JP2015069098A - Black photosensitive resin composition and cured film of the same, and color filter and touch panel including the cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black photosensitive resin composition which prevents coating film defects in a reduced-pressure drying process, which can give a coating film excellent in film thickness uniformity, and which is suitable for obtaining a cured film to be used for a color filter or a touch panel.SOLUTION: The black photosensitive resin composition is a black photosensitive composition comprising (A) a predetermined alkali-soluble resin, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a black pigment, and (E) a solvent. The (E) solvent contains a high boiling point solvent having a boiling point of 200°C to 260°C under an atmospheric pressure, a solvent viscosity of 2.0 to 3.2 mPa s at 25°C, and a surface tension of 23 to 32 dyn/cm; and the content of the high boiling point solvent is 1 to 10 mass% of the whole solvent amount.

Description

  The present invention relates to a black photosensitive resin composition and a cured film thereof, and further to a color filter and a touch panel for a display device having the cured film.

  The color filter of a liquid crystal display device usually has red, green, and blue pixels on a transparent substrate surface such as glass or a plastic sheet on which a black film for separating each pixel is formed, and in a striped or mosaic color. Manufactured by a pattern forming method. This black film plays the role of preventing the deterioration of contrast and color purity due to light leakage between pixels, and contains a light shielding material such as carbon black, titanium oxynitride or titanium black, and is a black photosensitive resin capable of alkali development. It is mainly to use a composition.

  In general, a color filter is obtained by applying a black photosensitive resin composition on a transparent substrate such as glass or plastic sheet using a spin coater or a slit coater, drying under reduced pressure using a vacuum dryer (VCD), and further using a hot plate. After carrying out the heat drying used, a black matrix is formed through exposure and development. Subsequently, a colored photosensitive resin composition of each color of red, green, and blue is sequentially formed on predetermined pixels of each color using the above process to manufacture a color filter.

  At present, a process of applying a black photosensitive composition on a substrate and drying under reduced pressure using VCD is common, but the solvent contained in the black photosensitive resin composition at the time of vacuum drying is There were problems such as bumping or uneven evaporation resulting in coating film defects (drying unevenness, surface roughness, craters) or a deterioration in film thickness uniformity.

  To solve this problem, Patent Document 1 discloses a colored photosensitive resin composition containing a hardly volatile solvent having a boiling point of 200 ° C. or more and 250 ° C. or less under atmospheric pressure in order to suppress coating film defects. Yes. However, in the situation where the required level for the film thickness uniformity of the coating film is increasing, there is still concern about whether the film thickness uniformity can be sufficiently obtained after sufficiently suppressing the coating film defects. Yes.

JP 2008-249822 A

  Accordingly, an object of the present invention is to provide a black photosensitive resin composition capable of preventing coating film defects during drying under reduced pressure and obtaining a coating film having excellent film thickness uniformity, and the black photosensitive resin composition. It is providing the coating film (cured film) using the thing, the color filter provided with the coating film, and a touch panel.

  When the black photosensitive resin composition contains a high-boiling solvent having a predetermined boiling point, a predetermined viscosity, and a predetermined surface tension, the coating film having good film thickness uniformity without surface defects. The inventors found that a film was obtained and completed the present invention. That is, the gist of the present invention is as follows.

(1) The present invention relates to (A) a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid. An acid or an acid anhydride thereof; and (b) an alkali-soluble resin obtained by reacting a tetracarboxylic acid or an acid dianhydride thereof; (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond; (C) A black photosensitive composition containing a photopolymerization initiator, (D) a black pigment, and (E) a solvent. (E) The solvent has a boiling point of 200 ° C. to 260 ° C. under atmospheric pressure, 25 A high-boiling solvent having a solvent viscosity of 2.0 to 3.2 mPa · s at 23 ° C. and a surface tension of 23 to 32 dyn / cm, and the content of the high-boiling solvent is 1 to 10% by mass of the total amount of the solvent It is characterized by A black photosensitive resin composition.

(2) The present invention is also a cured film obtained by patterning the black photosensitive resin composition according to (1) by a photolithography method, followed by thermosetting.

(3) The present invention is also a color filter having the cured film according to (2).

(4) The present invention is also a touch panel having the cured film according to (2).

  According to the present invention, it is possible to obtain a black photosensitive resin composition from which a coating film having a good film thickness uniformity without surface defects can be obtained, and applying the cured film to a color filter or a touch panel for a display device. Can do.

  The present invention is described in detail below.

