JP2015165297A - Photosensitive composition for light-shielding film, and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for a light-shielding film which retains high definition and high light shielding, secure sufficient development adhesion even in forming fine lines, and can provide a coating excellent in adhesion to a glass substrate.SOLUTION: A photosensitive resin composition for a light-shielding film contains (A) a prescribed polymerizable unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) a photoinitiator, and (D) a light-shielding component. The weight ratio of (A)/(B) is 50/50 to 90/10. The content of the (C) component is 2-30 pts.wt. relative to the total content 100 pts.wt. of the (A) component and the (B) component. The photoinitiator of the (C) component contains a compound represented by the general formula (I) in the figure.

Description

  The present invention relates to a photosensitive resin composition for a light shielding film and a cured product thereof, and more specifically, an alkaline aqueous solution development type photosensitive resin composition for a light shielding film suitable for forming a fine light shielding film on a transparent substrate. The light-shielding film obtained by curing and the cured product thereof is suitably used when forming a color filter or a touch panel.

  A color liquid crystal display device has a liquid crystal part for controlling the amount of light transmitted or reflected and a color filter as components, and the manufacturing method of the color filter is usually applied to the surface of a transparent substrate such as glass or plastic sheet. A method is used in which a black matrix is formed, and subsequently, different hues of red, green, and blue are sequentially formed in a color pattern such as a stripe shape or a mosaic shape.

  In recent years, color liquid crystal display devices have been used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. The color filter is one of the important members that influence the visibility of the color liquid crystal display device. In order to improve the visibility, that is, to obtain a clear image, red (R), green ( G), blue (B), and other pixels need to have higher color purity than before, and the black matrix needs to achieve higher light shielding. For this purpose, a colorant is added to the photosensitive resin composition. Must be added in large amounts.

  Also, in recent years, ultra-high definition (400 Pixel Per Inch or higher) technology to obtain Full High Definition resolution is required for small and medium-sized panels such as smartphones, and high definition is an indispensable technology trend. . In order to achieve high definition, it is necessary to make each pixel size of red, green and blue finer, but the aperture ratio of the color filter (area ratio of RGB pixels through which the backlight is transmitted) must not be reduced. It is necessary for high brightness, and the thinning of the black matrix is also required at the same time. That is, the line width of the black matrix is conventionally 6 to 8 μm, but recently, a 4 to 5 μm size has been required.

  Further, there is a tendency to increase the backlight intensity in order to increase the luminance, and accordingly, in order to prevent light leakage from the black matrix, it is necessary to increase the light shielding of the black matrix around the RGB. In order to ensure high light shielding, the thickness of the black matrix can be increased. However, increasing the thickness makes it more susceptible to the development process and increases the variation in the line width of the black matrix within the mother glass surface. . In particular, in the case of a thin line of 4 to 5 μm, variations in line width have a great influence on display performance such as occurrence of display unevenness. Therefore, in order to secure a target light shielding degree with a thin film thickness as much as possible, it is necessary to improve the light shielding property per unit film thickness. However, since the content of the black pigment in the resin composition is usually increased, as a result, the blending ratio of the binder resin, acrylate component, etc. contributing to curability becomes relatively small, and the coating film is sufficiently cured. It becomes difficult, the adhesiveness of a coating film and a glass substrate falls, and the problem that peeling etc. become easy to produce arises.

  By the way, a PCT (Pressure Cooker Test) is generally performed as a durability test (reliability test) in a liquid crystal panel. This test method is performed under severe conditions of a temperature of 121 ° C., a humidity of 100%, and an atmospheric pressure of 2 atm. The liquid crystal panel is left for a period of time, and the presence or absence of liquid crystal leakage sealed between the color filter substrate and the TFT substrate of the liquid crystal panel is checked. The black matrix exists between each color of red, green, and blue. In addition to improving the contrast, it also functions as an outer frame light-shielding film for the color filter. A part of the outer frame light-shielding film is connected to the counter substrate via a sealing material. They are pasted together. For this reason, the black matrix is also required to have a high adhesion strength that does not peel off from the glass substrate even under severe conditions such as PCT. In particular, in recent years, there is a strong need for high light shielding even in the outer frame light shielding film in order to improve the visibility of the liquid crystal panel.

  As described above, in a photosensitive resin composition having a high content of light shielding material and difficult to be cured, a fine line pattern having good pattern dimension stability, pattern adhesion, and sharpness of the edge shape of the pattern can be obtained at a low exposure amount. It is required to obtain a wide development margin and to form a black matrix and an outer frame light-shielding film with high adhesion and high adhesion to a glass substrate even in durability tests such as PCT. In addition, for the same purpose as the color filter outer frame light shielding film, there is an increasing demand for forming a light shielding film on the outer frame or the like of the touch panel.

  Therefore, for example, Patent Documents 1 to 3 propose a photosensitive resin composition for a black matrix containing an oxime ester-based compound as a highly sensitive photopolymerization initiator. However, it is difficult to exhibit sufficient performance in terms of obtaining a fine line pattern with a wide development margin that has excellent pattern dimensional stability at low exposure, good pattern adhesion, and sharp edge shape. There is no specific description regarding adhesion in durability tests such as PCT.

JP 2005-242279 A JP 2006-53569 A JP 2008-100755 A

  The present invention has been made in view of the above-mentioned problems, and the object of the present invention is also in the case where a fine line of, for example, 5 μm is formed in the photosensitive resin composition while maintaining high definition and high light shielding. An object of the present invention is to provide a photosensitive resin composition for a light-shielding film that sufficiently secures development adhesion and is excellent in adhesion to a glass substrate. The present invention also provides a cured product such as a light-shielding film pattern formed by photolithography using the photosensitive resin composition, and further provides a color filter and a touch panel containing the cured product.

As a result of studies conducted by the present inventors to solve the above-described problems, the light of a photosensitive resin composition containing a polymerizable unsaturated group-containing alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a light-shielding component. By blending an oxime-based photopolymerization initiator having a specific chemical structure as a polymerization initiator, it is possible to sufficiently secure development adhesion even in the formation of fine lines while maintaining high definition and high light shielding, The inventors have found that a light-shielding film having excellent adhesion to a glass substrate can be obtained, and completed the present invention.
That is, the gist of the present invention is as follows.

但し、一般式（Ｉ）において、R₁およびR₂は、炭素Cが１〜２０個のアルキル基又は炭素Cが６〜２０個のアリール基を示し、前記アルキル基又はアリール基はエーテル結合を含んでもよく、また前記アルキル基又はアリール基における水素原子の一部が以下に示す置換基で置換されていてもよい。置換基としては、炭素Cが2〜12個のアルケニル基、炭素Cが4〜8個のシクロアルケニル基、炭素Cが2〜12個のアルキニル基、炭素Cが3〜１０個のシクロアルキル基、フェニル基、ナフチル基、ハロゲンで置換されていてもよい炭素Ｃが１〜５のアルコキシ基、又はハロゲンである。R₃は、炭素Cが6〜20個のアリール基、または、炭素5〜20個のヘテロアリール基を示す。 (1) The following components (A) to (D),
(A) a polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting a reaction product of a compound having two or more epoxy groups with (meth) acrylic acid and a polyvalent carboxylic acid or an anhydride thereof;
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator, and
(D) In a photosensitive resin composition for a light-shielding film comprising as an essential component one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and light-shielding materials,
The weight ratio (A) / (B) of the component (A) and the component (B) is 50/50 to 90/10, and the total amount of the component (A) and the component (B) is 100 parts by weight ( C) 2-30 parts by weight of component,
And the photosensitive resin composition for light shielding films characterized by including the compound represented by the following general formula (I) as a photoinitiator of (C) component.

However, in the general formula (I), R ₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group represents an ether bond. In addition, a part of hydrogen atoms in the alkyl group or aryl group may be substituted with the following substituents. As the substituent, carbon C has 2 to 12 alkenyl groups, carbon C has 4 to 8 cycloalkenyl groups, carbon C has 2 to 12 alkynyl groups, and carbon C has 3 to 10 cycloalkyl groups. , Phenyl group, naphthyl group, carbon C which may be substituted with halogen is 1-5 alkoxy group, or halogen. R ₃ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms.

但し、一般式（II）において、R₁およびR₂は、炭素Cが１〜２０個のアルキル基又は炭素Cが６〜２０個のアリール基を示し、前記アルキル基又はアリール基はエーテル結合を含んでもよく、また前記アルキル基又はアリール基における水素原子の一部が以下に示す置換基で置換されていてもよい。置換基としては、炭素Cが2〜12個のアルケニル基、炭素Cが4〜8個のシクロアルケニル基、炭素Cが2〜12個のアルキニル基、炭素Cが3〜１０個のシクロアルキル基、フェニル基、ナフチル基、ハロゲンで置換されていてもよい炭素Ｃが１〜５のアルコキシ基、又はハロゲンである。 (2) The photosensitive resin composition for light-shielding films according to (1), wherein the photopolymerization initiator of component (C) contains a compound represented by the following general formula (II):

However, in General Formula (II), R ₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group has an ether bond. In addition, a part of hydrogen atoms in the alkyl group or aryl group may be substituted with the following substituents. As the substituent, carbon C has 2 to 12 alkenyl groups, carbon C has 4 to 8 cycloalkenyl groups, carbon C has 2 to 12 alkynyl groups, and carbon C has 3 to 10 cycloalkyl groups. , Phenyl group, naphthyl group, carbon C which may be substituted with halogen is 1-5 alkoxy group, or halogen.

但し、一般式（III）において、Ｒ_４及びＲ_５は、独立に水素原子、-O-CH₃、-O-CH₂CH₃、-O-(CH₂)_n＋１CH₃、-O-CH₂CF₃、又は、-O-CH₂（CF₂）_nCHF₂を示す。ただし、R_４またはR_５のいずれか１つは水素原子である。ｎは１〜３の整数である。 (3) The photosensitive resin composition for a light-shielding film according to (1), wherein the photopolymerization initiator of the component (C) contains a compound represented by the following formula (III).

