JP2012027448A - Photosensitive resin composition for black resist and color filter light shielding film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for black resist which is capable of forming a pattern having excellent pattern dimensional stability, good development margin and sharpness of its edge shape even in the case of a thick film, and which provides a smooth coating surface and prevents deterioration of surface roughness caused by heat curing shrinkage in a subsequent heat baking process.SOLUTION: A photosensitive resin composition for black resist comprises: as essential components, (A) a dendritic polymer having two or more ethylenically polymerizable groups at a terminal; (B) an unsaturated group-containing compound obtained by reacting a reactant of an epoxy compound having two glycidyl ether groups derived from bisphenols and a (meth)acrylic acid with a polybasic carboxylic acid or an anhydride thereof; (C) a photoinitiator; and (D) one or more shielding components selected from a black organic pigment, a mixed color organic pigment and a light shielding material. A light shielding film is formed from the photosensitive resin composition.

Description

  The present invention relates to an alkaline aqueous solution developing type photosensitive resin composition for black resist for forming a fine light-shielding film on a transparent substrate, and a color filter light-shielding film formed using the same.

A color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic sheet, and then sequentially applies three or more different hues such as red, green and blue in a striped or mosaic shape. It is formed with a color pattern. The black matrix is called a light shielding film because it plays a role of improving contrast by suppressing color mixing between colors or preventing malfunction of TFT due to light leakage.
A typical method for producing a color filter is a pigment dispersion method in which a photopolymerizable composition containing a color material is applied onto a transparent substrate, and image exposure, development, and curing as necessary are repeated to form a color filter image. There is. This method is widely used because it has high accuracy such as the position and film thickness of the color filter pixels, is excellent in durability such as light resistance and heat resistance, and has few defects such as pinholes.

  In recent years, in order to achieve high brightness and high definition, a resin black matrix, which is one of color filter-related materials, is required to have higher light shielding than ever before, and further thickening is required. In recent years, it has been attracting attention that a color filter is manufactured by an inkjet method in which exposure is unnecessary and a coloring material can be applied only to a necessary portion. In this ink jet system, the black matrix itself is used as a partition wall, so that a thick film is essential. Furthermore, various types of color filters have been studied for improving the panel performance and reducing the cost, and the resin black matrix is increasingly required to be thicker than before.

  However, as the film thickness of the resin black matrix increases, the difference in crosslink density in the film thickness direction at the exposed part increases, making it more difficult to achieve high sensitivity and obtain a well-shaped black pattern. Become. Furthermore, in the subsequent thermal firing process, there is a difference in the crosslink density in the film thickness direction at the exposed part, resulting in a difference in the thermal curing shrinkage between the coating surface and the substrate, increasing the coating surface roughness. However, the surface smoothness deteriorates and the subsequent formation of red, blue and green pixels is adversely affected. Although it is possible to prevent the surface roughness from increasing by changing the exposure conditions and the thermal baking conditions, it is not preferable because the patterning characteristics and reliability may be impaired.

  Patent Document 1 reports that a black resist to which an acrylic copolymer is added as an alkali-soluble resin is effective in suppressing wrinkles in a thick film having a thickness of 1 μm or more. However, in the examples, since an acrylic copolymer having no photoreactive group is added as an alkali-soluble resin, when the process conditions are severe such as low exposure amount and over-development, high sensitivity and development adhesion can be obtained. There is a limit.

  Patent Document 2 discloses a dendritic polymer in which a small amount of a polyvalent mercapto compound is added to a polyfunctional acrylate with respect to the ethylenic double bond of the polyfunctional acrylate, which is a UV-curable ink. There is a potential demand for materials. Here, the dendritic polymer is also referred to as a dendrimer or a hyperbranched polymer.

JP 2007-286478 A International Publication No. 2008/47620

  Therefore, the object of the present invention is to solve the above problems and form a pattern having excellent pattern dimensional stability and excellent development margin and sharpness of the edge shape of the pattern even when the film thickness is 1.2 μm or more. Furthermore, in the subsequent thermal baking process, the coating film surface is smooth and surface roughness does not deteriorate due to thermal curing shrinkage, and the cross-sectional shape of the pattern can also maintain the trapezoidal shape after development. It is providing the photosensitive resin composition for a certain black resist. Another object of the present invention is to provide a light-shielding film formed using this photosensitive resin composition for black resist.

