JP2009075446A - Resin black matrix, light shielding photosensitive resin composition and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin black matrix excellent in light blocking effect and having such a sufficiently high volume resistivity and a sufficiently low relative dielectric constant as not to cause problems such as a short circuit and malfunction even when formed on a TFT element substrate. <P>SOLUTION: The resin black matrix has an optical density of ≥3, a volume resistivity of ≥1×10<SP>13</SP>Ω cm and a relative dielectric constant at 1 kHz of ≤6. The resin black matrix preferably has a crossing angle θ to a substrate of 40-90°. A light shielding photosensitive resin composition for forming the resin black matrix is also provided which contains an alkali-soluble resin, a photopolymerization initiator, an ethylenically unsaturated compound and a light shielding pigment, wherein a content of the light shielding pigment is 30-50 wt.% based on a total solid content and a carbon black is contained as the light shielding pigment in an amount of 2-20 wt.% based on the total solid content. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a resin black matrix and a light-shielding photosensitive resin composition for producing the resin black matrix, and particularly a resin suitable for an active matrix liquid crystal display element substrate using a switching element composed of a thin film transistor (TFT). The present invention relates to a black matrix and a light-shielding photosensitive resin composition for producing the black matrix.
The present invention also relates to a liquid crystal display device having such a resin black matrix.

  The resin black matrix for liquid crystal display elements is used to prevent light leakage from the drive electrodes in the liquid crystal display element. Generally, it is a stripe-shaped or lattice-shaped light-shielding material pattern formed on a transparent substrate such as glass or plastic sheet that is paired with the TFT element substrate using a photolithography method.

  Recently, in order to cope with higher definition and higher brightness of color liquid crystal displays, in active matrix liquid crystal displays, a color filter on array method (COA method) in which a color filter is provided on the TFT element substrate side, A black matrix on array method (BOA method) in which only the black matrix is provided on the TFT element substrate side has been proposed. According to this method, compared with the case where a black matrix is formed on the color filter side, it is not necessary to take an alignment margin with the active element side, so that the aperture ratio can be increased. Can be planned.

  In order to cope with this, a resin black matrix provided with a volume resistivity of a certain level or more so as not to cause a short circuit of an electric circuit even when directly mounted on a TFT element is disclosed in JP-A-10-114873 and JP-A-10-114873. Japanese Patent Laid-Open No. 2002-311232, Japanese Patent Laid-Open No. 2005-215150, and the like. However, simply increasing the volume resistivity is not sufficient to stabilize the operation of the TFT, and it is necessary to lower the relative dielectric constant below a certain level.

  In order to give the resin black matrix a certain volume resistivity, it is known that the ratio of carbon black used as a light-shielding pigment of the resin black matrix is suppressed, and other pigments are used in combination. This alone reduces the optical density of the resin black matrix and impairs the originally required light shielding function. It is also difficult to lower the dielectric constant.

  In the resin black matrix, the following measures are conventionally known as methods for maintaining a high volume resistivity value and a low relative dielectric constant in combination with an optical density of a certain level or more. The current situation is that no results have been obtained.

-The carbon black concentration in the light-shielding pigment is kept low in order to keep the light-shielding pigment concentration at a certain level or more and to ensure a high volume resistance value and a low relative dielectric constant.
・ By covering the carbon black with a polyfunctional epoxy resin or applying a special oxidation treatment to the surface, the volume resistivity is secured while the carbon black concentration is set high, and the carbon blacks Use a dispersing agent and a dispersing resin that make the two close to each other.
-Keep the relative dielectric constant low by using a porous carbon black or applying a material with a low relative dielectric constant to components other than the light shielding pigment.

In the resin black matrix, in order to achieve a desired optical density using only organic pigments other than carbon black as the light-shielding pigment, the content needs to be very high. In the case of a high-definition display, if the light-shielding material that does not have developability itself is excessively mixed, these light-shielding materials remain on the substrate as a residue, etc. Causes the sharpness of the edge shape of the necessary pattern to be significantly reduced.
JP-A-10-114873 JP 2002-311232 A JP-A-2005-215150

  The present invention has been made in view of the above-described conventional circumstances, has an excellent light shielding property, and has a sufficiently high volume that does not cause problems such as a short circuit and malfunction even when formed on a TFT element substrate. An object is to provide a resin black matrix exhibiting a resistivity and a sufficiently low relative dielectric constant.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a resin black matrix shown below, and have completed the present invention.