However, in the general formula (III), R ₄ and R ₅ are independently a hydrogen atom, —O—CH ₃ , —O—CH ₂ CH ₃ , —O— (CH ₂ ) _{n + 1} CH ₃ , —O—CH _{2 represents} CF ₃ or —O—CH ₂ (CF ₂ ) _n CHF ₂ . However, any one of R ₄ or R ₅ is a hydrogen atom. n is an integer of 1 to 3.

(4) The photosensitive resin composition for a light-shielding film according to (1), wherein the photopolymerization initiator of the component (C) contains a compound represented by the following formula (IV).

但し、一般式（V）において、Ｒ_６及びＲ_７は、独立に水素原子、炭素数１〜５のアルキル基、又はハロゲン原子を示し、Ｘは、‐CO‐、−SO₂−、‐C(CF₃)₂−、-Si(CH₃)₂‐、-CH₂‐、-C(CH₃)₂‐、-O-、フルオレン-9,9-ジイル基又は単結合を示し、ｌは０〜１０の数である。 (5) As component (A), a polymerizable compound obtained by further reacting a reaction product of a compound represented by the following general formula (V) and (meth) acrylic acid with a polyvalent carboxylic acid or an anhydride thereof. The photosensitive resin composition for light-shielding films according to any one of (1) to (4), wherein a saturated group-containing alkali-soluble resin is used.

In the general formula (V), R ₆ and R ₇ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X represents —CO—, —SO ₂ —, —C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or a single bond, It is a number from 0 to 10.

(6) The content of the light shielding component in the component (D) is 40 to 70% by mass with respect to the solid content in the photosensitive resin composition for the light shielding film, according to any one of (1) to (5). Photosensitive resin composition for light shielding film.
(7) (D) The photosensitive resin composition for light shielding films in any one of (1)-(6) whose light shielding component is carbon black.
(8) A coating film formed by curing the photosensitive resin composition for a light shielding film according to any one of (1) to (7).
(9) The photosensitive resin composition for a light-shielding film according to any one of (1) to (7) is applied on a transparent substrate and prebaked, and then exposed to an ultraviolet exposure device, developed with an alkaline aqueous solution, and post-baked. A color filter comprising a light-shielding film produced in the above manner.
(10) The photosensitive resin composition for a light-shielding film according to any one of (1) to (7) is applied on a transparent substrate and prebaked, and then exposed to an ultraviolet exposure device, developed with an alkaline aqueous solution, and post-baked. A touch panel comprising a light-shielding film manufactured in the above manner.

Hereinafter, the present invention will be described in detail.
As the polymerizable unsaturated group-containing alkali-soluble resin of the component (A), preferably, an epoxy compound having two glycidyl ether groups derived from bisphenols is added to (meth) acrylic acid (this is “acrylic acid and (Or methacrylic acid)), and an epoxy (meth) acrylate acid adduct obtained by reacting the resulting compound having a hydroxy group with a polyvalent carboxylic acid or its anhydride. The epoxy compound derived from bisphenols means an epoxy compound obtained by reacting bisphenols with epihalohydrin or an equivalent thereof. Since the component (A) has both a polymerizable unsaturated double bond and a carboxyl group, it provides excellent photocurability, good developability and patterning characteristics to the photosensitive resin composition, and improves the physical properties of the light-shielding film.

  A preferred example of the component (A) is derived from an epoxy compound represented by the general formula (V). This epoxy compound is derived from bisphenols and first reacted with an unsaturated group-containing monocarboxylic acid. The reaction product of this epoxy compound and unsaturated group-containing monocarboxylic acid is reacted with (a) dicarboxylic acid or tricarboxylic acid or acid anhydride thereof, and (b) tetracarboxylic acid or acid dianhydride thereof. A polymerizable unsaturated group-containing alkali-soluble resin is obtained. Hereinafter, the case where (A) component is obtained using the compound of general formula (V) is demonstrated.

  Examples of bisphenols that give an epoxy compound of the general formula (V) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and bis (4-hydroxy-3,5-dichlorophenyl). ) Ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoro Propane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy -3,5-dimethylphenyl) dimethyl Silane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5- Dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5) -Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4 -Hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ) Ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9 , 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5 -Dibromophenyl) fluorene, 4,4'-biphenol, 3,3'-biphenol and the like. Among these, bisphenols in which X in the general formula (V) is a fluorene-9,9-diyl group can be particularly preferably used.

  In obtaining the alkali-soluble resin (A), preferably, the bisphenols and epichlorohydrin are reacted to obtain an epoxy compound having two glycidyl ether groups. Since this reaction generally involves oligomerization of a diglycidyl ether compound, an epoxy compound of the general formula (V) is obtained. Usually, l has an average value of 0 to 10 (not necessarily an integer) because a plurality of values coexist, but a preferable average value of l is 0 to 3. When the value of l exceeds the upper limit, when the photosensitive resin composition using an alkali-soluble resin synthesized using the epoxy compound is used, the viscosity of the composition becomes too high and the coating cannot be performed successfully. Alkali solubility cannot be sufficiently provided, and alkali developability becomes very poor.

  The polymerizable unsaturated group-containing alkali-soluble resin of the present invention can be obtained from an epoxy compound derived from bisphenols as described above, but other than such an epoxy compound, for example, a phenol novolac type epoxy compound, The thing obtained from the epoxy compound which has two glycidyl ether groups, such as a cresol novolak-type epoxy compound, can also be used.

  Next, for the compound of the general formula (V), for example, acrylic acid or methacrylic acid as an unsaturated group-containing monocarboxylic acid or both of them are reacted, and the reaction product having a hydroxy group thus obtained is reacted. (A) a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof. In that case, it is preferable to make it react in the range from which the molar ratio of (a) / (b) will be 0.01-10. By this reaction, a polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth) acrylate acid adduct is obtained.

  (A) Dicarboxylic acid or tricarboxylic acid or acid anhydride thereof used for epoxy (meth) acrylate acid adduct includes chain hydrocarbon dicarboxylic acid or tricarboxylic acid or acid anhydride, alicyclic dicarboxylic acid or tricarboxylic acid Acids or anhydrides thereof, aromatic dicarboxylic acids or tricarboxylic acids or anhydrides thereof are used. Here, as the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, for example, succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citrate malic acid, malonic acid, glutaric acid, There are compounds such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and the like, and dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced, or an acid anhydride thereof may be used. Examples of the alicyclic dicarboxylic acid or tricarboxylic acid or acid anhydrides thereof include compounds such as cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid, and more It may be a dicarboxylic acid or a tricarboxylic acid or an acid anhydride into which a substituent is introduced. Furthermore, examples of the aromatic dicarboxylic acid or tricarboxylic acid or acid anhydride thereof include compounds such as phthalic acid, isophthalic acid, trimellitic acid, and the like, and further, dicarboxylic acid or tricarboxylic acid having an arbitrary substituent introduced therein or An acid anhydride may be used.

  The (b) tetracarboxylic acid or acid dianhydride used in the epoxy (meth) acrylate acid adduct is a chain hydrocarbon tetracarboxylic acid or acid dianhydride or alicyclic tetracarboxylic acid or The acid dianhydride or aromatic polycarboxylic acid or acid dianhydride is used. Here, examples of the chain hydrocarbon tetracarboxylic acid or its acid dianhydride include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and the like. Carboxylic acid or its acid dianhydride may be sufficient. Examples of the alicyclic tetracarboxylic acid or its acid dianhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, Furthermore, it may be a tetracarboxylic acid or an acid dianhydride having an arbitrary substituent introduced therein. Furthermore, examples of the aromatic tetracarboxylic acid and its acid dianhydride include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and acid dianhydrides thereof. It may be a tetracarboxylic acid or its acid dianhydride having a substituent introduced therein.

  The molar ratio (a) / (b) of (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride to (b) tetracarboxylic acid or its acid dianhydride used for the epoxy (meth) acrylate acid adduct is As described above, it is preferably 0.01 to 10. When the molar ratio (a) / (b) deviates from the above range, the optimum molecular weight cannot be obtained. In the photosensitive resin composition using (A), alkali developability, heat resistance, solvent resistance, pattern shape, etc. Since it deteriorates, it is not preferable. In addition, there exists a tendency for alkali solubility to become large and molecular weight to become large, so that molar ratio (a) / (b) is small.

  The epoxy (meth) acrylate acid adduct can be produced by a known method, for example, a method described in JP-A-8-278629, JP-A-2008-9401, or the like, by the above-described steps. First, as a method for reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound of the general formula (V), for example, an epoxy group of the epoxy compound and an equimolar amount of an unsaturated group-containing monocarboxylic acid are added to a solvent, In the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.), there is a method of reacting by heating and stirring at 90 to 120 ° C. while blowing air. Next, as a method of reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound as a reaction product, a predetermined amount of an epoxy acrylate compound, an acid dianhydride, and an acid monoanhydride is added to a solvent, and a catalyst (odor In the presence of tetraethylammonium bromide, triphenylphosphine, etc.), the reaction is carried out by heating and stirring at 90 to 130 ° C.

  About the weight average molecular weight (Mw) of polymerizable unsaturated group containing alkali-soluble resin (A), it is preferable that it is the range of 2000-50000, and it is more preferable that it is between 2000-7000. If the weight average molecular weight (Mw) is less than 2000, the adhesion of the pattern during development of the photosensitive resin composition using (A) cannot be maintained, pattern peeling occurs, and the weight average molecular weight (Mw) is If it exceeds 50000, a development residue and a residual film of an unexposed part are likely to remain. Furthermore, (A) desirably has an acid value in the range of 30 to 200 mgKOH / g. If this value is less than 30 mgKOH / g, alkali development of the photosensitive resin composition using (A) cannot be performed well, or special development conditions such as strong alkali are required, and if it exceeds 200 mgKOH / g, (A) Neither of these is preferable because the alkali developer penetrates into the used photosensitive resin composition too quickly and peeling development occurs. In addition, about the polymerizable unsaturated group containing alkali-soluble resin of (A), even if it uses only 1 type, it can also use 2 or more types of mixtures.