  As a result of investigations to solve the above problems, the present inventors have further reacted a reaction product of an aromatic epoxy compound derived from bisphenols with (meth) acrylic acid with a polybasic carboxylic acid or an anhydride thereof. The above-mentioned problems can be solved by blending an unsaturated group-containing compound obtained by mixing with a dendritic polymer having two or more polymerizable reactive groups at the end as a photopolymerizable compound having an ethylenically unsaturated bond. As a result, the present invention has been completed.

The present invention includes the following components (A) to (D):
(A) Dendritic polymer having two or more ethylenic polymerizable groups at its terminal (B) A reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and (meth) acrylic acid Further, an unsaturated group-containing compound obtained by reacting with a polybasic carboxylic acid or an anhydride thereof,
(C) a photopolymerization initiator, and (D) one or more light-shielding components selected from black organic pigments, mixed-color organic pigments and light-shielding materials,
Is a photosensitive resin composition for a black resist, characterized in that it contains as an essential component.

（式中、Ｒ¹は水素又は炭素数１〜４のアルキル基を表し、Ｒ²は多価アルコールＲ³（ＯＨ）ｍのｍ個のヒドロキシル基うちｎ個のヒドロキシル基を式中のエステル結合に供与した残り部分を表し、ｍ及びｎは、独立に２〜２０の整数を表すが、ｍ≧ｎである。）

（式中、Ｒ⁴は単結合又は２〜６価の炭素数１〜６の炭化水素基含有基であり、ｐはＲ⁴が単結合であるときは２であり、Ｒ⁴が２〜６価の基であるときは、２〜６の整数を表す。） Here, the component (A) is a part of the carbon-carbon double bond in the (meth) acrylate group of the polyfunctional (meth) acrylate compound represented by the following general formula (1). It is advantageous to be a dendritic polymer obtained by adding the indicated multivalent mercapto compound.

(In the formula, R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ² represents an ester bond in which n hydroxyl groups out of m hydroxyl groups of the polyhydric alcohol R ³ (OH) m are represented. And m and n independently represent an integer of 2 to 20, where m ≧ n.)

(In the formula, R ⁴ is a single bond or a 2 to 6-valent C 1-6 hydrocarbon group-containing group, p is 2 when R ⁴ is a single bond, and R ⁴ is 2-6. When it is a valent group, it represents an integer of 2 to 6.)

  Moreover, the addition ratio with respect to the carbon-carbon double bond of the mercapto group of the polyvalent mercapto compound represented by the general formula (2) and the polyfunctional (meth) acrylate compound represented by the general formula (1) is a mercapto group. The molar ratio of / double bond is preferably 1/100 to 1/3.

（但し、式中、Ｒ₁₁及びＲ₁₂は水素原子、炭素数１〜５のアルキル基又はハロゲン原子のいずれかであり、Ｘは‐ＣＯ‐、−ＳＯ₂−、‐Ｃ（ＣＦ₃）₂−、−Ｓｉ（ＣＨ₃）₂‐、−ＣＨ₂‐、−Ｃ（ＣＨ₃）₂‐、−Ｏ−、下記式（４）で表される９，９−フルオレニル基又は単結合を示し、ｎは０〜１０の整数である）

The component (B) was obtained by further reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and (meth) acrylic acid with a polybasic carboxylic acid or its anhydride. Although it is an unsaturated group containing compound, it is preferable that the epoxy compound which has these two glycidyl ether groups is an epoxy compound represented by following General formula (3).

(In the formula, R ₁₁ and R ₁₂ are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is —CO—, —SO ₂ —, —C (CF ₃ ) _2. —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, a 9,9-fluorenyl group represented by the following formula (4) or a single bond; n is an integer of 0 to 10)

  The component (D) is a light shielding component, but is preferably carbon black. Moreover, it is preferable that the said (D) component is mix | blended in the ratio of 30 to 50 weight% of the solid component in the photosensitive resin composition for black resists. Here, the solid component in the photosensitive resin composition for black resist includes a reactive component that reacts after curing and remains as a solid content, and refers to a component other than the solvent.

  Furthermore, the present invention is a color filter light-shielding film formed from the above-described photosensitive resin composition for black resist.

