method is preferably 40 占 폚 or more and 150 占 폚 or less, and more preferably 60 占 폚 or more and 130 占 폚 or less.

When a polymer (A1) having a repeating unit (A1c) having a carbon double bond in the side chain is obtained, a compound having the carbon double bond is added to the obtained polymer after the polymerization. Any suitable method may be employed as a method for adding the compound having a carbon double bond. For example, in the presence of a polymerization inhibitor and a catalyst, a compound having a carbon-carbon double bond is reacted with a part or all (preferably a part) of the acid group of the repeating unit (A1b) having an acid group in the side chain, (A1c) having a carbon-carbon double bond can be formed.

The addition amount of the compound having a carbon-carbon double bond is preferably 5 parts by mass or more, more preferably 10 parts or less, per 100 parts by mass of the polymer after polymerization (that is, the polymer before the addition of the compound having carbon double bond) More preferably not less than 15 parts by mass, particularly preferably not less than 20 parts by mass. Within such a range, a photosensitive composition having excellent exposure sensitivity can be obtained. When such a photosensitive composition is used, there is a tendency to obtain a pattern which is easy to form a dense cured coating film and excellent in substrate adhesion. When the addition amount of the compound having a carbon double bond is within the above range, a hydroxyl group is sufficiently generated by addition of a compound having a carbon double bond, and a photosensitive composition excellent in solubility in an alkali developer can be obtained. The upper limit of the amount of addition of the compound having carbon double bond is preferably 170 parts by mass or less based on 100 parts by mass of the polymer after polymerization (that is, the polymer before addition of the compound having carbon double bond) Is not more than 150 parts by mass, and more preferably not more than 140 parts by mass. When the addition amount of the compound having a carbon double bond is within the above range, the storage stability and solubility of the photosensitive composition can be maintained.

Examples of the polymerization inhibitor include alkylphenol compounds such as 6-tert-butyl-2,4-xylenol. Examples of the catalyst include tertiary amines such as dimethylbenzylamine and triethylamine.

The content of the resin (B2) described above is preferably from 1% by mass to 95% by mass, more preferably from 3% by mass to 85% by mass, more preferably from 5% by mass to 70% by mass, based on the solid content of the photosensitive composition Particularly preferred.

When the photosensitive composition contains the resin (B2) in an amount within this range, it is easy to form a photosensitive film of a photosensitive composition and to form a cured film having good mechanical properties and shape.

When the resin (B2) is alkali-soluble, it is easy to realize good alkali developability.

≪ Colorant (C) >

The photosensitive composition comprises a colorant (C) containing a lactam-based pigment. Therefore, by using the above photosensitive composition, it is easy to form a cured product having excellent light shielding properties.

The lactam-based pigment is not particularly limited as long as it is a pigment comprising a compound containing a lactam skeleton which is a cyclic skeleton containing a -CO-NH- bond. The lactam-based pigment preferably exhibits black from the viewpoint of the light shielding property of the cured product.

Preferable examples of the lactam-based pigment that exhibits black include, for example, a compound represented by the following formula (c-1).

[56]

In the formula (c-1), X ^c represents a double bond, and each of Ge isomers is independently E or Z-form, and each of R ^c1 independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, R ^c2 independently represents a hydrogen atom, a methyl group or a phenyl group, and each R ^c3 independently represents a hydrogen atom, a methyl group or a chlorine atom.

The compounds represented by the formula (c-1) may be used alone or in combination of two or more.

R ^c1 is preferably bonded at the 6-position of the dihydroinduron ring from the viewpoint of easy production of the compound represented by the formula (c-1), and R ^c3 is preferably bonded to the 4-position of the dihydroinduron ring. From the same viewpoint, R ^c1 , R ^c2 and R ^c3 are preferably hydrogen atoms.

The compound represented by the formula (c-1) has an EE, ZZ, or EZ form as a geometric isomer, but may be a single compound or a mixture of these geometric isomers.

The compound represented by the formula (c-1) can be produced, for example, by the method described in WO 2000/24736 and WO-A-2010/081624.

In the colorant (C), the ratio of the mass of the lactam-based pigment to the total mass of the pigment and the dye is preferably 3% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more. The upper limit is, for example, 90% or less, preferably 60% or less.

In order to disperse the lactam-based pigment well in the photosensitive composition, the average particle diameter of the lactam-based pigment is preferably 10 nm or more and 1000 nm or less.