  Next, (B) as the photopolymerizable monomer having at least one ethylenically unsaturated bond, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) (Meth) acrylic acid esters having a hydroxyl group such as acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene Glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate Rate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate (Meth) acrylic acid esters such as sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and one or two of these More than seeds can be used. Note that (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxy group.

  The blending ratio of these component (A) and component (B) is 50/50 to 90/10 in weight ratio (A) / (B), preferably 60/40 to 80/20. When the blending ratio of the component (A) is less than 50/50, the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed area, so that the solubility in an alkali developer is lowered. There arises a problem that the pattern edge is not jagged and sharp, and when it is more than 90/10, the ratio of the photoreactive functional group in the resin is small and the formation of a crosslinked structure is insufficient. Since the valence is too high and the solubility in the alkaline developer in the exposed area becomes high, there is a risk that the formed pattern may be thinner than the target line width or the pattern may be easily lost. is there.

  In addition, as the photopolymerization initiator of the component (C), the compound represented by the general formula (I) is contained as an essential component, and radical species are generated by irradiation with ultraviolet light or the like to form a photopolymerizable compound. Addition initiates radical polymerization and cures the composition. Of these, 1- [11- (2-ethylhexyl) -8- (2,4,6-trimethylbenzoyl) represented by general formula (II), more preferably general formula (III), and further represented by formula (IV) is preferable. ) -11H-benzo [a] carbazol-5-yl]-[4- (2,2,3,3-tetrafluoropropoxy) -phenyl] -methanone oxime O-acetate can achieve high sensitivity. Particularly preferred. Regarding the production of the general formula (I), for example, the production method is described in International Publication Pamphlet WO2012 / 045736A1.

  In the present invention, one or more other photopolymerization initiators or sensitizers can be used in combination with the photopolymerization initiator represented by the general formula (I). Here, as other photopolymerization initiators or sensitizers, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert Acetophenones such as butyl acetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5 -Diphenylbiimidazole, 2- (o- Methoxyphenyl) -4,5-diphenylbiimidazole, biimidazole compounds such as 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2 -Halomethyl such as trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Diazole compounds, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Metoki Styryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine and other halomethyl-S-triazine compounds, 1,2-octanedione, 1- [ 4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-o-benzoate, 1- (4-methyl O-acyloxime compounds such as sulfanylphenyl) butane-1,2-dione-2-oxime-o-acetate, 1- (4-methylsulfanylphenyl) butan-1-oneoxime-o-acetate, benzyldimethyl ketal Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-iso Sulfur compounds such as lopyrthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, anthraquinones such as 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, etc. Examples thereof include thiol compounds such as organic peroxides, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole.

  Including the photopolymerization initiator represented by the general formula (I), these photopolymerization initiators and sensitizers can be used alone or in combination of two or more. it can. Moreover, although it does not act as a photopolymerization initiator or a sensitizer by itself, a compound capable of increasing the ability of the photopolymerization initiator or the sensitizer can be added by using in combination. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine which are effective when used in combination with benzophenone.

  The amount of the photopolymerization initiator used as the component (C) is 2 to 30 parts by mass, preferably 5 to 25 parts by mass, more preferably 100 parts by mass in total of the components (A) and (B). 5 to 20 parts by mass. When the blending ratio of component (C) is less than 2 parts by mass, the rate of photopolymerization becomes slow and the sensitivity decreases. On the other hand, when it exceeds 30 parts by mass, the sensitivity is too strong and the pattern line There is a possibility that the width becomes thicker than that of the pattern mask, and a line width that is faithful to the mask cannot be reproduced, or the pattern edge does not become jagged and sharp. The photopolymerization initiator of the component (C) contains the photopolymerization initiator represented by the general formula (I) as an essential component, but the amount is independent even if no other component (C) is added. The amount of the photopolymerization initiator represented by the general formula (I) is preferably 70 to 100% by mass in the total amount of the component (C). Preferably there is.

  In the component (D), the light shielding component selected from a black organic pigment, a mixed color organic pigment, or a light shielding material is preferably excellent in heat resistance, light resistance and solvent resistance. Here, examples of the black organic pigment include perylene black, cyanine black, and aniline black. Examples of the mixed color organic pigment include those obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like into a pseudo black color. Examples of the light shielding material include inorganic black pigments such as carbon black, chromium oxide, iron oxide, and titanium black, and two or more kinds can be appropriately selected and used. In particular, carbon black has light shielding properties and surface smoothness. In view of good compatibility, dispersion stability, and compatibility with resin.

  These light shielding components are preferably preliminarily dispersed in a dispersion medium to obtain a light shielding dispersion, and then blended as a photosensitive resin composition for a light shielding film. Here, examples of the dispersion medium include propylene glycol monomethyl ether acetate and 3 methoxybutyl acetate. The blending ratio of the light-shielding component (D) in the light-shielding dispersion is 20 to 80% by weight, preferably 40 to 70% by weight, based on the total solid content of the composition of the present invention. . At that time, when an organic pigment such as aniline black or cyanine black or a carbon-based light shielding component such as carbon black is used, the range of 40 to 60% by mass is particularly preferable. When the amount is less than 20% by mass, the light shielding property is not sufficient. If it exceeds 80% by mass, the content of the photosensitive resin as the original binder is reduced, which causes an undesired problem that the development characteristics are impaired and the film forming ability is impaired.

  In the photosensitive resin composition of this invention, it is preferable to adjust a viscosity using a solvent other than said (A)-(D). Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2- Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, Glycol ethers such as reethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Examples include acetic acid esters such as ethyl ether acetate, and the like, and these can be dissolved and mixed to form a uniform solution-like composition.

  Further, the photosensitive resin composition of the present invention includes a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent, a coupling agent, a surfactant and the like as necessary. Additives can be blended. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like, and examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like. Examples of the material include glass fiber, silica, mica, and alumina, and examples of the antifoaming agent and leveling agent include silicone-based, fluorine-based, and acrylic compounds. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. Examples of the coupling agent include 3- (glycidyloxy) propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, Examples include silane coupling agents such as 3-ureidopropyltriethoxysilane.

  The photosensitive resin composition of this invention contains the said (A)-(D) component or these and a solvent as a main component. It is desirable that the components (A) to (D) are contained in a total of 80% by mass, preferably 90% by mass or more, in the solid content excluding the solvent (the solid content includes a monomer that becomes a solid content after curing). Although the quantity of a solvent changes with target viscosity, it is good to make it contain in the range of 70-90 mass% in the photosensitive resin composition.

  The photosensitive resin composition for a light shielding film in the present invention is excellent as, for example, a resin composition for forming a color filter light shielding film, and a method for forming a light shielding film includes the following photolithography methods. First, the photosensitive resin composition is applied on a transparent substrate, and then the solvent is dried (prebaked). Then, a photomask is applied on the film thus obtained, and ultraviolet rays are irradiated to expose the exposed portion. There is a method in which the pattern is formed by curing and further elution using an aqueous alkali solution to elute unexposed portions, and post baking (thermal baking) is performed as post-drying.

  As a transparent substrate to which the photosensitive resin composition is applied, in addition to a glass substrate, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) is deposited or patterned with a transparent electrode such as ITO or gold. Can be illustrated. As a method of applying the solution of the photosensitive resin composition on the transparent substrate, in addition to a known solution dipping method and spray method, any method such as a roller coater machine, a land coater machine, a slit coater machine, or a spinner machine can be used. Methods can also be employed. After applying to a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate or the like. The heating temperature and heating time in the pre-baking are appropriately selected according to the solvent to be used, and are performed, for example, at a temperature of 60 to 110 ° C. for 1 to 3 minutes.

  The exposure performed after pre-baking is performed by an ultraviolet exposure apparatus, and only the resist corresponding to the pattern is exposed by exposing through a photomask. The exposure apparatus and the exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, or a deep ultraviolet lamp, and the photosensitive resin composition in the coating film is photocured.

  The alkali development after the exposure is performed for the purpose of removing the resist in the unexposed portion, and a desired pattern is formed by this development. Examples of the developer suitable for the alkali development include, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. Particularly, sodium carbonate, potassium carbonate, lithium carbonate, and the like. It is better to develop at a temperature of 23 to 28 ° C. using a weakly alkaline aqueous solution containing 0.05 to 3% by mass of carbonate such as a commercially available developing machine or ultrasonic cleaner. It can be formed precisely.

  After the development, heat treatment (post-bake) is preferably performed at a temperature of 180 to 250 ° C. and a condition of 20 to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned light-shielding film and the substrate. This is performed by heating with an oven, a hot plate or the like, as in the pre-baking. The patterned light-shielding film of the present invention is formed through each step by the above photolithography method.

  As described above, the photosensitive resin composition of the present invention is suitable for forming a fine pattern by operations such as exposure and alkali development. Further, the photosensitive resin composition for a light-shielding film of the present invention can be suitably used as a coating material, and is particularly suitable as a color filter ink used in a liquid crystal display device or a photographing element. The light shielding film is useful as a color filter, a black matrix for liquid crystal projection, a light shielding film, a light shielding film for a touch panel, and the like.

  The photosensitive resin composition for a light-shielding film of the present invention can sufficiently secure development adhesion even when, for example, a thin line having a line width of about 5 μm is formed while maintaining high definition and high light shielding. Also, it has excellent adhesion to the glass substrate.

  Hereinafter, although an embodiment of the present invention is described concretely based on an example and a comparative example, the present invention is not limited to these.

  First, Synthesis Example 1 of the (A) polymerizable unsaturated group-containing alkali-soluble resin of the present invention is shown. Evaluation of the resin in the synthesis example was performed as follows.

[Solid content]
1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W ₀ (g)], weighed [W ₁ (g)], and heated at 160 ° C. for 2 hours [W ₂ ( g)] from the following equation.
Solid content concentration (% by weight) = 100 × (W ₂ −W ₀ ) / (W ₁ −W ₀ )

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator (trade name COM-1600 manufactured by Hiranuma Seisakusho Co., Ltd.).

[Molecular weight]
Gel permeation chromatography (GPC) [trade name HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper- H5000 (1 bottle) [manufactured by Tosoh Corporation], temperature: 40 ° C., speed: 0.6 ml / min], and weight average molecular weight (as standard polystyrene [Tosoh Corporation PS-oligomer kit] converted value) Mw).