  (A) in the black photosensitive resin composition of the present invention is obtained by reacting (a) with a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid. It is an alkali-soluble resin obtained by reacting (i) dicarboxylic acid or tricarboxylic acid or acid anhydride thereof, and (b) tetracarboxylic acid or acid dianhydride thereof. Here, the molar ratio of (a) / (b) is preferably 0.1 to 10.

  Examples of bisphenols used as a raw material for (A) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, 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) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dimethylphenyl) dimethylsilane, 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, -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-3,5-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 Derivatives. Among these, those having a 9,9-fluorenyl group are particularly preferably used.

一般式（Ｉ）の式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を表し、Ａは、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、９，９−フルオレニル基又は直結合を表す。ｌは０〜１０の数である。好ましいＲ_１、Ｒ_２、Ｒ_３、及びＲ_４は水素原子であり、好ましいＡは９，９−フルオレニル基である。また、ｌは通常複数の値が混在するため平均値０〜１０（整数とは限らない）となるが、好ましいｌの平均値は０〜３である。ｌの値が上限値を超えると、当該エポキシ化合物を使用して合成したアルカリ可溶性樹脂を用いた黒色感光性樹脂組成物としたとき、該組成物の粘度が大きくなりすぎて塗工がうまく行かなくなったり、アルカリ可溶性を十分に付与できずアルカリ現像性が非常に悪くなったりする。 Next, 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 following general formula (I) is obtained.

In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and A is — CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, 9,9-fluorenyl group Or it represents a direct bond. l is a number from 0 to 10. Preferred R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen atoms, and preferred A is a 9,9-fluorenyl group. In addition, since l generally has a plurality of values, the average value is 0 to 10 (not necessarily an integer), but the preferable average value of l is 0 to 3. When the value of l exceeds the upper limit, when the black photosensitive resin composition using the alkali-soluble resin synthesized using the epoxy compound is used, the viscosity of the composition becomes too high and the coating is performed successfully. In other words, the alkali solubility cannot be sufficiently imparted, and the alkali developability becomes very poor.

（式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を表し、Ｒ_５は、水素原子又はメチル基を表し、Ａは、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、９，９−フルオレニル基又は直結合を表し、Ｘは４価のカルボン酸残基を表し、Ｙ_１及びＹ_２は、それぞれ独立して水素原子又は−ＯＣ−Ｚ−（ＣＯＯＨ）_ｍ（但し、Ｚは２価又は３価カルボン酸残基を表し、ｍは１〜２の数を表す）を表し、ｎは１〜２０の数を表す。） Next, the compound of general formula (I) is reacted with acrylic acid or methacrylic acid as an unsaturated group-containing monocarboxylic acid, or both, and the resulting reaction product having a hydroxy group is subjected to (a) dicarboxylic acid or A tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof are preferably reacted in a range where the molar ratio of (a) / (b) is 0.1 to 10, and An alkali-soluble resin having the structure of an epoxy (meth) acrylate acid adduct represented by the general formula (II) is obtained.

Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. A represents —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—. , 9,9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ are each independently a hydrogen atom or —OC—Z— (COOH) _m (wherein Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 to 2, and n represents a number of 1 to 20.)

  Since this epoxy (meth) acrylate acid adduct (II) is an alkali-soluble resin having both an ethylenically unsaturated double bond and a carboxyl group, it is excellent as (A) of the black photosensitive resin composition of the present invention. It gives photocurability, good developability, and patterning characteristics, and provides a good pattern shape.

  (A) Dicarboxylic acid or tricarboxylic acid or acid anhydride thereof used in the epoxy (meth) acrylate acid adduct of general formula (II) which is (A) of the present invention includes a chain hydrocarbon dicarboxylic acid or tricarboxylic acid. An acid or an acid anhydride thereof, an alicyclic dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, an aromatic dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof is 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 further, dicarboxylic acid or tricarboxylic acid having an arbitrary substituent introduced therein 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 having a substituent introduced therein. 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. An acid anhydride may be used.

  The (b) tetracarboxylic acid or acid dianhydride used in the epoxy (meth) acrylate acid adduct of the general formula (II) which is (A) of the present invention includes a chain hydrocarbon tetracarboxylic acid. Or its acid dianhydride, alicyclic tetracarboxylic acid or its acid dianhydride, or aromatic polyhydric carboxylic acid or its 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, and further, a tetracarboxylic acid into which a substituent is introduced. 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, a tetracarboxylic acid or an acid dianhydride having a substituent introduced therein may be used. 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, and further substitution It may be a tetracarboxylic acid having an introduced group or an acid dianhydride thereof.