The colorant (C) may contain various pigments together with the lactam-based pigment for the purpose of adjusting the color. The pigment that can be used in combination with the lactam-based pigment is not particularly limited. For example, in the color index (CI, published by The Society of Dyers and Colourists), a compound classified as a pigment, (CI) number as described below can be used.

Examples of suitable yellow pigments include C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the numbers are described below), 3,11,12,13,14,15,16,17,20,24,31,35,55,60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, .

Examples of suitable orange pigments include C.I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the numbers are described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 55, 59, 61, 63, 64, 71, and 73, respectively.

Examples of suitable purple pigments include C.I. Pigment Violet 1 (hereinafter, the same is true of C. I. Pigment Violet), and only numbers are given), 19, 23, 29, 30, 32, 36, 37, 38, 39,

Examples of suitable red pigments include C.I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only numbers are given), 2,3,4,5,6,7,8,9,10,11,12,14,15,16 48: 3, 48: 4, 49: 1, 49: 1, 48, : 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: : 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217 , 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264 and 265.

Examples of suitable blue pigments include C.I. 15, 6, 16, 22, 60, 64, and 66 are formed in the same manner as in Example 1 except that Pigment Blue 1 (hereinafter, "CI Pigment Blue" .

Examples of pigments of other colors that may be suitably used include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 37, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Brown pigments such as Pigment Brown 28, C.I. Pigment Black 1, C.I. Pigment Black 7 and the like.

It is also preferable that the colorant (C) contains a black pigment other than the lactam-based pigment together with the lactam-based pigment. The photosensitive composition containing a black pigment is suitably used for forming a black matrix or a black column spacer in a liquid crystal display panel or for forming a bank for partitioning a light emitting layer in an organic EL device.

Examples of other black pigments include metal oxides such as carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, complex oxides, Sulphates, metal carbonates, organic, and inorganic pigments. Of these black pigments, carbon black is preferred because of its ease of availability, ease of formation of a cured film having excellent light shielding properties and high electrical resistance.

Further, the color of the black pigment is not limited to black, which is an achromatic color in the color scheme, but may be a violet black, a blue colored black, or a red colored black.

As the carbon black, known carbon black such as channel black, furnace black, thermal black, and lamp black can be used. Resin-coated carbon black may also be used.

As carbon black, carbon black to which an acidic group is introduced is also preferable. The acid group introduced into the carbon black is a functional group which shows acidity as defined by Brensted. Specific examples of the acidic group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. The acid group introduced into the carbon black may form a salt. The cation forming the acidic group and the salt is not particularly limited within the range not hindering the object of the present invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions and the like, and alkali metal ions such as sodium ion, potassium ion and lithium ion, and ammonium ion are preferable.

Among the carbon black treated with the acid group described above, it is preferable to select from the group consisting of a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, and a sulfonic acid group in view of achieving high resistance of the light- Is preferably a carbon black having at least one functional group.

The method of introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.

1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or the like or an indirect substitution method using a sulfite or a bisulfite hydrogen salt.

2) A method of diazotizing a carbon black with an organic compound having an amino group and an acidic group.

3) A method of reacting an organic compound having a halogen atom and an acidic group and carbon black having a hydroxyl group by the Williamson etherification method.

4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.

5) A method in which carbonyl black is subjected to a Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acid group protected by a protecting group, followed by deprotection.

Among these methods, the method 2) is preferable because the introduction of the acidic group is easy and safe. The organic compound having an amino group and an acidic group used in the method 2) is preferably a compound in which an amino group and an acidic group are bonded to an aromatic group. Examples of such compounds include aminobenzenesulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

The number of moles of the acid group introduced into the carbon black is not particularly limited within the range not hindering the object of the present invention. The number of moles of the acid group introduced into the carbon black is preferably from 1 mmol to 200 mmol, more preferably from 5 mmol to 100 mmol, per 100 g of carbon black.

The carbon black into which the acidic group has been introduced may be coated with a resin.