Abbreviations used in the synthesis examples and comparative synthesis examples are as follows.
BPFE: Reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxirane. In the compound of the general formula (V), a compound in which X is a fluorene-9,9-diyl group and R ₆ and R ₇ are hydrogen.
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis Example 1]
In a 500 ml four-necked flask with a reflux condenser, charge 78.63 g (0.17 mol) of BPFE, 24.50 g (0.34 mol) of acrylic acid, 0.45 g of TPP, and 114 g of PGMEA, and stir for 12 hours under heating at 100 to 105 ° C. As a result, a reaction product was obtained.

  Next, 25.01 g (0.085 mol) of BPDA and 12.93 g (0.085 mol) of THPA were added to the obtained reaction product, stirred for 6 hours under heating at 120 to 125 ° C., and an alkali-soluble resin solution containing a polymerizable unsaturated group ( A) -1 was obtained. The obtained resin solution had a solid content concentration of 55.8 wt%, an acid value (in terms of solid content) of 103 mg KOH / g, and an Mw of 2600 by GPC analysis.

[Comparative Synthesis Example 1]
In a 1000 ml four-necked flask with a nitrogen inlet tube and a reflux tube, 51.65 g (0.60 mol) of methacrylic acid, 38.44 g (0.38 mol) of methyl methacrylate, 36.33 g (0.22 mol) of cyclohexyl methacrylate, 5.91 g of AIBN, and 368 g of DMDG The mixture was stirred and polymerized at 80 to 85 ° C. under a nitrogen stream for 8 hours. Furthermore, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.44 g of TPP, and 0.055 g of 2,6-di-tert-butyl-p-cresol were charged in the flask, and stirred at 80 to 85 ° C. for 16 hours, polymerizable unsaturated A group-containing alkali-soluble resin solution (A) -2 was obtained. The obtained polymerizable unsaturated group-containing alkali-soluble resin had a solid content concentration of 32% by mass, an acid value (in terms of solid content) of 110 mgKOH / g, and Mw by GPC analysis of 18080.

  Next, Synthesis Examples 2 to 4 of the photopolymerization initiator represented by (C) the general formula (I) are shown.

フェニルヒドラジン１６．２２ｇ（０．１８ｍｏｌ）とα−テトラロン２６．８９ｇ（０．１８ｍｏｌ）を４００ｍｌエタノール中で濃塩酸１８ｍｌ存在下加熱し、４時間リフラックス状態で反応させた。反応溶液をエバポレーターにてエタノール除去し、シクロヘキサン／トルエン（５０／５０）で再結晶させることで、反応生成物３８．２５ｇを得た。この反応物３０．８２ｇ（０．１４ｍｏｌ）をキシレン２４０ｍｌに溶解し、触媒として５％Ｐｄ／Ｃ ９．２３ｇを添加して加熱し、１時間リフラックス状態で反応させた。反応液を冷却して酢酸エチル２４０ｍｌを加え、セライトで触媒等を濾過した後、エバポレーターにて溶剤を留去させて結晶を析出させた。これを濾過することで白色の固体化合物２４．６４ｇを得た。得られた化合物は^１Ｈ−ＮＭＲにて構造式（VI）の化合物であることを確認した。
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３中）：δ（ｐｐｍ）＝７．３０−７．７０（ｍ，６Ｈ）、８．００−８．２０（ｍ，４Ｈ）、８．８０（ｂｒ，１Ｈ） [Synthesis Example 2]
The compound of structural formula (IV) was synthesized by performing the following 6-step reaction.
Step 1: Synthesis of 11H-benzo [a] carbazole [Structural Formula (VI)]

16.22 g (0.18 mol) of phenylhydrazine and 26.89 g (0.18 mol) of α-tetralone were heated in 400 ml ethanol in the presence of 18 ml of concentrated hydrochloric acid and reacted in a reflux state for 4 hours. Ethanol was removed from the reaction solution with an evaporator, and recrystallization was performed with cyclohexane / toluene (50/50) to obtain 38.25 g of a reaction product. 30.82 g (0.14 mol) of this reaction product was dissolved in 240 ml of xylene, added with 9.23 g of 5% Pd / C as a catalyst, heated, and reacted in a reflux state for 1 hour. The reaction solution was cooled, 240 ml of ethyl acetate was added, the catalyst and the like were filtered through celite, and then the solvent was distilled off with an evaporator to precipitate crystals. This was filtered to obtain 24.64 g of a white solid compound. The obtained compound was confirmed by ¹ H-NMR to be the compound of structural formula (VI).
¹ H-NMR spectrum (in CDCl ₃ ): δ (ppm) = 7.30-7.70 (m, 6H), 8.00-8.20 (m, 4H), 8.80 (br, 1H)

１１Ｈ−ベンゾ［ａ］カルバゾール〔構造式（VI）〕２１．７２ｇ（０．１０ｍｏｌ）をＤＭＦ １００ｍＬに溶解させて氷浴にて０℃に冷却した後、水素化ナトリウム４．０４ｇ（０．１０１ｍｏｌ）を添加して１時間保持した。その後に１−ブロモ−２−エチルヘキサン２７．０４ｇ（０．１４ｍｏｌ）を添加し、３０分保持した後に氷浴を外して室温まで温度を戻した後、一晩反応させた。反応液を氷水に注ぎ込んで反応を停止させた後、酢酸エチルにて２回抽出して有機相を集め、純水および飽和食塩水にて洗浄し、硫酸マグネシウムを添加して乾燥させた後に、エバポレーターにて有機溶剤を除去することで黄色液状の粗製物３３．２３ｇを得た。得られた粗製物は精製せずに次の反応に用いた。得られた粗製物について^１Ｈ−ＮＭＲにて構造を同定し、構造式（VII）の化合物であることを確認した。
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３）：δ（ｐｐｍ）＝０．８０−０．９２（ｍ，６Ｈ）、１．１６−１．４７（ｍ，８Ｈ）、２．２７（ｍ，１Ｈ）、４．６５−４．６９（ｍ，２Ｈ）、７．２７（ｔｄ，１Ｈ）、７．４４−７．５９（ｍ，４Ｈ）、７．６６（ｄ，１Ｈ）、８．０２（ｄ，１Ｈ）、８．１４（ｄ，１Ｈ）、８．１８（ｄ，１Ｈ）、８．５４（ｄ，１Ｈ） Step 2: Synthesis of 11- (2-ethylhexyl) -11H-benzo [a] carbazole [Structural Formula (VII)]

11H-benzo [a] carbazole [Structural Formula (VI)] (21.72 g, 0.10 mol) was dissolved in DMF (100 mL) and cooled to 0 ° C. in an ice bath, and then sodium hydride (4.04 g, 0.101 mol). ) Was added and held for 1 hour. Thereafter, 27.04 g (0.14 mol) of 1-bromo-2-ethylhexane was added, and after maintaining for 30 minutes, the ice bath was removed and the temperature was returned to room temperature, followed by reaction overnight. The reaction solution was poured into ice water to stop the reaction, and extracted twice with ethyl acetate to collect the organic phase, washed with pure water and saturated brine, dried by adding magnesium sulfate, The organic solvent was removed with an evaporator to obtain 33.23 g of a yellow liquid crude product. The obtained crude product was used in the next reaction without purification. The structure of the obtained crude product was identified by ¹ H-NMR and confirmed to be the compound of structural formula (VII).
¹ H-NMR spectrum (CDCl ₃ ): δ (ppm) = 0.80-0.92 (m, 6H), 1.16-1.47 (m, 8H), 2.27 (m, 1H), 4.65-4.69 (m, 2H), 7.27 (td, 1H), 7.44-7.59 (m, 4H), 7.66 (d, 1H), 8.02 (d, 1H), 8.14 (d, 1H), 8.18 (d, 1H), 8.54 (d, 1H)

構造式（VII）の化合物１９．８３ｇ（６０ｍｍｏｌ）を塩化メチレン（２００ｍＬ）に溶解させ、氷浴にて０℃に冷却して３０分保持した後に２，４，６−トリメチルベンゾイルクロリド１１．５１ｇ（６３ｍｍｏｌ）および塩化アルミニウム８．４ｇ（６３ｍｍｏｌ）を添加、その後氷浴を外して室温に戻し、２時間反応させた。２時間後に氷浴にて再度０℃にした後、塩化アルミニウム８．４ｇ（６３ｍｍｏｌ）を加え、滴下ロートより２−フルオロベンゾイルクロリド９．９９ｇ（６３ｍｍｏｌ）を２時間かけて滴下した。滴下終了後、氷浴を外して室温に戻し、室温下で３時間反応させた。反応液を氷水に注ぎ込んで反応を停止させた後、塩化メチレンにて２回抽出を行い、有機相を集め、純水および飽和食塩水にて洗浄して硫酸マグネシウムを添加して乾燥させた。その後、ノルマルヘキサン８００ｍＬを加えて塩化メチレンと同時に除去・濃縮することでベージュ色の固体物を析出させた。これをろ過し、ノルマルヘキサンにて洗浄して乾燥させて、ベージュ色の固体物３４．３９ｇを得た。得られた化合物は^１Ｈ−および^１９Ｆ−ＮＭＲにて構造を同定し、構造式（VIII）の化合物であることを確認した。
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３）：δ（ｐｐｍ）＝０．８４（ｔ）、０．８９（ｔ）、１．１８−１．４２（ｍ）、２．２０（ｓ），２．２８−２．３１（ｍ）、２．４０（ｓ）、４．７２−４．７６（ｍ）、６．９６（ｓ）、７．１９（ｔ）、７．２９（ｔ）、７．５２−７．６０（ｍ）、７．７０−７．８４（ｍ）、８．３８（ｓ）、８．６３−８．６６（ｍ）、９．５６（ｄ）
^１９Ｆ−ＮＭＲスペクトル（ＣＤＣｌ_３）：δ（ｐｐｍ）＝−１１１．５８ Step 3: 1- [11- (2-Ethylhexyl) -8- (2-fluorobenzoyl) -11H-benzo [a] carbazol-5-yl]-(2,4,6-trimethylphenyl) -methanone [structure Synthesis of Formula (VIII)]