  The photosensitive resin composition for a black resist of the present invention can be suitably used as a coating material, and in particular, a color filter ink used for a liquid crystal display device or a photographing element, and a light-shielding film formed thereby. It is useful as a color filter, a black matrix for liquid crystal projection, and the like. Further, the photosensitive composition for black resist of the present invention is not limited to the color filter ink of the color liquid crystal display as described above, but various multicolor display material ink materials such as a color liquid crystal display device, a color facsimile, and an image sensor. Can also be used.

  Hereinafter, the present invention will be described in detail. The photosensitive resin composition for black resists of the present invention (hereinafter sometimes abbreviated as photosensitive resin composition) contains the components (A) to (D) as essential components. Hereinafter, the components (A) to (D) will be described.

  The dendritic polymer as component (A) is a multi-branched polymer having two or more ethylenic polymerizable groups at its terminals. The ethylenic polymerizable group is preferably derived from a (meth) acrylate compound, but is not limited thereto. Here, the ethylenically polymerizable group is a group having a carbon-carbon double bond, and a conjugated compound such as an α, β-unsaturated carbonyl compound in which a carbonyl group is bonded to the carbon-carbon double bond. Is known to undergo a Michael addition reaction with a vinyl group having the strongest interaction with a nucleophile such as a mercapto compound. Therefore, if a compound having a plurality of ethylenically polymerizable groups such as an α, β-unsaturated carbonyl compound and a compound having a plurality of nucleophilic groups such as a polyvalent mercapto compound are reacted, If there is an addition reaction at the β-position carbon relative to the group and there are a plurality of groups where the addition reaction occurs, a large number of branches are produced, resulting in a dendritic polymer. Such a dendritic polymer is known from Patent Document 2 and can be obtained by the method described in such a document.

  As the dendritic polymer which is component (A), a polyfunctional (meth) acrylate compound represented by the general formula (1) and a polyvalent mercapto compound represented by the general formula (2) are added by Michael addition (β for the carbonyl group). To the carbon-carbon double bond). Here, Michael addition of the polyvalent mercapto compound represented by the general formula (2) to the polyfunctional (meth) acrylate compound represented by the general formula (1) indicates that the resulting dendritic polymer is still carbon-carbon. The carbon-carbon double bond of the compound represented by the general formula (1) remains in the range of 0.1 to 50 mol% as a whole so that radiation polymerization based on the double bond can be performed. Preferably, it is done.

For example, the mercapto group of the polyvalent mercapto compound represented by the general formula (2) and the carbon-carbon double bond of the polyfunctional (meth) acrylate compound represented by the general formula (1) (in the general formula (1), CH ₂ = C (R ¹ )-represents a double bond, and in the case of calculation of the molar ratio, it is referred to as a double bond.) The addition ratio is 1/100 to 1/1 in terms of a mercapto group / double bond molar ratio 3 is preferable, 1/50 to 1/5 is more preferable, and 1/20 to 1/8 is particularly preferable.

  The dendritic polymer preferably has a sufficient amount of functional groups for radiation polymerization. For this purpose, the molecular weight of the dendritic polymer is preferably in the range of 100,000 to 10,000 molecular weight per mole of carbon-carbon double bond. Moreover, the preferable weight average molecular weight (Mw) of a dendritic polymer is 1000-20000, More preferably, it is 8000-15000.

In the general formula (1), R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ² represents n hydroxyl groups among m hydroxyl groups of the polyhydric alcohol R ³ (OH) _m. It is the remaining part donated to the ester bond. Preferably, R ³ (OH) _m is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a plurality of molecules of the polyhydric alcohol are alcohols. It is a polyhydric alcohol ether formed by dehydration condensation through an ether bond, or an ester of these polyhydric alcohol or polyhydric alcohol ether and hydroxy acid. In the said General formula (1), m and n represent the integer of 2-20 independently, but it is m> = n. Preferably, m and n are integers of 2 to 10, where m ≧ n.

  Preferred specific examples of the polyfunctional (meth) acrylate compound represented by the general formula (1) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (Meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, trimethylolethane Tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified Pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, epichlorohydrin-modified hexahydrophthalic acid di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, ethylene oxide modified neopentyl glycol di (meth) acrylate, Pyrene oxide modified neopentyl glycol di (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, trimethylolpropane benzoate (meth) acrylate, tris ((meth)) (Meth) such as (acryloxyethyl) isocyanurate, alkoxy-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, etc. ) Acrylic acid esters can be mentioned. These compounds may be used alone or in combination of two or more.