When a photosensitive composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light shielding property and insulation property and low surface reflectance. Further, by the coating treatment with the resin, there is no particular adverse effect on the dielectric constant of the light-shielding cured film formed using the photosensitive composition. Examples of the resin that can be used for coating carbon black include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glidal resin, epoxy resin and alkylbenzene resin, and thermosetting resins such as polystyrene, polycarbonate, polyethylene terephthalate , Polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyethersulfopolyphenylene sulfone, polyarylate, polyether And a thermoplastic resin such as an ether ketone. The covering amount of the resin with respect to the carbon black is preferably 1% by mass or more and 30% by mass or less with respect to the sum of the mass of the carbon black and the mass of the resin.

As the black pigment, a perylene pigment can be preferably used. Specific examples of the perylene pigments include perylene pigments represented by the following formula (c-2), perylene pigments represented by the following formula (c-3), and perylene pigments represented by the following formula (c-4) . As commercial products, products such as K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33 and 34 and the like can be suitably used as a perylene pigment.

[57]

In formula (c-2), R ^c4 and R ^c5 each independently represent an alkylene group having 1 to 3 carbon atoms and R ^c6 and R ^c7 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group or an acetyl group .

[58]

In the formula (c-3), R ^c8 and R ^c9 each independently represent an alkylene group having 1 to 7 carbon atoms.

[59]

In formula (c-4), R ^c10 and R ^c11 each independently represent a hydrogen atom, an alkyl group having 1 to 22 carbon atoms and may contain a hetero atom of N, O, S or P. When R ^c10 and R ^c11 are alkyl groups, the alkyl groups may be linear or branched.

The compound represented by the formula (c-2), the compound represented by the formula (c-3) and the compound represented by the formula (c-4) Can be synthesized by using the method described in Japanese Patent Publication No. 63-26784. Namely, a heating reaction is carried out in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines as raw materials. The desired product can be obtained by reprecipitating the obtained preparation in sulfuric acid or recrystallizing it in water, an organic solvent or a mixed solvent thereof.

In order to disperse the perylene pigment in the photosensitive composition well, the mean particle diameter of the perylene pigment is preferably 10 nm or more and 1000 nm or less.

In addition, fine particles containing silver tin (AgSn) as a main component (hereinafter referred to as " AgSn alloy fine particles ") are also preferably used as a black pigment together with a lactam-based pigment. The AgSn alloy fine particles may be a main component of the AgSn alloy, and other metal components, for example, Ni, Pd, Au or the like may be contained.

The average particle diameter of the AgSn alloy fine particles is preferably 1 nm or more and 300 nm or less.

When the AgSn alloy is represented by the chemical formula AgxSn, the range of x in which a chemically stable AgSn alloy is obtained is 1? X? 10, and the range of x in which chemical stability and blackness are simultaneously obtained is 3?

Here, when the mass ratio of Ag in the AgSn alloy is obtained in the range of x,

When x = 1, Ag / AgSn = 0.4762

When x = 3, 3 · Ag / Ag 3 Sn = 0.7317

When x = 4, 4 · Ag / Ag4Sn = 0.7843

When x = 10, 10? Ag / Ag10Sn = 0.9008

.

Therefore, the AgSn alloy is chemically stable when it contains Ag in an amount of 47.6 mass% or more and 90 mass% or less, and when Ag contains 73.17 mass% or more and 78.43 mass% or less Ag, the AgSn alloy effectively exhibits chemical stability and blackness Can be obtained.

The AgSn alloy fine particles can be produced using a conventional fine particle synthesis method. Examples of the method for synthesizing fine particles include a gas phase reaction method, a spray pyrolysis method, an atomization method, a liquid phase reaction method, a freeze drying method, and a hydrothermal synthesis method.

The AgSn alloy fine particles have a high insulating property, but depending on the use of the photosensitive composition, the surface may be covered with an insulating film in order to further increase the insulating property. As a material of such an insulating film, a metal oxide or an organic polymer compound is suitable.

As the metal oxide, a metal oxide having an insulating property such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania) .

As the organic polymer compound, a resin having an insulating property, for example, polyimide, polyether, polyacrylate, polyamine compound and the like are suitably used.

The thickness of the insulating film is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less, in order to sufficiently increase the insulating property of the surface of the AgSn alloy fine particles.

The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, the use of an alkoxide such as tetraethoxysilane or aluminum triethoxide is preferable because an insulating film having a uniform film thickness can be formed at a relatively low temperature.