19.83 g (60 mmol) of the compound of structural formula (VII) was dissolved in methylene chloride (200 mL), cooled to 0 ° C. in an ice bath and held for 30 minutes, and then 11.51 g of 2,4,6-trimethylbenzoyl chloride. (63 mmol) and 8.4 g (63 mmol) of aluminum chloride were added, and then the ice bath was removed and the temperature was returned to room temperature, followed by reaction for 2 hours. After 2 hours, the temperature was again set to 0 ° C. in an ice bath, 8.4 g (63 mmol) of aluminum chloride was added, and 9.99 g (63 mmol) of 2-fluorobenzoyl chloride was added dropwise from the dropping funnel over 2 hours. After completion of the dropwise addition, the ice bath was removed, the temperature was returned to room temperature, and the reaction was allowed to proceed at room temperature for 3 hours. The reaction solution was poured into ice water to stop the reaction, and extracted twice with methylene chloride. The organic phase was collected, washed with pure water and saturated brine, dried by adding magnesium sulfate. Thereafter, 800 mL of normal hexane was added and removed and concentrated simultaneously with methylene chloride to precipitate a beige solid. This was filtered, washed with normal hexane and dried to give 34.39 g of a beige solid. The structure of the obtained compound was identified by ¹ H- and ¹⁹ F-NMR and confirmed to be the compound of structural formula (VIII).
¹ H-NMR spectrum (CDCl ₃ ): δ (ppm) = 0.84 (t), 0.89 (t), 1.18-1.42 (m), 2.20 (s), 2.28 -2.31 (m), 2.40 (s), 4.72-4.76 (m), 6.96 (s), 7.19 (t), 7.29 (t), 7.52 -7.60 (m), 7.70-7.84 (m), 8.38 (s), 8.63-8.66 (m), 9.56 (d)
¹⁹ F-NMR spectrum (CDCl ₃ ): δ (ppm) =-11.58

構造式（VIII）の化合物２９．９４ｇ（５０ｍｍｏｌ）をピリジン（１００ｍＬ）に溶解させ、２，２，３，３−テトロフルオロー１−プロパノール９．９ｇ（７５ｍｍｏｌ）と水酸化ナトリウム３．０ｇ（７５ｍｍｏｌ）を加え、７０℃にて一晩攪拌した。所定の反応時間後、室温に冷却して純水に注ぎ込み、酢酸エチルで抽出、純水及び飽和食塩水で洗浄した。硫酸マグネシウムを添加し乾燥後、濃縮し、得られた粗製物を、塩化メチレンを溶離液としてシリカゲルカラムクロマトグラフィーにて精製することで白色固体１８．１３ｇを得た。得られた化合物は^１Ｈ−および^１９Ｆ−ＮＭＲにて構造を同定し、構造式（IX）の化合物であることを確認した。
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３）：δ（ｐｐｍ）＝０．８２（ｔ）、０．８７（ｔ）、１．１６−１．５６（ｍ）、２．１９（ｓ），２．２６−２．２９（ｍ）、２．３９（ｓ）、４．３０−４．３４（ｔ）、４．６５−４．７７（ｍ）、５．３５−５．６０（ｍ）、６．９５（ｓ）、７．１５−７．２０（ｍ）、７．２９（ｔ）、７．５２−７．６０（ｍ）、７．７０−７．７７（ｍ）、８．６３−８．６６（ｍ）、９．５６（ｄ）
^１９Ｆ−ＮＭＲスペクトル（ＣＤＣｌ_３）：δ（ｐｐｍ）＝−１４０．９２、−１２６．３０ Step 4: 1- [11- (2-Ethylhexyl) -8- (2,4,6-trimethylbenzoyl) -11H-benzo [a] carbazol-5-yl]-[4- (2,2,3 Synthesis of 3-tetrafluoropropoxy) -phenyl] -methanone [Structural Formula (IX)]

29.94 g (50 mmol) of the compound of the structural formula (VIII) is dissolved in pyridine (100 mL), 9.9 g (75 mmol) of 2,2,3,3-tetrofluoro-1-propanol and 3.0 g (75 mmol) of sodium hydroxide. And stirred at 70 ° C. overnight. After a predetermined reaction time, the mixture was cooled to room temperature, poured into pure water, extracted with ethyl acetate, and washed with pure water and saturated brine. Magnesium sulfate was added, dried and concentrated, and the resulting crude product was purified by silica gel column chromatography using methylene chloride as an eluent to give 18.13 g of a white solid. The structure of the obtained compound was identified by ¹ H- and ¹⁹ F-NMR and confirmed to be the compound of structural formula (IX).
¹ H-NMR spectrum (CDCl ₃ ): δ (ppm) = 0.82 (t), 0.87 (t), 1.16-1.56 (m), 2.19 (s), 2.26 -2.29 (m), 2.39 (s), 4.30-4.34 (t), 4.65-4.77 (m), 5.35-5.60 (m), 6. 95 (s), 7.15-7.20 (m), 7.29 (t), 7.52-7.60 (m), 7.70-7.77 (m), 8.63-8 .66 (m), 9.56 (d)
¹⁹ F-NMR spectrum (CDCl ₃ ): δ (ppm) = − 140.92, −126.30

構造式（IX）の化合物１４．２２ｇ（２０ｍｍｏｌ）をピリジン（１００ｍＬ）に溶解させた後、塩酸ヒドロキシアンモニウム０．６７ｇ（２１ｍｍｏｌ）を添加した。その後に１３０℃に昇温して６時間反応させた。反応終了後は室温まで冷却してから、反応液を純水に注ぎ、塩化メチレンで抽出して有機相を集め、純水および飽和食塩水で洗浄して硫酸マグネシウムを添加し乾燥させた。その後、エバポレーターで濃縮することで淡黄色の固体状物１３．０６ｇを得た。得られた化合物は^１Ｈ−および^１９Ｆ−ＮＭＲにて構造を同定し、構造式（X）の化合物であることを確認した。
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３）：δ（ｐｐｍ）＝０．８２（ｔ）、０．８７（ｔ）、１．１６−１．５６（ｍ）、２．１９（ｓ），２．２６−２．２９（ｍ）、２．３９（ｓ）、４．２５−４．３０（ｔ）、４．６５−４．７７（ｍ）、５．３０−５．５５（ｍ）、６．９５（ｓ）、７．１０（ｄ）、７．１５−７．２０（ｍ）、７．４５−７．６０（ｍ）、７．７０−７．７７（ｍ）、８．４２−８．６６（ｍ）、９．５６（ｄ）
^１９Ｆ−ＮＭＲスペクトル（ＣＤＣｌ_３）：δ（ｐｐｍ）＝−１４０．９２、−１２６．３０ Step 5: 1- [11- (2-Ethylhexyl) -8- (2,4,6-trimethylbenzoyl) -11H-benzo [a] carbazol-5-yl]-[4- (2,2,3 Synthesis of 3-tetrafluoropropoxy) -phenyl] -methanone oxime [Structural Formula (X)]

After dissolving 14.22 g (20 mmol) of the compound of the structural formula (IX) in pyridine (100 mL), 0.67 g (21 mmol) of hydroxyammonium hydrochloride was added. Thereafter, the temperature was raised to 130 ° C. and reacted for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, poured into pure water, extracted with methylene chloride, the organic phase was collected, washed with pure water and saturated brine, added with magnesium sulfate and dried. Then, 13.06 g of a pale yellow solid was obtained by concentrating with an evaporator. The structure of the obtained compound was identified by ¹ H- and ¹⁹ F-NMR and confirmed to be the compound of the structural formula (X).
¹ H-NMR spectrum (CDCl ₃ ): δ (ppm) = 0.82 (t), 0.87 (t), 1.16-1.56 (m), 2.19 (s), 2.26 -2.29 (m), 2.39 (s), 4.25-4.30 (t), 4.65-4.77 (m), 5.30-5.55 (m), 6. 95 (s), 7.10 (d), 7.15-7.20 (m), 7.45-7.60 (m), 7.70-7.77 (m), 8.42-8 .66 (m), 9.56 (d)
¹⁹ F-NMR spectrum (CDCl ₃ ): δ (ppm) = − 140.92, −126.30

Step 6: 1- [11- (2-Ethylhexyl) -8- (2,4,6-trimethylbenzoyl) -11H-benzo [a] carbazol-5-yl]-[4- (2,2,3 Synthesis of 3-tetrafluoropropoxy) -phenyl] -methanone oxime O-acetate [Structural Formula (IV)] After dissolving 7.26 g (10 mmol) of the compound of Structural Formula (X) in ethyl acetate (150 mL), ice bath The mixture was cooled to 0 ° C. and 3.04 g (30 mmol) of triethylamine and 2.35 g (30 mmol) of acetyl chloride were added in this order. After the addition, the reaction solution was allowed to react for 2.5 hours, poured into pure water, extracted with ethyl acetate, the organic phase was collected, washed with pure water and saturated brine, dried over magnesium sulfate. After drying, the solvent was removed to obtain 7.03 g of a pale yellow to white solid. The structure of the obtained compound was identified by ¹ H- and ¹⁹ F-NMR and confirmed to be the compound of the structural formula (IV).
¹ H-NMR spectrum (CDCl ₃ ): δ (ppm) = 0.82 (t), 0.87 (t), 1.16-1.56 (m), 2.05 (s), 2.19 (S), 2.6-2.29 (m), 2.39 (s), 4.30-4.34 (t), 4.65-4.77 (m), 5.39-5. 65 (tt), 6.95 (s), 7.01 (d), 7.15-7.20 (m), 7.39 (d), 7.46-7.53 (m), 7. 70-7.77 (m), 8.35 (s), 8.42 (s), 8.63 (d), 9.56 (d)
¹⁹ F-NMR spectrum (CDCl ₃ ): δ (ppm) = − 140.66, −126.32