In the general formula (2), R ⁴ is a single bond or a C 2-6 divalent hydrocarbon group-containing group, p is 2 when R ⁴ is a single bond, R ⁴ When is a 2-6 valent group, the integer of 2-6 is represented. Preferably, R ⁴ is a single bond or an optionally substituted hydrocarbon group having 1 to 6 carbon atoms or a hydrocarbon group that may further contain an oxygen atom in the skeleton of the hydrocarbon group, This may be linear or branched. Further, these hydrocarbon group-containing groups may further have a carbonyloxy group bonded to a part of the thiomethyl group (HSCH ₂ —) appearing in the general formula (2). In addition, when an oxygen atom is included in the skeleton of the hydrocarbon group, both ends are preferably hydrocarbon groups. p represents an integer of 2 to 6 and corresponds to the valence of R ⁴ . Therefore, p is 2 when R ⁴ represents a single bond, p is 2 to ⁴ when R ⁴ has 1 carbon, and p is 2 to 4 when R ⁴ has 2 to 6 carbons. 2-6.

  Examples of the polyvalent mercapto compound represented by the general formula (2) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bisdimercaptoethanethiol, trimethylolpropane tri (Mercaptoacetate), trimethylolpropane tri (mercaptopropionate), pentaerythritol tetra (mercaptoacetate), pentaerythritol tri (mercaptoacetate), pentaerythritol tetra (mercaptopropionate), dipentaerythritol hexa (mercaptoacetate) And dipentaerythritol hexa (mercaptopropionate).

  In the synthesis of the dendritic polymer, a polymerization inhibitor can be added as necessary. As the polymerization inhibitor, hydroquinone compounds and phenol compounds generally used for preventing polymerization of (meth) acrylate compounds can also be used in the present invention. Specific examples thereof include, but are not limited to, hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, dibutylhydroxytoluene, 2,4,6-tri-tert-butylphenol (BHT) and the like. .

  Confirmation of completion of the synthesis of the dendritic polymer can be confirmed by liquid chromatography, gel filtration chromatography, or other general analytical instruments.

  When synthesizing a dendritic polymer, the polyvalent mercapto compound represented by the general formula (2) undergoes a Michael addition reaction to the double bond of the polyfunctional (meth) acrylate compound represented by the general formula (1). This reaction can be carried out by mixing a polyfunctional (meth) acrylate compound and a polyvalent mercapto compound and adding a basic catalyst at room temperature to 100 ° C. The reaction time is usually about 30 minutes to about 20 hours, preferably 6 to 12 hours.

  The detailed mechanism that the dendritic polymer has excellent characteristics as a photosensitive resin composition for a black resist is not clear. However, dendritic polymers using thiols and acrylates generally have a unique structure and are not susceptible to reaction inhibition by oxygen or solvents in radical polymerization, and are cured at low energy. It is considered that when the light shielding film is made thick, it has particularly excellent characteristics.

  The amount of the dendritic polymer contained in the photosensitive resin composition for black resist of the present invention is suitably 5 to 40% by weight, preferably 10 to 40% of the total amount of the components (A) and (B). % By weight. Moreover, when using a polymeric component (E) elsewhere, it is preferable that it is 20 to 35 weight% of the total amount of polymerizable components. When the content of the dendritic polymer is smaller than this range, the effect of suppressing the surface roughness of the coating film is lowered, and the coating film surface roughness may be increased. On the other hand, if the content of the dendritic polymer is larger than this range, development delay or pattern linearity may be deteriorated.

  In addition to the above components (A) and (B), the photosensitive resin composition for black resist of the present invention further comprises a photopolymerizable or radically polymerizable compound having an ethylenically unsaturated bond as the component (E). It can also be used. As said (E) component, polyfunctional (meth) acrylate is mentioned preferably. The component (E) is not the same as the components (A) and (B).

  Examples of the bifunctional (meth) acrylate as the component (E) include 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2 , 4-Dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) ) Acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (me ) Acrylate, bisphenol F polyethoxydi (meth) acrylate, and the like.

  Trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, and the like.

  Tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, ethoxylated penta Examples include erythritol tetra (meth) acrylate.

  Furthermore, as pentafunctional or hexafunctional (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene Examples include alkylene oxide-modified hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  When the photosensitive resin composition for black resist contains the above component (E), the content is suitably 10 to 50 parts by weight based on the total of 100 parts by weight of the components (A) and (E). And preferably 20 to 40 parts by weight.