A preferable combination of the colorant (C) is a combination of a lactam-based pigment and C.I. Piquant Blue 16 and C.I. Pigment Blue 60, a combination of a lactam-based pigment, carbon black and C.I. Piquant Blue 16 and C.I. ≪ tb > < tb >

In these combinations, C.I. Piquant Blue 16 and C.I. The total amount of the pigment blue 60 is preferably 10% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less, with respect to the mass of the colorant (C). When the colorant (C) comprises a combination of a lactam-based pigment and carbon black, the mass of the lactam-based pigment in the total of the mass of the lactam-based pigment and the mass of the carbon black is preferably 5% by mass or more and 99% More preferably 40 mass% or more and 95 mass% or less, and still more preferably 60 mass% or more and 90 mass% or less.

In order to uniformly disperse the above-described pigment in the photosensitive composition, a dispersant may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of polyethylene imine type, urethane resin type or acrylic resin type. Particularly, when carbon black is used as a pigment, it is preferable to use an acrylic resin-based dispersant as a dispersant.

In addition, corrosive gas resulting from the dispersing agent may be generated from the cured film. For this reason, it is also an example of a preferable embodiment that the pigment is dispersed without using a dispersant.

As the coloring agent, the inorganic pigment and the organic pigment may be used alone or in combination of two or more. When used in combination, the organic pigment may be added in an amount of 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment And more preferably in a range of 20 parts by mass or more and 40 parts by mass or less.

Further, in the photosensitive composition, a pigment and a dye may be combined and used as a coloring agent. The dye may be appropriately selected from known materials.

Examples of the dye applicable to the photosensitive composition include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes And the like.

In addition, these dyes can be dispersed in an organic solvent or the like by lakening (coagulation) and used as the colorant (C).

In addition to these dyes, dyes described in, for example, JP-A Nos. 2013-225132, 2014-178477, 2013-137543, JP-A-2011-38085, 2014-197206, Can be preferably used.

The amount of the colorant (C) to be used in the photosensitive composition can be appropriately selected within a range not to impair the object of the present invention, and is typically 2% by mass or more and 75% by mass or less with respect to the mass of the entire solid content of the photosensitive composition , And more preferably 3 mass% or more and 70 mass% or less.

When a pigment is used as the colorant (C), the pigment is preferably added to the photosensitive composition after being made into a dispersion in which the pigment is dispersed in the presence or absence of a dispersant at a proper concentration.

In the present specification, the amount of the above-mentioned pigment to be used can be defined as a value including the existing dispersing system.

≪ Other components >

The photosensitive composition may contain various additives as required. Specific examples of the additives include a solvent, a surface conditioner, a sensitizer, a curing accelerator, a photo-crosslinking agent, a photosensitizer, a dispersant, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, And the like. Any of the additives may be conventionally known. Examples of the surfactant include anionic compounds, cationic compounds, and nonionic compounds. Examples of the adhesion improving agent include conventionally known silane coupling agents. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, and the like. Examples of the defoaming agent include a silicone compound and a fluorine compound.

Examples of the chain transfer agent include a mercaptan-based compound, a halogen-based compound, a quinone-based compound, and? -Methylstyrene dimer. By containing the chain transfer agent, the pattern shape (particularly, the CD variation of the hole pattern and the exposure margin) can be well controlled. Among them, 2,4-diphenyl-4-methyl-1-pentene (? -Methylstyrene dimer) is preferable in addition to the above effects in that it can reduce the amount of the compound to be added, coloring and odor.

When a solvent is used in the photosensitive composition, examples of the solvent to be used include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono Methyl ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, Propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene Glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (Poly) alkylene glycol monoalkyl ethers such as monoethyl ether; (Poly) alkylene ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n- Butyl acetate, isobutyl acetate, isopentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, Other esters such as methyl, ethyl acetoacetate and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; And amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone, or two or more solvents may be used in combination.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (GPMEA), propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (MEDG) Cyclohexanone and 3-methoxybutyl acetate (MBA) are preferable because they exhibit excellent solubility in the above-mentioned components (A1) and (A2) and optionally used component (B), and propylene glycol monomethyl ether acetate , 3-methoxybutyl acetate is particularly preferred. The content of the solvent may be appropriately determined depending on the use of the photosensitive composition, but may be, for example, about 50 parts by mass or more and 900 parts by mass or less based on 100 parts by mass of the total solid content of the photosensitive composition.