構造式（VII）の化合物４．１８ｇ（１２．６ｍｍｏｌ）を塩化メチレン（４０ｍＬ）に溶解させ、氷浴にて０℃に冷却して３０分保持した後に２，４，６−トリメチルベンゾイルクロリド２．３８ｇ（１３．０ｍｍｏｌ）および塩化アルミニウム１．７７ｇ（１３．３ｍｍｏｌ）を添加、その後氷浴を外して室温に戻し、２時間反応させた。その後に氷浴にて再度０℃にした後、塩化アルミニウム１．７７ｇ（１３．３ｍｍｏｌ）を加え、滴下ロートよりアセチルクロリド１．０２ｇ（１３．０ｍｍｏｌ）を３０分かけて滴下した。滴下終了後、氷浴を外して室温に戻し、室温下で３時間反応させた。
反応液を氷水に注ぎ込んで反応を停止させた後、塩化メチレンにて２回抽出して有機相を集め、純水および飽和食塩水にて洗浄し、硫酸マグネシウムにて乾燥させた。その後、ノルマルヘキサン２３０ｍＬを加えて塩化メチレンと同時に除去・濃縮することでベージュ色の固体物を析出させた。
これをろ過し、ノルマルヘキサンにて洗浄して乾燥させることで、ベージュ色の固体物を得た（収量４．９１ｇ、収率７５．０％）。
得られた化合物は^１Ｈ−ＮＭＲにて構造を同定した。
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３） δ（ｐｐｍ）：０．８２（ｔ）、０．９０（ｔ）、１．１８−１．４５（ｍ）、２．２０（ｓ），２．２９−２．３０（ｍ）、２．４１（ｓ）、２．７２（ｓ）、４．７４−４．７７（ｍ）、６．９８（ｓ）、７．５８（ｄ）、７．７０−７．７９（ｍ）、８．１０（ｄｄ）、８．３９（ｓ）、８．６０（ｄ）、８．６４（ｄ）、９．５３（ｄ）． [Synthesis Example 3]
Using the compound of Structural Formula (VII) obtained in Step 2 of Synthesis Example 2, the following reaction from Step 3 is carried out to obtain a compound of Structural Formula (XII) which is one of the compounds of General Formula (I) Synthesized.
Step 3: Synthesis of 1- [11- (2-ethylhexyl) -5- (2,4,6-trimethylbenzoyl) -11H-benzo [a] carbazol-8-yl] -ethanone [Structural Formula (XI)]

2.18 g (12.6 mmol) of the compound of structural formula (VII) was dissolved in methylene chloride (40 mL), cooled to 0 ° C. in an ice bath and kept for 30 minutes, and then 2,4,6-trimethylbenzoyl chloride 2 .38 g (13.0 mmol) and aluminum chloride 1.77 g (13.3 mmol) were added, and then the ice bath was removed and the temperature was returned to room temperature, followed by reaction for 2 hours. Thereafter, the temperature was again 0 ° C. in an ice bath, and 1.77 g (13.3 mmol) of aluminum chloride was added, and 1.02 g (13.0 mmol) of acetyl chloride was added dropwise from the dropping funnel over 30 minutes. After completion of the dropwise addition, the ice bath was removed, the temperature was returned to room temperature, and the reaction was allowed to proceed at room temperature for 3 hours.
The reaction solution was poured into ice water to stop the reaction, and extracted twice with methylene chloride to collect the organic phase, washed with pure water and saturated brine, and dried over magnesium sulfate. Thereafter, 230 mL of normal hexane was added and removed and concentrated simultaneously with methylene chloride to precipitate a beige solid.
This was filtered, washed with normal hexane and dried to obtain a beige solid (yield 4.91 g, yield 75.0%).
The structure of the obtained compound was identified by ¹ H-NMR.
¹ H-NMR spectrum (CDCl ₃ ) δ (ppm): 0.82 (t), 0.90 (t), 1.18-1.45 (m), 2.20 (s), 2.29- 2.30 (m), 2.41 (s), 2.72 (s), 4.74-4.77 (m), 6.98 (s), 7.58 (d), 7.70- 7.79 (m), 8.10 (dd), 8.39 (s), 8.60 (d), 8.64 (d), 9.53 (d).

構造式（XI）の化合物４．９１ｇ（９．４９ｍｍｏｌ）をトルエン（１０ｍＬ）およびピリジン（２ｍＬ）に溶解させたのち、８０℃に昇温し、酢酸ナトリウム０．８２ｇ（１０．０ｍｍｏｌ）、塩酸ヒドロキシアンモニウム０．６９ｇ（１０．０ｍｍｏｌ）を加え、１００℃にて一晩攪拌した。その後、氷浴で０℃に冷却し、トリエチルアミン２．８８ｇ（２８．５ｍｍｏｌ）およびアセチルクロリド０．７７ｇ（９．８ｍｍｏｌ）を加えて室温に戻して２時間反応させた。その後に反応液を純水に注ぎ込み、トルエンにて抽出して有機相を集め、純水及び飽和食塩水にて洗浄した。洗浄液は硫酸マグネシウムを用いた乾燥後に濃縮し、粗製物をｔｅｒｔ−ブチルメチルエーテルにて洗浄することで白色固体を得た（収量３．３０ｇ、収率６０．５％）。
得られた化合物は^１Ｈ−ＮＭＲにて構造を同定した。
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３） δ（ｐｐｍ）：０．８２（ｔ）、０．８７（ｔ）、１．１９−１．３９（ｍ）、２．２６（ｓ），２．２７−２．３０（ｍ）、２．２９（ｓ）、２．３９（ｓ）、２．５０（ｓ）、４．７２−４．７６（ｍ）、６．９６（ｓ）、７．１６−７．１８（ｍ）、７．２４−７．２７（ｍ）、７．５７（ｄ）、７．６９−７．７７（ｍ）、７．８７（ｄｄ）、８．３１（ｓ）、８．３８（ｓ）、８．６４（ｄ）、９．５３（ｄ）． Step 4: 1- [11- (2-Ethylhexyl) -5- (2,4,6-trimethylbenzoyl) -11H-benzo [a] carbazol-8-yl] -ethanone oxime O-acetate [Structural Formula (XII )]

After dissolving 4.91 g (9.49 mmol) of the compound of structural formula (XI) in toluene (10 mL) and pyridine (2 mL), the temperature was raised to 80 ° C., and 0.82 g (10.0 mmol) of sodium acetate, hydrochloric acid Hydroxyammonium 0.69g (10.0mmol) was added, and it stirred at 100 degreeC overnight. Thereafter, the mixture was cooled to 0 ° C. in an ice bath, 2.88 g (28.5 mmol) of triethylamine and 0.77 g (9.8 mmol) of acetyl chloride were added, and the mixture was returned to room temperature and reacted for 2 hours. Thereafter, the reaction solution was poured into pure water, extracted with toluene, the organic phase was collected, and washed with pure water and saturated brine. The washing liquid was concentrated after drying using magnesium sulfate, and the crude product was washed with tert-butyl methyl ether to obtain a white solid (yield 3.30 g, yield 60.5%).
The structure of the obtained compound was identified by ¹ H-NMR.
¹ H-NMR spectrum (CDCl ₃ ) δ (ppm): 0.82 (t), 0.87 (t), 1.19-1.39 (m), 2.26 (s), 2.27- 2.30 (m), 2.29 (s), 2.39 (s), 2.50 (s), 4.72-4.76 (m), 6.96 (s), 7.16- 7.18 (m), 7.24-7.27 (m), 7.57 (d), 7.69-7.77 (m), 7.87 (dd), 8.31 (s), 8.38 (s), 8.64 (d), 9.53 (d).

構造式（VII）の化合物４．１８ｇ（１２．６ｍｍｏｌ）を塩化メチレン（４０ｍＬ）に溶解させ、氷浴にて０℃に冷却して３０分保持した後に２，４，６−トリメチルベンゾイルクロリド２．３８ｇ（１３．０ｍｍｏｌ）および塩化アルミニウム１．７７ｇ（１３．３ｍｍｏｌ）を添加、その後氷浴を外して室温に戻し、２時間反応させた。その後に氷浴にて再度０℃にした後、塩化アルミニウム１．７７ｇ（１３．３ｍｍｏｌ）を加え、滴下ロートより２−エトキシベンゾイルクロリド２．４１ｇ（１３．０ｍｍｏｌ）を３０分かけて滴下した。滴下終了後、氷浴を外して室温に戻し、室温下で３時間反応させた。
反応液を氷水に注ぎ込んで反応を停止させた後、塩化メチレンにて２回抽出を行い、有機相を集め、純水および飽和食塩水にて洗浄し、硫酸マグネシウムにて乾燥させた。その後、ノルマルヘキサン２３０ｍＬを加えて塩化メチレンと同時に除去・濃縮することでベージュ色の固体物を析出させた。
これをろ過し、ノルマルヘキサンにて洗浄して乾燥させることで、ベージュ色の固体物を得た（収量４．７１ｇ、収率７２．０％）。
得られた化合物は^１Ｈ−ＮＭＲにて構造を同定した。
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３） δ（ｐｐｍ）：０．７８−０．９０（ｍ）、１．１５−１．４２（ｍ）、２．０６（ｓ）２．０７（ｓ）、２．１８（ｓ）、２．１９（ｓ）、２．２２−２．３２（ｍ）、２．３８（ｓ）、２．３９（ｓ）、３．７４（ｑ）、４．００（ｑ）、４．６９−４．７６（ｍ）、６．８４（ｄ）、６．９４（ｓ）、７．００−７．０５（ｍ）、７．４２−７．５１（ｍ）、７．２８（ｄ）、７．６７−７．７６（ｍ）、８．２０（ｓ）、８．３０（ｓ）、８．３６−８．４０（ｍ）、８．６２（ｄ）、９．５４（ｄ）、９．６０（ｄ）． [Synthesis Example 4]
Using the compound of Structural Formula (VII) obtained in Step 2 of Synthesis Example 2, the following reaction from Step 3 is performed, and the compound of Structural Formula (XV), which is one of the compounds of General Formula (I), is obtained. Synthesized.
Step 3: 1- [11- (2-Ethylhexyl) -8- (2-ethoxybenzoyl) -11H-benzo [a] carbazol-5-yl]-(2,4,6-trimethylphenyl) -methanone [structure Synthesis of Formula (XIII)]