  The unsaturated group-containing compound (B) is a polybasic carboxylic acid or an anhydride thereof obtained by further reacting an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth) acrylic acid. It is the unsaturated group containing compound obtained by making it react, and this epoxy compound or unsaturated group containing compound is well-known.

  The unsaturated group-containing compound is prepared by reacting (meth) acrylic acid (which means acrylic acid and / or methacrylic acid) with an epoxy compound having two glycidyl ether groups derived from bisphenols. An epoxy (meth) acrylate acid adduct obtained by reacting the obtained compound having a hydroxy group with a polybasic carboxylic acid or an anhydride thereof. And the epoxy compound induced | guided | derived from bisphenol means the epoxy compound obtained by making bisphenol and epihalohydrin react, or its equivalent. Since the unsaturated group-containing compound (B) has both an ethylenically unsaturated double bond and a carboxyl group, it has excellent photocurability, good developability, and patterning characteristics for the photosensitive resin composition for black resist. The physical properties of the light shielding film are improved.

As the component (B), an epoxy compound having two glycidyl ether groups derived from bisphenols is preferably an epoxy compound represented by the above general formula (3). In the general formula (3), R ₁₁ and R ₁₂ are any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a halogen atom, and X is —CO—, —SO ₂ —, —C (CF ₃ ) ₂ −, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, a 9,9-fluorenyl group or a single bond represented by the above formula (4) N is an integer of 0-10.

  The unsaturated group-containing compound as component (B) is preferably derived from an epoxy compound represented by formula (3). This epoxy compound is derived from bisphenols. Therefore, since an unsaturated group-containing compound is understood by explaining bisphenols, preferred specific examples will be explained by bisphenols. Examples of bisphenols that give preferable unsaturated group-containing compounds include the following. 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) dimethyl Silane, 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 and the like, or X is the 9,9-fluorenyl group described above 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-dibromo Phenyl) fluorene and the like, and further compounds such as 4,4′-biphenol and 3,3′-biphenol.

  Examples of the polybasic carboxylic acid or acid anhydride thereof that can react with a hydroxy group in an epoxy (meth) acrylate molecule obtained by reacting such an epoxy compound with (meth) acrylic acid include, for example, malee. Acids, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, etc. and their acid anhydrides, and pyromellitic Examples thereof include aromatic polyvalent carboxylic acids such as acids, benzophenone tetracarboxylic acids, biphenyl tetracarboxylic acids, and biphenyl ether tetracarboxylic acids, and acid dianhydrides thereof. And about the usage-amount of an acid anhydride and an acid dianhydride, the ratio suitable for forming a fine pattern by exposure and alkali image development operation can be selected.

  About the unsaturated group containing compound of (B) component, even if it uses only 1 type, the mixture of 2 or more types can also be used. Moreover, reaction with an epoxy compound and (meth) acrylic acid, reaction with the epoxy (meth) acrylate obtained by this reaction, and a polybasic acid or its acid anhydride can employ | adopt a well-known method, It is not particularly limited.

  As the photopolymerization initiator of the component (C), benzophenone, Michler ketone, N, N′tetramethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, Aromatic ketones such as 2-ethylanthraquinone and phenanthrene, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoins such as methyl benzoin and ethyl benzoin, 2- (o-chlorophenyl) -4,5 -Phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4 5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p- Halomethyldiazole compounds such as cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-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-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine Halomethyl-S-triazine compounds such as 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,2-dimethoxy-1,2-diphenylethane 1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 2-benzyl-2-dimethylamino-1- [4-morpholinophenyl] -butanone, , 1-hydroxy - cyclohexyl - photopolymerization initiators such as phenyl ketone.

  These photoinitiators can be used individually or in mixture of 2 or more types. In addition, although it does not act as a photopolymerization initiator or sensitizer by itself, it is also possible to add a compound that can increase the ability of the photopolymerization initiator or sensitizer by using in combination with the above compound. it can. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

  The amount of the photopolymerization initiator used as the component (C) is suitably 3 to 30 parts by weight based on the total of 100 parts by weight of the components (A) and (B). More preferably, it is 5 to 20 parts by weight. When the blending ratio of the component (C) is less than 3 parts by weight, the speed of photopolymerization becomes slow and the sensitivity is lowered. On the other hand, when it exceeds 30 parts by weight, the sensitivity is too strong and the pattern line The width becomes thicker than that of the pattern mask, and there is a possibility that a line width that is faithful to the mask cannot be reproduced or that the pattern edge is not sharp.