≪ Method of preparing photosensitive composition >

The photosensitive composition according to the present invention can be prepared by uniformly stirring and mixing the above components, uniformly dissolving and dispersing the components, and then filtering the resultant solution with a filter such as a 0.2 μm membrane filter, if necessary.

&Quot; Method of forming a hardened product and hardened product "

The method of forming a cured product is the same as the conventional method of forming a cured product formed by using a photosensitive composition except that the above-described photosensitive composition is used.

The method of forming a cured product using the above-described photosensitive composition is not particularly limited, and can be appropriately selected from conventionally employed methods. The cured product is formed as a molded product having a desired shape by controlling the shape of the coated film at the time of applying the photosensitive composition or by combining position-selective exposure and development. Examples of the method for forming a suitable cured product include a coating film forming step of forming a coating film using the above-mentioned photosensitive composition and an exposure step of exposing the coating film. When the exposure is performed in a position-selective manner, the exposed coating film may be developed with a developer to obtain a patterned cured product.

First, in the coating film forming step, for example, a non-contact type coating such as a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, a spinner (rotary coating device), a curtain flow coater, The photosensitive composition according to the present invention is applied using the apparatus, and the solvent is removed by drying (pre-baking) if necessary to form a coating film.

A photosensitive composition filled in a concave portion of a substrate having concavities and convexities or a photosensitive composition filled in a concave portion of a mold is also referred to as a " coating film " for convenience.

Then, the formed coating film is provided in the exposure process. In the exposure step, the coating film is irradiated with a radiation such as ArF excimer laser, KrF excimer laser, F ₂ excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X-ray, g- Or an electromagnetic wave to expose the coating film. Exposure to the coating film may be performed selectively through a negative type mask. The exposure dose varies depending on the composition of the photosensitive composition, but is preferably, for example, about 10 mJ / cm ² to about 600 mJ / cm ² or less.

The exposed coating film is developed as needed.

The above-mentioned photosensitive composition is hardly dissolved excessively in an alkali developing solution after exposure. Therefore, by using the above-described photosensitive composition, it is easy to form a patterned cured product having a good shape using the exposed portion as a convex portion and the unexposed portion as a concave portion.

In the developing process, the exposed coating film is developed with a developing solution to form a patterned cured product in a desired shape. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

If necessary, post-baking may be performed on the cured product after exposure or the patterned cured product after development, and further heat curing may be carried out. The post bake temperature is preferably 150 ° C or more and 270 ° C or less.

The cured product is formed using the above-described photosensitive composition. The cured product is preferably a black matrix or black column spacer used for various image display apparatus panels. The black matrix or black column spacer made of the cured product formed by using the photosensitive composition described above is excellent in cross-sectional shape and excellent in adhesion to the substrate even when cured at a low exposure dose. Therefore, an image display panel having such a black matrix or a black column spacer is suitably used in various image display devices such as a liquid crystal display device and an organic EL display device.

When the cured film composed of the above-mentioned cured product is used for applications requiring a light shielding property such as a black matrix or a black column spacer, the OD value of the cured film is preferably 1.2 or more per 1 μm as an OD value of the cured film formed under the following conditions . The upper limit is not particularly limited, but is, for example, 3 or less per 1 m.

≪ Cured film forming condition &

First, the photosensitive composition is applied on a wafer substrate by a spin coater (1H-360S, manufactured by Mikasa). Then, the coated film on the wafer substrate was heated at 180 캜 for 20 minutes to obtain a cured film for OD value measurement of about 1.0 탆 in film thickness.

The above cured film forming conditions are simulated conditions in which no exposure is performed. Further, the change in the OD value due to the presence or absence of exposure to the cured film is small.

The OD value of the cured film formed can be measured using, for example, a transmittance meter (D-200II, manufactured by GretagMarkbeth).

When the photosensitive composition is used to perform exposure through a halftone mask to form a patterned cured film, the patterned cured product to be formed may have a sufficient difference in height between the Fulton-exposed portion and the halftone-exposed portion A sufficient height of the halftone exposure unit can be ensured. Therefore, the cured film formed using the above photosensitive composition is suitably used as a black column spacer used in a display panel such as a liquid crystal display panel.

≪ Photosensitive adhesive >

The above-described photosensitive composition can be suitably used as a photosensitive adhesive. When the photosensitive composition containing the colorant (C) is used as a photosensitive adhesive, the visibility and light shielding property of the adhesive or the cured product of the adhesive are good.