2.18 g (12.6 mmol) of the compound of structural formula (VII) was dissolved in methylene chloride (40 mL), cooled to 0 ° C. in an ice bath and kept for 30 minutes, and then 2,4,6-trimethylbenzoyl chloride 2 .38 g (13.0 mmol) and aluminum chloride 1.77 g (13.3 mmol) were added, and then the ice bath was removed and the temperature was returned to room temperature, followed by reaction for 2 hours. Thereafter, the temperature was again 0 ° C. in an ice bath, and 1.77 g (13.3 mmol) of aluminum chloride was added, and 2.41 g (13.0 mmol) of 2-ethoxybenzoyl chloride was added dropwise from the dropping funnel over 30 minutes. After completion of the dropwise addition, the ice bath was removed, the temperature was returned to room temperature, and the reaction was allowed to proceed at room temperature for 3 hours.
The reaction solution was poured into ice water to stop the reaction, and extracted twice with methylene chloride. The organic phase was collected, washed with pure water and saturated brine, and dried over magnesium sulfate. Thereafter, 230 mL of normal hexane was added and removed and concentrated simultaneously with methylene chloride to precipitate a beige solid.
This was filtered, washed with normal hexane and dried to obtain a beige solid (yield 4.71 g, yield 72.0%).
The structure of the obtained compound was identified by ¹ H-NMR.
¹ H-NMR spectrum (CDCl ₃ ) δ (ppm): 0.78-0.90 (m), 1.15-1.42 (m), 2.06 (s) 2.07 (s), 2 .18 (s), 2.19 (s), 2.22-2.32 (m), 2.38 (s), 2.39 (s), 3.74 (q), 4.00 (q ), 4.69-4.76 (m), 6.84 (d), 6.94 (s), 7.00-7.05 (m), 7.42-7.51 (m), 7 .28 (d), 7.67-7.76 (m), 8.20 (s), 8.30 (s), 8.36-8.40 (m), 8.62 (d), 9 .54 (d), 9.60 (d).

構造式（XIII）の化合物４．７１ｇ（９．１１ｍｍｏｌ）をピリジン（５ｍＬ）に溶解させたのち、塩酸ヒドロキシアンモニウム０．７６ｇ（１０．９ｍｍｏｌ）を加え、１３０℃にて６時間反応させた。反応終了後は室温まで冷却させてから、反応液を純水に注ぎ、塩化メチレンで抽出して有機相を集め、純水および飽和食塩水で洗浄して硫酸マグネシウムで乾燥させた。その後、エバポレーターで濃縮することで淡黄色の固体状物を得た（収量４．８５ｇ、収率９０．６％）。
得られた化合物は^１Ｈ−ＮＭＲにて構造を同定した。
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３） δ（ｐｐｍ）：０．７８−０．９０（ｍ）、１．１５−１．４２（ｍ）、２．０６（ｓ）２．０７（ｓ）、２．１８（ｓ）、２．１９（ｓ）、２．２２−２．３２（ｍ）、２．３８（ｓ）、２．３９（ｓ）、３．７４（ｑ）、４．００（ｑ）、４．６９−４．７６（ｍ）、６．８４（ｄ）、６．９４（ｓ）、７．００−７．０５（ｍ）、７．４２−７．５１（ｍ）、７．４４（ｄ）、７．６７−７．７６（ｍ）、８．２０（ｓ）、８．３０（ｓ）、８．３６（ｓ）、８．５２（ｓ）、８．６２（ｄ）、９．５４（ｄ）、９．６０（ｄ）． Step 4: 1- [11- (2-Ethylhexyl) -8- (2-ethoxybenzoyl) -11H-benzo [a] carbazol-5-yl]-(2,4,6-trimethylphenyl) -methanone oxime [ Synthesis of structural formula (XIV)]

After dissolving 4.71 g (9.11 mmol) of the compound of the structural formula (XIII) in pyridine (5 mL), 0.76 g (10.9 mmol) of hydroxyammonium hydrochloride was added and reacted at 130 ° C. for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, poured into pure water, extracted with methylene chloride, the organic phase was collected, washed with pure water and saturated brine, and dried over magnesium sulfate. Then, the pale yellow solid was obtained by concentrating with an evaporator (yield 4.85 g, yield 90.6%).
The structure of the obtained compound was identified by ¹ H-NMR.
¹ H-NMR spectrum (CDCl ₃ ) δ (ppm): 0.78-0.90 (m), 1.15-1.42 (m), 2.06 (s) 2.07 (s), 2 .18 (s), 2.19 (s), 2.22-2.32 (m), 2.38 (s), 2.39 (s), 3.74 (q), 4.00 (q ), 4.69-4.76 (m), 6.84 (d), 6.94 (s), 7.00-7.05 (m), 7.42-7.51 (m), 7 .44 (d), 7.67-7.76 (m), 8.20 (s), 8.30 (s), 8.36 (s), 8.52 (s), 8.62 (d ), 9.54 (d), 9.60 (d).

構造式（XIV）の化合物４．８５ｇ（９．１１ｍｍｏｌ）を塩化メチレン（５０ｍＬ）に溶解させた後に氷浴にて０℃に冷却し、トリエチルアミン２．７６ｇ（２７．３ｍｍｏｌ）、アセチルクロリド０．７４ｇ（９．３８ｍｍｏｌ）の順に添加した。添加後、２．５時間反応させた後に反応液を純水へ注ぎ、酢酸エチルで抽出して有機相を集め、純水および飽和食塩水で洗浄し、硫酸マグネシウムにて乾燥させた。乾燥後、溶剤を飛ばして淡黄〜白色の固体状物を得た（収量５．０２ｇ、収率９６．０％）。
得られた化合物は^１Ｈ−ＮＭＲにて構造を同定した。
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３） δ（ｐｐｍ）：０．７８−０．９０（ｍ）、１．１５−１．４２（ｍ）、２．０６（ｓ）２．０７（ｓ）、２．１８（ｓ）、２．１９（ｓ）、２．２２−２．３２（ｍ）、２．３８（ｓ）、２．３９（ｓ）、３．７４（ｑ）、４．００（ｑ）、４．６９−４．７６（ｍ）、６．８４（ｄ）、６．９４（ｓ）、７．００−７．０５（ｍ）、７．４２−７．５１（ｍ）、７．６０（ｄ）、７．６７−７．７６（ｍ）、８．２０（ｓ）、８．３０（ｓ）、８．３６（ｓ）、８．４５（ｓ）、８．６２（ｄ）、９．５４（ｄ）、９．６０（ｄ）． Step 5: 1- [11- (2-Ethylhexyl) -8- (2-ethoxybenzoyl) -11H-benzo [a] carbazol-5-yl]-(2,4,6-trimethylphenyl) -methanone oxime O -Synthesis of acetate [Structural Formula (XV)]

After dissolving 4.85 g (9.11 mmol) of the compound of the structural formula (XIV) in methylene chloride (50 mL), the mixture was cooled to 0 ° C. in an ice bath, 2.76 g (27.3 mmol) of triethylamine, and 0.81 of acetyl chloride. 74 g (9.38 mmol) was added in that order. After the addition, the reaction was allowed to proceed for 2.5 hours, and the reaction solution was poured into pure water, extracted with ethyl acetate, and the organic phase was collected, washed with pure water and saturated brine, and dried over magnesium sulfate. After drying, the solvent was removed to obtain a pale yellow to white solid (yield 5.02 g, yield 96.0%).
The structure of the obtained compound was identified by ¹ H-NMR.
¹ H-NMR spectrum (CDCl ₃ ) δ (ppm): 0.78-0.90 (m), 1.15-1.42 (m), 2.06 (s) 2.07 (s), 2 .18 (s), 2.19 (s), 2.22-2.32 (m), 2.38 (s), 2.39 (s), 3.74 (q), 4.00 (q ), 4.69-4.76 (m), 6.84 (d), 6.94 (s), 7.00-7.05 (m), 7.42-7.51 (m), 7 .60 (d), 7.67-7.76 (m), 8.20 (s), 8.30 (s), 8.36 (s), 8.45 (s), 8.62 (d ), 9.54 (d), 9.60 (d).

(Examples 1-4, Comparative Examples 1-6)
Next, although this invention is demonstrated concretely based on the Example and comparative example which concern on manufacture of the photosensitive resin composition and its hardened | cured material, this invention is not limited to these. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions and cured products thereof in the following Examples and Comparative Examples are as follows.

(Polymerizable unsaturated group-containing alkali-soluble resin)
(A) -1 component: alkali-soluble resin solution obtained in Synthesis Example 1
(A) -2 component: alkali-soluble resin solution obtained in Comparative Synthesis Example 1

(Photopolymerizable monomer)
(B): Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Kogyo Co., Ltd., trade name A-TMMT)

(Photopolymerization initiator)
(C) -1: Compound represented by formula (IV) obtained in Synthesis Example 2 above
(C) -2: Compound represented by the formula (XII) obtained in Synthesis Example 3 above
(C) -3: Compound represented by the formula (XV) obtained in Synthesis Example 4 above
(C) -4: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (product name, manufactured by BASF Japan Ltd.) Irgacure OXE02)

(Light-shielding dispersion pigment)
(D): Propylene glycol monomethyl ether acetate dispersion having a carbon black concentration of 25.0% by mass and a polymer dispersant concentration of 5.0% by mass (solid content: 30.0%)

(Silane coupling agent)
(E): 3-mercaptopropyltrimethoxysilane (trade name: KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.)

(solvent)
(F) -1: Propylene glycol monomethyl ether acetate
(F) -2: Cyclohexanone

(Surfactant)
(G): BYK-330 (by Big Chemie)

  The said mixing | blending component was mix | blended in the ratio shown in Table 1, and the photosensitive resin composition of Examples 1-4 and Comparative Examples 1-6 was prepared. In addition, all the numerical values in Table 1 represent parts by mass.

[Evaluation]
Using the photosensitive resin compositions for black resists of Examples 1 to 4 and Comparative Examples 1 to 6, the following evaluations were performed. These evaluation results are shown in Table 2.