  The light shielding component such as the black organic pigment, the mixed color organic pigment or the light shielding material as the component (D) 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 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 the light shielding material include carbon black, chromium oxide, iron oxide, and titanium black. Two or more kinds can be appropriately selected and used. In particular, carbon black has light shielding properties, surface smoothness, and dispersion stability. And the compatibility with the resin is preferable.

  About the mixture ratio of the light-shielding component of (D) component, the ratio of 30 to 50 weight% is preferable with respect to the solid component in the photosensitive resin composition for black resists. If it is less than 30% by weight, the light-shielding property will not be sufficient, and thermosetting shrinkage will increase and the surface roughness of the coating film may increase. If it exceeds 50% by weight, the shrinkage due to thermosetting is reduced and the deterioration of the surface roughness is suppressed, but the content of the photosensitive resin as the original binder is reduced, so that the development characteristics are impaired and the film forming ability is impaired. Undesired problems arise.

  In the photosensitive resin composition for black resists of this invention, the said (A)-(D) component is included as an essential component, and the said (E) component is included as an arbitrary component. Here, the components (A), (B), and (E) are polymerizable components, the component (C) is a component that initiates and accelerates polymerization of these polymerizable components, and the component (D) is light-shielded. It is a component that gives sex. Therefore, the ratio of the polymerizable component ((A) + (B) + (E)) in the solid component excluding the solvent in the photosensitive resin composition for black resist is in the range of 40 to 60% by weight ( The proportion of component (C) is preferably in the range of 2 to 12% by weight, and the proportion of component (D) is preferably in the range of 30 to 50% by weight. Of the polymerizable components, the proportion of the component (A) is 10 to 50% by weight, preferably 20 to 40% by weight of the total polymerizable component, and the proportion of the component (B) is the total polymerization. The proportion of the component (E) is in the range of 0 to 25% by weight of the total polymerizable component. Furthermore, the ratio of the (A), (B) and (E) components is more preferable when the (E) component is blended. The (A) component is 20 to 35% by weight, the (B) component is 75 to 60% by weight, ( E) Component ranges from 5 to 15% by weight.

  In the photosensitive resin composition for a black resist of the present invention, it is preferable to adjust the viscosity by using a solvent in addition to the components (A) to (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 black resist resin composition of the present invention may contain additives such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, and an antifoaming agent as necessary. it can. 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 silicon-based, fluorine-based, and acrylic-based compounds.

  The resin composition for black resist of the present invention contains the above components (A) to (D) or these and a solvent as main components. The total amount of the components (A) to (D) in the solid component excluding the solvent may be 70% by weight or more, preferably 80% by weight, more preferably 90% by weight or more. The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 10 to 30% by weight.

  The color filter light-shielding film of the present invention is formed by a photolithography method using the photosensitive resin composition for black resist of the present invention. As the manufacturing process, first, the photosensitive resin composition is applied to the substrate surface as a solution, and then the solvent is dried (prebaked), and then a photomask is applied on the coating thus obtained, Examples include a method in which an exposed portion is cured by irradiating ultraviolet rays, a pattern is formed by performing development in which an unexposed portion is eluted with an alkaline aqueous solution, and post-baking is performed as post-drying. Here, as a substrate on which the photosensitive resin composition solution is applied, a transparent electrode such as ITO or gold is vapor-deposited or patterned on glass or a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.). Etc. are used.

  As a method for applying the solution of the photosensitive resin composition to the substrate, any method such as a method using a roller coater machine, a land coater machine or a spinner machine in addition to a known solution dipping method or spray method may be adopted. Can do. 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 exposure machine, and only the resist corresponding to the pattern is exposed by exposing through a photomask. The exposure machine and the exposure irradiation conditions are appropriately selected, and light exposure is performed using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a deep ultraviolet lamp, and the resin composition for black resist 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 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 good to develop at a temperature of 23 to 27 ° C. using a weakly alkaline aqueous solution containing 0.03 to 1% by weight 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 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 black resist resin composition of the present invention is suitable for forming a fine pattern by an operation such as exposure and alkali development. A light-shielding film having excellent light-shielding properties, adhesion, electrical insulation, heat resistance, and chemical resistance can be obtained.