The above-mentioned photosensitive composition can form a cured product having excellent adhesion even in exposure at a low exposure dose. Therefore, for example, when the adhesive layer is formed by forming an adhesive layer having a thickness of 1 占 퐉 or more and 500 占 퐉 or less, the above-described photosensitive adhesive is suitably used.

Particularly, in the manufacture of automobiles, motorcycles, bicycles, railway vehicles, aircrafts, ships and various building members, and welding of various products by industrial robots, screwing, Is changed to adhesion using the photosensitive adhesive described above, there is no disconnection of screws or screws due to metal fatigue or the like when the bonded final product is lightened or when bonding is performed by screw fixing or screw fixing, And that corrosion due to battery curing does not occur when a different kind of metal is bonded.

The bonding method using the above photosensitive adhesive is not particularly limited. The above-mentioned photosensitive adhesive can be used in a method of adhering an adherend surface to various articles.

As a typical bonding method,

Forming an adhesive layer made of a photosensitive adhesive on one or both sides of the opposing surface to be adhered,

And then curing the adhesive layer by exposure.

The method for forming the adhesive layer made of the photosensitive adhesive is not particularly limited. Typically, a photosensitive adhesive is applied to one or both of the opposite surfaces to be adhered to form an adhesive layer.

Further, a photosensitive adhesive may be injected into the gaps in a state in which gaps having a desired width are formed between the glued surfaces.

The number of articles to be bonded may be one, or may be two or more. In the case where the material of the object to be bonded has flexibility and flexibility, the number of articles to be bonded may be one. When the number of articles to be bonded is one, for example, a case in which a single rectangular plastic plate is bent into a cylindrical shape and a joint portion of the plastic plate is bonded.

The exposure is carried out in the same manner as the formation of the above-mentioned cured film. When the article to be adhered is transparent, a method of irradiating exposure light to the adhesive layer is not particularly limited. In this case, the adhesive layer may be irradiated with the exposure light while transmitting the article to be adhered, or the exposure light may be irradiated so that the exposure light enters from the end face of the adhesive layer.

When the article to be adhered is made of an opaque material such as a metal, the exposure is performed so that the exposure light enters from the end face of the adhesive layer.

«Other uses»

The above-mentioned photosensitive composition can be used for various uses in which photosensitive compositions are conventionally used, such as formation of an etching mask in semiconductor processing, glass processing, and the like.

The above-described photosensitive composition can also be applied to the formation of a photosensitive composition layer in a stereolithography method by so-called 3D printing, which includes a step of forming a photosensitive composition layer.

The lamination of the layers cured by exposure in 3D printing is a so-called self-adhesion to a layer of the cured product formed using the photosensitive composition. Therefore, the stereolithography method using 3D printing using the photosensitive adhesive composed of the photosensitive composition described above is also included in the above-described bonding method using a photosensitive adhesive as an embodiment.

Since the above-mentioned photosensitive composition is excellent in light transmittance, even when the thickness of the photosensitive composition layer is made thick, the photosensitive composition layer can be cured well in a short time by exposure. Therefore, when the above-described photosensitive composition is applied to stereolithography by 3D printing, the number of times of lamination and the number of exposures of the photosensitive composition layer can be reduced by increasing the film thickness of the photosensitive composition layer, Can be manufactured.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Examples 1 to 4, Comparative Example 1 and Comparative Example 2]

, 9 parts by mass of the photopolymerizable compound (B1), 40 parts by mass of the resin (B2) of the kind described in Table 2 and 50 parts by mass of the colorant (C) were added to 1 part by mass of the photopolymerization initiator (A) Dissolved in a solvent, and dispersed to prepare a photosensitive composition. The types and ratios (% by mass) of the photopolymerization initiator (A) are as shown in Table 2.

As the photopolymerization initiator (A), the following PI-1 and PI-2 were used. The light absorption characteristics of these photopolymerization initiators are shown in Table 1 below.

[60]

As photopolymerizable compound (B1), dipentaerythritol hexaacrylate was used.

As the resin (B2), a resin B2a prepared in the following Preparation Example 1 and an acrylic resin B2b, a resin B2c and a resin B2d made of the following structural units were used. The numerical value at the lower right of the parenthesis in the following formula is the content (mass%) of each structural unit in the resin.