<Evaluation of development characteristics (pattern line width / pattern linearity)>
Each photosensitive resin composition obtained above was applied on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 μm, at 90 ° C. Pre-baked for 1 minute. Thereafter, the exposure gap was adjusted to 100 μm, a 5 μm negative photomask was covered on the dried coating film, and a short wavelength cut filter (model number LU0350, manufactured by Asahi Spectroscopic Co., Ltd. (340 nm or less) When the mercury lamp wavelength is cut)) (Example 1, Comparative Examples 1 to 4) and not (Examples 2 to 4, Comparative Examples 5 and 6), the i-line illuminance exceeds 30 mW / cm ² The photosensitive portion was photocured by irradiating with 80 mJ / cm ² of ultraviolet light with a high pressure mercury lamp.

Next, this exposed coated plate is +10 seconds and +15 from the development time (break time = BT) at which a pattern begins to appear at 25 ° C. in a 0.08% potassium hydroxide aqueous solution at a shower developing pressure of 1 kgf / cm ^2. After developing for 2 seconds, spray washing with 5 kgf / cm ² pressure is performed to remove the unexposed portion of the coating film to form a pixel pattern on the glass substrate, and then heat at 230 ° C. for 30 minutes using a hot air dryer. The line width and pattern linearity with respect to the mask width of the 5 μm line after post-baking were evaluated. If the pattern image does not appear even after the development time of 80 seconds, development is impossible. Each evaluation method is as follows.

Pattern line width: A pattern line width having a mask width of 5 μm was measured using a length measuring microscope (“XD-20” manufactured by Nikon Corporation).
Pattern linearity: A 5 μm mask pattern after post-baking is observed with a microscope, ○ where there is no peeling on the substrate and no pattern edge is observed, ○ is partially recognized, △ is recognized throughout X was evaluated.

<Evaluation of OD / μm>
Each photosensitive resin composition obtained above was applied on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 μm, at 90 ° C. Pre-baked for 1 minute. After that, a short wavelength cut filter (model number LU0350, manufactured by Asahi Spectroscopy Co., Ltd. (cutting a mercury lamp wavelength of 340 nm or less)) is put on the dried coating film without covering with a negative photomask (Example) 1 and Comparative Examples 1 to 4) (Example 2, Comparative Examples 5 and 6), an ultraviolet ray of 80 mJ / cm ² was irradiated with an ultrahigh pressure mercury lamp with an i-line illuminance of 30 mW / cm ² , and a photosensitive part The photocuring reaction was performed.

Next, this exposed coated plate was developed in a 0.08% aqueous potassium hydroxide solution at 25 ° C. at a shower developing pressure of 1 kgf / cm ² for 60 seconds, and then washed with 5 kgf / cm ² pressure of spray water. After hot post-baking at 230 ° C. for 30 minutes using a hot air dryer, the OD of the light irradiation part was evaluated using a Macbeth transmission densitometer. Furthermore, the film thickness of the light irradiation part was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD / μm.

<Evaluation of adhesion>
Each photosensitive resin composition obtained above was applied on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 μm, at 90 ° C. Pre-baked for 1 minute. Then, when a short wavelength cut filter (model number LU0350, manufactured by Asahi Spectroscopy Co., Ltd. (cutting a mercury lamp wavelength of 340 nm or less)) is placed on the coating film without using a negative photomask (Example 1, comparison) In Examples 1 to 4) and when not mounted (Examples 2 to 4, Comparative Examples 5 and 6), solid exposure was performed at 80 mJ / cm ² with an ultrahigh pressure mercury lamp with an i-line illuminance of 30 mW / cm ² , and a hot air dryer It was used and post-baked at 230 ° C. for 30 minutes. And about the post-baked board | substrate obtained above, the adhesive strength with a sealing glass board | substrate was evaluated as follows by the evaluation method according to the JISK6856-1994 three-point bending adhesion test method.

  Each of the post-baked substrate and the glass substrate (Corning 1737) not coated with the resin composition was cut into 20 mm × 63 mm strips to prepare test pieces. Post-baked coating plate and glass substrate not coated with photosensitive resin composition are overlapped with a certain amount of sealant epoxy adhesive (Structbond XN-21s (Mitsui Chemicals)) Both substrates (test pieces) were bonded together so that the thickness was 8 mm. When laminated, the sealant epoxy adhesive has a circular shape and a diameter of about 5 mm. Thereafter, the superposed test pieces were pre-baked at 90 ° C. for 20 minutes, followed by post-baking at 150 ° C. for 2 hours to prepare three-point bent test pieces. Furthermore, the sample for the comparative test which bonded together the glass piece which is not apply | coated 20 mm x 63 mm with the same method as the above was created.

  In the test piece obtained above, the coated plate and the counter substrate (uncoated substrate) or the uncoated glass substrate for comparison test are supported by two supports so that the overlapping part is centered (2 The length of the support at the point is 3 cm), and the load is applied at a speed of 1 mm / min using “UCT-100” manufactured by Orientec from directly above the overlapped portion to observe the peeled surface. And the load at that time were read, divided by the application area of the sealant epoxy adhesive, and the weight per unit area was defined as the adhesion strength. Further, after performing PCT (pressure cooker test) under the conditions of 121 ° C., 100% RH, 2 atm, and 5 hours, the same adhesion strength test was performed to evaluate the adhesion strength before and after PCT. The adhesion strength of each composition was shown as a relative value when the adhesion strength between the glasses to which no resist was applied before and after PCT was 100, respectively. Before and after PCT, 60 or more was evaluated as ◯, and less than 60 was evaluated as ×.

  As a result, the coating films obtained from the photosensitive resin compositions of Examples 1 to 4 had good line width, pattern linearity, and adhesion strength. On the other hand, none of the coating films obtained from the photosensitive resin compositions for black resists of Comparative Examples 1 to 6 had good line width, pattern linearity, and adhesion strength. For example, even in compositions having good adhesion strength as in Comparative Example 3 and Comparative Example 6, the pattern tends to be thin in developability, the pattern edge tends to be jagged, and the linearity of the pattern tends to be deteriorated. It can be seen that it is difficult to stably form a thin line such as the following.

Claims (10)

The following (A) to (D) ingredients,
(A) a polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting a reaction product of a compound having two or more epoxy groups with (meth) acrylic acid and a polyvalent carboxylic acid or an anhydride thereof;
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator, and
(D) In a photosensitive resin composition for a light-shielding film comprising as an essential component one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and light-shielding materials,
The weight ratio (A) / (B) of the component (A) and the component (B) is 50/50 to 90/10, and the total amount of the component (A) and the component (B) is 100 parts by weight ( C) 2-30 parts by weight of component,
And the photosensitive resin composition for light shielding films characterized by including the compound represented by the following general formula (I) as a photoinitiator of (C) component.

However, in the general formula (I), R ₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group represents an ether bond. In addition, a part of hydrogen atoms in the alkyl group or aryl group may be substituted with the following substituents. As the substituent, carbon C has 2 to 12 alkenyl groups, carbon C has 4 to 8 cycloalkenyl groups, carbon C has 2 to 12 alkynyl groups, and carbon C has 3 to 10 cycloalkyl groups. , Phenyl group, naphthyl group, carbon C which may be substituted with halogen is 1-5 alkoxy group, or halogen. R ₃ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms. 2. The photosensitive resin composition for a light-shielding film according to claim 1, wherein the photopolymerization initiator of component (C) contains a compound represented by the following general formula (II).

However, in General Formula (II), R ₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group has an ether bond. In addition, a part of hydrogen atoms in the alkyl group or aryl group may be substituted with the following substituents. As the substituent, carbon C has 2 to 12 alkenyl groups, carbon C has 4 to 8 cycloalkenyl groups, carbon C has 2 to 12 alkynyl groups, and carbon C has 3 to 10 cycloalkyl groups. , Phenyl group, naphthyl group, carbon C which may be substituted with halogen is 1-5 alkoxy group, or halogen. 2. The photosensitive resin composition for a light-shielding film according to claim 1, wherein the photopolymerization initiator of component (C) contains a compound represented by the following general formula (III).

However, in the general formula (III), R ₄ and R ₅ are independently a hydrogen atom, —O—CH ₂ CH ₃ , —O— (CH ₂ ) _{n + 1} CH ₃ , —O—CH ₂ CF ₃ , or -O-CH ₂ (CF ₂ ) _n CHF ₂ is shown. However, any one of R ₄ or R ₅ is a hydrogen atom. n is an integer of 1 to 3. 2. The photosensitive resin composition for a light-shielding film according to claim 1, wherein the photopolymerization initiator as the component (C) contains a compound represented by the following formula (IV).

(A) Component containing a polymerizable unsaturated group obtained by reacting a compound represented by the following general formula (V) with (meth) acrylic acid and further reacting with a polyvalent carboxylic acid or its anhydride An alkali-soluble resin is used, The photosensitive resin composition for light shielding films in any one of Claims 1-4 characterized by the above-mentioned.

In the general formula (V), R ₆ and R ₇ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X represents —CO—, —SO ₂ —, —C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or a single bond, It is a number from 0 to 10.   (D) Content of the light shielding component in a component is 40-70 mass% with respect to solid content in the photosensitive resin composition for light shielding films, The photosensitive property for light shielding films in any one of Claims 1-5. Resin composition.   (D) The light shielding component is carbon black, The photosensitive resin composition for light shielding films in any one of Claims 1-6.   A coating film formed by curing the photosensitive resin composition for a light-shielding film according to claim 1.   A light shielding film prepared by applying the photosensitive resin composition for a light shielding film according to any one of claims 1 to 7 on a transparent substrate, prebaking, then exposing with an ultraviolet exposure device, developing with an alkaline aqueous solution, and postbaking. A color filter characterized by having a membrane.   A light shielding film prepared by applying the photosensitive resin composition for a light shielding film according to any one of claims 1 to 7 on a transparent substrate, prebaking, then exposing with an ultraviolet exposure device, developing with an alkaline aqueous solution, and postbaking. A touch panel comprising a film.