Embodiments of the present invention will be specifically described below based on examples and comparative examples.

Synthesis example 1
In a 1 L four-necked flask, 20 g of pentaerythritol tetra (mercaptoacetate) (mercapto group 0.19 mol), 212 g of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (carbon-carbon double bond 2. 12 mol), 58 g of propylene glycol monomethyl ether acetate, 0.1 g of hydroquinone and 0.01 g of benzyldimethylamine were added and reacted at 60 ° C. for 12 hours to obtain a dendritic polymer A. About the obtained dendritic polymer A, disappearance of mercapto groups was confirmed by an iodometry method. The obtained dendritic polymer A had a weight average molecular weight Mw of 10,000.
Weight average molecular weight Mw is gel filtration chromatography (HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 ( 1) (made by Tosoh Co., Ltd.), temperature: 40 ° C., speed: 0.6 ml / min), and converted by standard polystyrene (PS-oligomer kit, produced by Tosoh Co., Ltd.).

The abbreviations of the compounds used in Examples and Comparative Examples are shown below.
(A component)
(A) -1: Dendritic polymer A solution obtained in Synthesis Example 1 (E component)
(A) -2: Trimethylolpropane triacrylate (Sartomer Japan KK, trade name SR351S)
(A) -3: Urethane acrylate oligomer (average acrylic functional group number 15, Mw: 5000) (manufactured by Negami Kogyo Co., Ltd., trade name UN-3320HS)

(B component)
(B) -1: Propylene glycol monomethyl ether acetate solution of acid anhydride polycondensate of epoxy acrylate having a fluorene skeleton (resin solid content concentration = 56.1% by weight, trade name V259ME manufactured by Nippon Steel Chemical Co., Ltd.)
(Alkali-soluble resin)
(B) -2: Mw 9000, acid value 80 N-phenylmaleimide / acrylic acid / styrene copolymer propylene glycol monomethyl ether acetate solution (resin solid content concentration = 35.5 wt%), (N-phenylmaleimide: acrylic acid) : Styrene = 19:22:59 mol%)
In addition, (b) -2 component is added in order to express a wrinkle suppression effect, and is alkali-soluble resin which does not have a photopolymerizable unsaturated bond.

(C component)
(C): Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (product name Irgacure, manufactured by BASF Japan Ltd.) OXE02)

(D component)
(D) Propylene glycol monomethyl ether acetate dispersion having a carbon black concentration of 25.0% by weight and a polymer dispersant concentration of 4.75% by weight (solid content 29.75% by weight)

(solvent)
(e) -1: Propylene glycol monomethyl ether acetate
(e) -2: Cyclohexanone (surfactant)
(f): Megafuck F475 (manufactured by DIC Corporation)
(Coupling agent)
(g): S-510 (manufactured by Chisso Corporation)

Examples 1-5, Comparative Examples 1-5
The said component was mix | blended in the ratio of Table 1, and the photosensitive resin composition for black resists which concerns on Examples 1-5 and Comparative Examples 1-5 was prepared. In Table 1, the upper numbers in (a) -1, (b) -1, (b) -2 and (d) indicate the amount (g) as a solution, and the numbers in () at the lower level are (a ) -1, (b) -1, and (b) -2 indicate the amount (g) of the solid component excluding the solvent, and (d) indicates the amount (g) of the light-shielding agent in the solution. The blending ratio is a ratio of the light shielding agent (D) component in the solid content of the photosensitive resin composition.
(A) -1, (a) -2, (a) -3 are photopolymerizable compounds, (b) -1 is an unsaturated group-containing resin, and (b) -2 is an alkali-soluble resin. (C) is a photopolymerization initiator, (d) is a light-shielding dispersed pigment, (e) -1 and (e) -2 are solvents, and (f) is a surfactant. , (G) is a silane coupling agent.

  Each component was uniformly mixed with the compounding ratio described in Table 1, and each photosensitive resin composition for black resist which concerns on Examples 1-5 and Comparative Examples 1-5 was obtained.