  (A) dicarboxylic acid or tricarboxylic acid or acid anhydride and (b) tetracarboxylic acid or acid diacid used in the epoxy (meth) acrylate acid adduct of general formula (II) which is (A) of the present invention. The molar ratio (a) / (b) with the anhydride is preferably 0.1 to 10, more preferably 0.2 to 3.0. When the molar ratio (a) / (b) deviates from the above range, the optimum molecular weight cannot be obtained. In the black photosensitive resin composition using (A), alkali developability, heat resistance, solvent resistance, pattern shape, etc. Is not preferable because it deteriorates. In addition, as the molar ratio (a) / (b) is smaller, the molecular weight increases and the alkali solubility tends to deteriorate.

  Moreover, it is preferable that the weight average molecular weight (Mw) is between 2000-10000, and the epoxy (meth) acrylate acid adduct of general formula (II) which is (A) of this invention is between 3000-7000. It is particularly preferred. When the weight average molecular weight (Mw) is less than 2000, the black adhesive resin composition using (A) cannot maintain the pattern adhesion at the time of development, resulting in pattern peeling, and the weight average molecular weight (Mw). If it exceeds 10,000, a development residue and a residual film of an unexposed part are likely to remain. Further, (A) desirably has an acid value in the range of 30 to 200 KOHmg / g. If this value is less than 30 KOHmg / g, the alkali development of the black photosensitive resin composition using (A) tends to deteriorate, so special development conditions such as strong alkali are required. On the other hand, when it exceeds 200 KOHmg / g, the penetration of the alkali developer into the black photosensitive resin composition using (A) becomes too fast, and peeling development occurs.

  The epoxy (meth) acrylate acid adduct of the general formula (II) used in the present invention is described in known methods, for example, JP-A-8-278629 and JP-A-2008-9401, by the above-described steps. It can manufacture by the method of. First, as a method for reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound of the general formula (I), for example, an epoxy group of an 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.

  Examples of the photopolymerizable monomer (B) having at least one ethylenically unsaturated bond in the black photosensitive resin composition of the present invention include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. , (Meth) acrylic acid esters having a hydroxyl group such as 2-ethylhexyl (meth) 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, penta Rithritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipenta Examples include (meth) acrylic acid esters such as erythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, These 1 type (s) or 2 or more types can be used. The photopolymerizable monomer having at least one ethylenically unsaturated bond is one having three or more photopolymerizable groups and capable of cross-linking molecules of the unsaturated group-containing alkali-soluble resin. It is preferable. Note that (B) the photopolymerizable monomer having at least one ethylenically unsaturated bond does not have a free carboxy group.

  Examples of the (C) photopolymerization initiator in the black photosensitive resin composition of the present invention include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, and trichloroacetophenone. Acetophenones such as p-tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Benzoin ethers, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbi Biazole compounds such as dazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4- Halomethylthiazole compounds such as oxadiazole, 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 (trichloroRmethyl) -1, 3,5-tri Azine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloro Halomethyl-S-triazine compounds such as methyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-o-benzo Art, o-acyloxy such as 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-o-acetate, 1- (4-methylsulfanylphenyl) butan-1-oneoxime-o-acetate Compounds, benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthio Sulfur compounds such as xanthone and 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumene Examples thereof include organic peroxides such as peroxides, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. Of these, o-acyloxime compounds are preferably used from the viewpoint of easily obtaining a highly sensitive black photosensitive resin composition. Two or more of these photopolymerization initiators can also be used. In addition, the photoinitiator as used in the field of this invention is used by the meaning containing a sensitizer.

  As the (D) black pigment in the black photosensitive resin composition of the present invention, a mixed color organic pigment or an inorganic pigment can be used without any particular limitation. Examples of black organic pigments include perylene black, cyanine black, and aniline black. Examples of mixed color organic pigments include those obtained by mixing at least two pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like into a pseudo black color. Examples of inorganic pigments include carbon black, chromium oxide, iron oxide, titanium black, titanium oxynitride, and titanium nitride. These light-shielding materials (black pigments) can be used alone or in appropriate combination of two or more, but carbon black, in particular, has light-shielding properties, surface smoothness, dispersion stability, and affinity for resins. It is preferable in terms of good points.

  The (E) solvent in the black photosensitive resin composition of this invention can use several types of solvents used for a general black photosensitive composition, and contains the specific high boiling point solvent which is demonstrated below. That is, the specific high-boiling solvent used has a boiling point of 200 ° C. to 260 ° C. under atmospheric pressure. Further, the solvent viscosity at 25 ° C. is 2.0 to 3.2 mPa · s. Furthermore, the surface tension is 23 to 32 dyn / cm. The boiling point in the atmosphere is more preferably 250 to 260 ° C., the melt viscosity at 25 ° C. is more preferably 2.2 to 2.8 mPa · s, and the surface tension is more preferably 24 to 28 dyn / cm.