In the following resin B2d, structural units derived from 3,4-epoxytricyclodecan-8-yl acrylate and structural units derived from 3,4-epoxytricyclodecan-9-yl acrylate And the resulting structural unit is the same mole.

[61]

[Preparation Example 1]

First, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid were added to a 500 mL four- And the mixture was heated and dissolved at 90 to 100 ° C while blowing air at a rate of 25 mL / min. Then, the solution was gradually elevated to a cloudy state and heated to 120 ° C to be completely dissolved. At this time, the solution gradually became a transparent point group, but stirring was continued. In the meantime, the acid value was measured, and the heating and stirring were continued until it was less than 1.0 mg KOH / g. It took 12 hours to reach the target price. Then, the mixture was cooled to room temperature to obtain bisphenol fluorene-type epoxy acrylate which was colorless transparent and solid and represented by the following formula.

[62]

Then, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed , The temperature was gradually raised, and the reaction was carried out at 110 to 115 ° C for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain a resin B2a which is a cardo resin. The disappearance of the acid anhydride group was confirmed by IR spectrum.

As the colorant (C), 20 parts by mass of C.I. Pigment Blue 16 and 20 parts by mass of C.I. Pigment Blue 60, 12 parts by mass of carbon black and 48 parts by mass of a lactam black pigment (compound represented by the following formula) were mixed and dispersed by a bead mill for 12 hours in the presence of a dispersing agent (20 mass% The black pigment composition thus obtained was used.

[0065]

As the organic solvent, a mixed solvent (mixing ratio (mass ratio), MBA: AN: PGMEA = 60:20:20) of 3-methoxybutyl acetate (MBA), cyclohexanone (AN) and propylene glycol monomethyl ether acetate ).

Using the obtained photosensitive compositions of Examples 1 to 4 and Comparative Examples 1 and 2, the sensitivity and pattern shape of the photosensitive composition were evaluated according to the following methods.

≪ Evaluation of sensitivity and pattern shape >

The photosensitive composition obtained in each of the Examples and Comparative Examples was applied on a glass substrate using a spinner, and then the coated film was dried at 100 캜 for 120 seconds to obtain a coated film having a thickness of about 2.5 탆.

Subsequently, exposure was performed on the coating film through a negative type mask for dot pattern formation of 10 mu m in diameter using an exposure apparatus (TME150RTO, manufactured by TOPCON Co., Ltd.).

After the exposure, a spraying phenomenon was carried out at 25 캜 for 60 seconds using an aqueous solution of potassium hydroxide at a concentration of 0.05% by mass as a developer.

The exposed coated film after development was post-baked at 230 캜 for 20 minutes to obtain a patterned cured film.

The pattern peeling of the formed dot pattern and the taper angle of the cross-sectional shape were confirmed by changing the exposure amount. The minimum exposure amount capable of forming a pattern is described. This minimum exposure amount is shown in Table 2 as sensitivity (mJ / cm 2).

The cross-sectional shape of the pattern formed at the same exposure amount as the sensitivity was observed with a microscope, and the taper angle, which is the angle formed by the substrate surface and the pattern end face, was measured.

Hereinafter, the taper angle will be described with reference to Figs. 1 (a) and 1 (b).

When the light-shielding pattern is formed by using the photosensitive composition, as shown in Fig. 1 (a), the cross section 1, which is a cross section in the width direction of the pattern, is formed on the upper side 1b, It is generally preferable to have a trapezoidal shape with a narrow width. At this time, the angle [theta] formed by the cross section 1 of the pattern and the substrate (not shown) becomes an acute angle close to 80 [deg.].

However, in the case where a light-shielding pattern is formed using a known photosensitive composition, when the above-mentioned angle? Is excessively small or as shown in FIG. 1 (b), as a part of the bottom of the pattern melts at the time of development, The undercuts 21 may be formed on both ends of the lower side 2a of the end face 2 in the width direction of the lower face 2a. When the undercut 21 is formed, the angle? Formed between the cross section 2 of the pattern and the substrate (not shown) becomes an obtuse angle.

When an undercut occurs in the light shielding pattern, for example, when such a pattern is used as a black matrix, a bubble remaining in the undercut portion may cause a deterioration in image quality in the image display apparatus.

Taking into consideration the above-mentioned condition concerning the sectional shape of the light shielding pattern, the sectional shape of the pattern was judged according to the following criteria based on the measured taper angle.