The black resist photosensitive resin composition obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 2.0 μm, and 90 Pre-baked for 1 minute at 0C. Thereafter, the exposure gap was adjusted to 80 μm, a negative photomask of line / space = 20 μm / 80 μm was put on the dried coating film, and an 80 mj / cm ² I-line illuminance of 30 mW / cm ^{2 with} an ultrahigh pressure mercury lamp. Ultraviolet rays were irradiated to carry out a photocuring reaction on the photosensitive part. Next, this exposed coated plate is +10 seconds and +20 from the development time (break time = BT) at which a pattern begins to appear at 25 ° C. in a 0.05% potassium hydroxide aqueous solution at a shower developing pressure of 1 kgf / cm ^2. After development for 2 seconds, spray washing with 5 kgf / cm ² pressure is performed to remove the unexposed part of the coating film to form a pixel pattern on the glass substrate, and then heat post at 230 ° C. for 30 minutes using a hot air dryer. The line width (μm) with respect to the mask width of the 20 μm line after baking, the pattern linearity, and the surface roughness Ra of the coating film were evaluated. The results are shown in Table 2. The evaluation method is as follows.

-Pattern line width The pattern line width with a mask width of 20 μm was measured using a length measuring microscope (trade name: XD-20, manufactured by Nikon Corporation).
・ Pattern linearity: A 20μm 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.
・ Pattern cross-sectional shape Cross-sectional shape of 20μm mask pattern before and after post-baking is observed with a scanning electron microscope (SEM), and the trapezoidal shape before post-baking is maintained after post-baking. When the shape of the trapezoid was changed to a semi-circular shape (kamaboko type), it was evaluated as x.
・ Surface roughness
Surface roughness (Ra) was measured using P-15 made by KLA-Tencor. The surface roughness (Ra) of the coating film after post-baking was evaluated as ○ when the surface roughness was less than 150 mm and x (defect) when the surface roughness was 150 mm or more.

  In Table 2, the left column of each example and comparative example is the result of the example of the development time BT + 10 seconds, and the right column is the result of BT + 20 seconds.

Claims (7)

The following (A) to (D) ingredients,
(A) a dendritic polymer having two or more ethylenic polymerizable groups at its ends;
(B) Unsaturated group content obtained by further reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and (meth) acrylic acid with a polybasic carboxylic acid or its anhydride Compound,
(C) a photopolymerization initiator, and (D) one or more light-shielding components selected from black organic pigments, mixed-color organic pigments and light-shielding materials,
A photosensitive resin composition for a black resist, comprising: (A) A component is shown by following General formula (2) in a part of carbon-carbon double bond in the (meth) acrylate group of the polyfunctional (meth) acrylate compound shown by following General formula (1). The photosensitive resin composition for a black resist according to claim 1, which is a dendritic polymer obtained by adding a polyvalent mercapto compound.

(Wherein R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ² represents an ester bond in which n hydroxyl groups out of m hydroxyl groups of polyhydric alcohol R ³ (OH) _m are represented by the formula: And m and n independently represent an integer of 2 to 20, where m ≧ n.)

(In the formula, R ⁴ is a single bond or a 2 to 6-valent C 1-6 hydrocarbon group-containing group, p is 2 when R ⁴ is a single bond, and R ⁴ is 2-6. When it is a valent group, it represents an integer of 2 to 6.)   The addition ratio of the mercapto group of the polyvalent mercapto compound represented by the general formula (2) to the carbon-carbon double bond of the polyfunctional (meth) acrylate compound represented by the general formula (1) is a mercapto group / two. The photosensitive resin composition for a black resist according to claim 2, wherein the molar ratio of the heavy bonds is 1/100 to 1/3. The black resist according to any one of claims 1 to 3, wherein the epoxy compound having two glycidyl ether groups derived from bisphenols in component (B) is an epoxy compound represented by the following general formula (3): Photosensitive resin composition.

(In the formula, R ₁₁ and R ₁₂ are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is —CO—, —SO ₂ —, —C (CF ₃ ) _{2. -, - Si (CH 3)} 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, shows a 9,9-fluorenyl group or a single bond represented by the following formula (4), n is an integer of 0 to 10)

  (D) A component is carbon black, The photosensitive resin composition for black resists in any one of Claims 1-4.   The photosensitive material for black resist according to any one of claims 1 to 5, wherein the light-shielding component (D) is blended in a proportion of 30 to 50% by weight with respect to the solid component in the photosensitive resin composition for black resist. Resin composition.   A color filter light-shielding film formed from the photosensitive resin composition for a black resist according to claim 1.