  Moreover, there exists an effect which suppresses the coating-film defect at the time of reduced pressure drying by making content of a high boiling point solvent into 1-10 mass% of the total amount of solvent, More preferably, it shall be 2-4 mass%. Further, since the high boiling point solvent remains until the final stage of drying under reduced pressure, it is possible to obtain a coating film that suppresses surface roughness and drying unevenness and has excellent in-plane film thickness uniformity. In order to satisfy the condition that the high boiling point solvent remains until the final stage of drying under reduced pressure, it is preferable that the weight reduction rate of the high boiling point solvent after heating at 100 ° C. for 60 seconds is 3% or less.

  Specific examples of the high boiling point solvent include 1,3-butylene glycol diacetate (1,3-BGDA), diethylene glycol monoethyl ether acetate (EDGAC), diethylene glycol monobutyl ether acetate (BDGAC), and diethylene glycol dibutyl ether (BDB). be able to. Among these, diethylene glycol dibutyl ether (BDB) is more preferable.

  In addition, (E) the solvent contains other solvents in addition to the high boiling point solvent. As the other solvent, one kind or plural kinds of solvents can be contained, and are not particularly limited. For example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-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, triethylene glycol Cole monoethyl ether, glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate A uniform solution-like composition can be obtained by dissolving and mixing several kinds of these.

  Further, the black photosensitive resin composition of the present invention may be added with a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, a surfactant and the like as necessary. An agent 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.

  The black photosensitive resin composition of this invention contains the said (A)-(E) component as a main component. In the black photosensitive resin composition, preferably, (E) in the solid content excluding the solvent (including the monomer component that becomes a solid content after photocuring), (A) with respect to 100 parts by mass, (B) Is 10 to 60 parts by mass, and (C) is 2 to 40 parts by mass with respect to the total mass of (A) and (B). More preferably, (B) is 30 to 50 parts by mass with respect to 100 parts by mass of (A), and (C) is 3 to 30 parts by mass with respect to the total mass of (A) and (B). Moreover, about (D) black pigment, it is good that content is 1-80 mass% or less with respect to solid content, More preferably, it is the range of 20-60 mass%.

  Examples of a method for forming a cured film using the black photosensitive resin composition of the present invention include a method using a photolithography method. As the formation method, first, a black photosensitive resin composition is applied to the substrate surface, and then the solvent is dried (prebaked), and then the exposed coating is irradiated with ultraviolet rays through a photomask. And a method of forming a pattern by carrying out development that elutes an unexposed portion using an aqueous alkali solution, followed by thermal curing (post-baking). Here, as the substrate to which the black photosensitive resin composition is applied, glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) is used.

  As a method of applying the black photosensitive resin composition to the substrate, any method such as a method using a roller coater machine, a land coater machine, a slit coater machine or a spinner machine in addition to a known solution dipping method or spray method is adopted. can do. After applying to a desired thickness by these methods, the coating film is formed by removing the solvent (prebaking). Pre-baking is performed by removing the solvent by vacuum drying (VCD) at 23 ° C. and 20 to 100 Pa for 15 to 60 seconds, and then heating with an oven, a hot plate or the like. The heating temperature and heating time in this 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 the pre-baking is performed by an exposure machine, and the photosensitive resin and the photosensitive monomer corresponding to the pattern are exposed by exposing through a photomask. The exposure machine and the exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a deep ultraviolet lamp.

  Alkali development after exposure is performed for the purpose of removing the unexposed portions of the coating film, and a desired pattern is formed by this development. Examples of the developer suitable for the alkali development include an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. It is preferable to develop at a temperature of 23 to 27 ° C. using a weakly alkaline aqueous solution containing 0.03 to 1% by mass of carbonate, and a fine image is precisely obtained using a commercially available developing machine or ultrasonic cleaner. Can be formed.

  After the development as described above, a heat treatment (post-bake) is performed at a temperature of 200 to 240 ° C. for 20 to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned black film and the substrate. This is done by heating with an oven, hot plate or the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