Table 2 shows the evaluation results of the cross-sectional shape (taper angle) of the pattern.

×: 20 to 30 degrees

?: 30 to 50 degrees

○: 50 to 65 degrees

◎: 65 to 80 degrees

As shown in Table 2, the photopolymerization initiator (A) contains two oxime ester compounds having a peak in the wavelength region of 320 nm or more and less than 400 nm in the light absorption spectrum, and 10 Or more of the compound represented by the formula (1) is not included as the photopolymerization initiator (A), and the peak wavelengths of the two oxime ester compounds are different from each other, even if the photosensitive composition contains a lactam- It can be seen that the formation of the pattern closely adhering well to the substrate at the low exposure dose and the favorable cross-sectional shape of the formed pattern can be achieved.

Claims (13)

1. A photosensitive composition comprising a photopolymerization initiator (A) and a colorant (C)
In the absorption spectrum, two or more oxime ester compounds having a peak in a wavelength region of 320 nm or more and less than 400 nm are contained,
Wherein the photopolymerization initiator (A) does not contain a compound exhibiting a gravimetric extinction coefficient of 10 or more at any one wavelength in a wavelength region of 400 nm or more,
The maximum wavelengths of the peaks with respect to the two or more kinds of oxime ester compounds are different from each other,
Wherein the colorant (C) contains a lactam pigment. The method according to claim 1,
Of the maximum wavelength of the peak of the two or more of the oxime ester compounds, the maximum wavelength of the long wavelength side of the maximum wavelength λ _{max to-r,} and the short wavelength side in the case of a λ _max-b, wherein λ _max- wherein the difference between _r and the? _max-b is 20 nm or more. The method according to claim 1 or 2,
Wherein the photopolymerization initiator (A) is represented by the following formula (a1):
However,

(In the formula (a1), R ¹ is a monovalent organic group, R ² is a hydrocarbon group which may have a substituent, or a heterocyclyl group which may have a substituent, R ³ is a monovalent organic group, and R ⁴ R ⁵ and R ⁶ are each independently a benzene ring which may have a substituent or a naphthalene ring which may have a substituent and m 1, m 2 and m 3 are each 0 or 1.)
(1) to (3):
(1) R ¹ includes a group represented by -OR ⁷ , and R ⁷ is a halogenoalkyl group.
(2) m2 is 1, R ⁴ comprises a group represented by -OR ⁷ , and R ⁷ is a halogenoalkyl group.
(3) R ³ is a branched chain alkyl group which may have a substituent.
(A1) satisfying at least one of the following conditions: (a2) an oxime ester compound
[Figure 2]

(In the formula (a2), CR represents a group represented by the following formula (a2a) or the following formula (a2b):
[Figure 3]

, R ^a1 is a hydrogen atom, a nitro group or a monovalent organic group, R ^a2 and R ^a3 each represent a straight chain alkyl group which may have a substituent, a straight chain alkoxy group which may have a substituent, Or a hydrogen atom, R ^a2 and R ^a3 may combine with each other to form a ring, R ^a4 is a monovalent organic group, and R ^a5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent An aliphatic hydrocarbon group or an aryl group which may have a substituent, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.)
(A2) represented by the following general formula (1). The method of claim 3,
Wherein in the formula (a2), the CR is a group represented by the formula (a2a). The method according to claim 1 or 2,
A photosensitive composition comprising a polymerizable base component (B), wherein the polymerizable base component (B) comprises a photopolymerizable compound (B1) or a photopolymerizable compound (B1) and a resin (B2). A method for forming a coating film using the photosensitive composition according to claim 1 or 2,
As for the coating film,
≪ / RTI > The method of claim 6,
The exposure is performed in a position-selective manner with respect to the coating film,
And developing the exposed coating film. A cured product of the photosensitive composition according to claim 1 or 2. A black matrix or black column spacer comprising the cured product of claim 8. A panel for an image display apparatus comprising the black matrix or black column spacer according to claim 9. An image display apparatus comprising the panel for an image display apparatus according to claim 10. A photosensitive adhesive comprising the photosensitive composition according to claim 1 or 2. As a method for bonding an adherend surface,
Forming an adhesive layer made of the photosensitive adhesive according to claim 12 on one or both sides of the opposite surface to be adhered,
And curing the adhesive layer by exposure.

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