[Preparation of black photosensitive resin composition]
Each solvent shown in Table 1 was used and blended according to the composition shown in Table 2 to prepare black photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2. The components used for each composition are shown below.
(A) Alkali-soluble resin: propylene glycol monomethyl ether acetate solution of an epoxy acrylate acid adduct having a fluorene skeleton (resin solid content concentration 56.5%, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name V-259ME)
(B) Photopolymerizable monomer: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name DPHA manufactured by Nippon Kayaku Co., Ltd.)
(C) Photopolymerization initiator: 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl] ethanone = O-acetyloxime (trade name Irgacure OXE02 manufactured by BASF)
(D) Black pigment: Carbon black dispersion of propylene glycol monomethyl ether acetate solvent having a carbon black concentration of 25 w% and a polymer dispersant of 6 w% (E) solvent:
(E) -1: Propylene glycol monomethyl ether acetate (PGMEA)
(E) -2: Diethylene glycol dimethyl ether (MDM)
(E) -3: Diethylene glycol ethyl methyl ether (EDM)
(E) -4a: diethylene glycol dibutyl ether (BDB)
(E) -4b: Diethylene glycol monobutyl ether acetate (BDGAC)
(E) -4c: 1,3-butylene glycol diacetate (1,3-BGDA)
(E) -4d: diethylene glycol monoethyl ether acetate (EDGAC)
(E) -5: Diethylene glycol diethyl ether (EDE)
(F) Surfactant (G) Silane coupling agent (1% propylene glycol monomethyl ether acetate solution)

  The weight change rates shown in Table 1 were determined by setting the hot plate temperature to 100 ° C., setting the petri dish on the hot plate, dropping each solvent, and measuring the weight loss of the solvent after 60 seconds. The solution viscosity was measured at 25 ° C. using an E-type viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.). The surface tension was measured at 23 ° C. using a fully automatic surface tension meter (BVP-Z type, manufactured by Kyowa Interface Science Co., Ltd.).

[Evaluation of uneven drying]
After coating and drying the black photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 using a glass plate (5 inch square) and a spin coater under the condition that the film thickness after drying was 1.6 μm, sodium The coated surface was observed by irradiation with lamp light. Drying conditions were VCD 23 ° C. 50 Pa 30 seconds and hot plate heating 100 ° C. 90 seconds. Table 3 shows the evaluation results based on the following criteria.
・ Criteria
○ No white mist on the coated surface × White mist on the coated surface

[Surface roughness (Å)]
After drying the black photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 using a glass plate (5 inch square) and a spin coater (drying conditions are the same as in the drying unevenness evaluation), the film thickness is 1. After coating and drying under the condition of .6 μm, the surface roughness (測定) was measured using a stylus type film thickness meter (P-15, manufactured by KLA-Tencor). Table 3 shows the evaluation results based on the following criteria.
・ Criteria
○ 60Å or less △ 60Å or more and 100Å or less × 100Å or more

[Crater observation]
After drying the black photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 using a glass plate (5 inch square) and a spin coater (drying conditions are the same as those during the evaluation of drying unevenness), the film thickness is 1 After coating and drying under the condition of .6 μm, the coated surface was observed using a metal microscope. Table 3 shows the evaluation results based on the following criteria.
・ Criteria ○ No crater on the coated surface × Crater on the coated surface

[Thickness uniformity]
After drying the black photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 using a glass plate (5 inch square) and a spin coater (drying conditions are the same as those during the evaluation of drying unevenness), the film thickness is 1 After coating and drying under a condition of .6 μm, film thickness measurement was carried out at five locations (central part + four corners) on the substrate using a stylus type film thickness meter (P-15, manufactured by KLA-Tencor). Table 3 shows the evaluation results based on the following criteria.
・ Criteria
○ Standard deviation is 0.05μm or less △ Standard deviation is 0.05μm or more and less than 0.1μm × Standard deviation is 0.1μm or more

  As is clear from the results in Table 3, it can be seen that the resin composition containing the high-boiling solvent according to the present invention is suitable for obtaining a cured film excellent in at least the evaluation regarding drying unevenness and surface condition. Furthermore, by determining the viscosity and surface tension areas as selection criteria for the high boiling point solvent, it is clear that the coating film flow is suppressed in the coating and drying process, and the film thickness is excellent in uniformity. became.

Claims (4)

  (A) For a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid, (a) a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, And (b) an alkali-soluble resin obtained by reacting tetracarboxylic acid or its acid dianhydride, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator. , (D) a black pigment and (E) a solvent, and (E) the solvent has a boiling point of 200 ° C. to 260 ° C. under atmospheric pressure and a solvent viscosity at 25 ° C. of 2. It contains 0 to 3.2 mPa · s and a high boiling point solvent having a surface tension of 23 to 32 dyn / cm, and the content of the high boiling point solvent is 1 to 10% by mass of the total amount of the solvent. Black photosensitivity Fat composition.   The cured film obtained by patterning the black photosensitive resin composition of Claim 1 by the photolithographic method, and carrying out subsequent thermosetting.   A color filter having the cured film according to claim 2.   A touch panel having the cured film according to claim 2.