[1] A resin black matrix having an optical density of 3 or more, a volume resistivity of 1 × 10 ¹³ Ω · cm or more, and a relative dielectric constant at 1 KHz of 6 or less.

[2] In the resin black matrix formed on the substrate, the optical density is 3 or more, the volume resistivity is 1 × 10 ¹³ Ω · cm or more, the relative dielectric constant at 1 KHz is 6 or less, and A resin black matrix characterized in that a crossing angle θ between a side surface of the resin black matrix and a plate surface of the substrate in a cross section perpendicular to the plate surface of the substrate is 40 ° to 90 °.

[3] An alkali-soluble resin, a photopolymerization initiator, an ethylenically unsaturated compound, and a light-shielding pigment, and the content of the light-shielding pigment is 30% by weight to 50% by weight with respect to the total solid content, and light shielding A light-shielding photosensitive resin composition for forming a resin black matrix according to [1] or [2], wherein carbon black is contained in an amount of 2% to 20% by weight based on the total solid content as a pigment for coatings .

[4] A liquid crystal display device having the resin black matrix according to [1] or [2].

According to the present invention, even when formed on a TFT element substrate, it has sufficient light shielding properties, a volume resistivity of 1 × 10 ¹³ Ωcm or more and a relative dielectric constant of 6 or less at 1 KHz, etc., even when formed on a TFT element substrate. Thus, a resin black matrix having a sufficiently high volume resistivity and a sufficiently low relative dielectric constant so as not to cause the above problem is provided.
The liquid crystal display device having the resin black matrix of the present invention is free from problems such as TFT failure and liquid crystal drive disturbance, and is excellent in reliability.

  Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. These contents are not specified.

In the present invention, “(meth) acrylic acid” means that both acrylic acid and methacrylic acid are included, and (meth) acrylic, (meth) acrylate, (meth) acryloyl groups, and the like have the same meaning. The term “(co) polymer” means that both a single polymer (homopolymer) and a copolymer (copolymer) are included, and “acid (anhydride)”, “(anhydrous)… acid "Is meant to include both acids and anhydrides. In the present invention, “acrylic resin” means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic ester having a carboxyl group.
In the present invention, the term “monomer” has a meaning corresponding to a so-called polymer substance, and includes a dimer, a trimer, an oligomer and the like in addition to a monomer (monomer) in a narrow sense.

[Resin black matrix]
The resin black matrix of the present invention is characterized in that the optical density is 3 or more, the volume resistivity is 1 × 10 ¹³ Ω · cm or more, and the relative dielectric constant at 1 KHz is 6 or less, preferably The crossing angle θ (hereinafter referred to as “substrate crossing angle θ”) between the side surface of the resin black matrix and the plate surface of the substrate in a cross section perpendicular to the plate surface of the substrate on which it is formed is 40 ° to 90 °. It is characterized by that.

<Optical density>
The optical density of the resin black matrix of the present invention is 3 or more, particularly preferably more than 3, more preferably 3.2 or more, and particularly preferably 3.5 or more. When the optical density of the resin black matrix is less than 3, the light transmitted through the resin black matrix adversely affects contrast and chromaticity.
The higher the optical density of the resin black matrix, the better. The upper limit is not particularly limited, but it is usually 6 or less.
The optical density of the resin black matrix is measured by the method shown in the Examples section described later.

<Volume resistivity>
The volume resistivity of the resin black matrix of the present invention is 1 × 10 ¹³ Ω · cm or more, preferably 1 × 10 ¹⁴ Ω · cm. When the volume resistivity of the resin black matrix is less than 1 × 10 ¹³ Ω · cm, the TFT element is easily short-circuited.
The volume resistivity of the resin black matrix is preferably as high as possible, and the upper limit thereof is not particularly limited, but is usually 1 × 10 ¹⁶ Ω · cm or less.
The volume resistivity of the resin black matrix is measured by the method shown in the Examples section described later.

<Relative permittivity>
The relative dielectric constant of the resin black matrix of the present invention is 6 or less at 1 KHz, preferably 5 or less. If the relative dielectric constant of the resin black matrix is larger than 6, it is difficult to accurately transmit the switching of the TFT element, and the liquid crystal driving may be disturbed.
The relative dielectric constant of the resin black matrix is preferably as small as possible, and the lower limit thereof is not particularly limited, but is usually 2.0 or more at 1 KHz.
The relative dielectric constant of the resin black matrix is measured by the method shown in the Examples section described later.

<Substrate crossing angle θ>
The substrate crossing angle θ of the resin black matrix of the present invention is preferably 40 ° to 90 °, more preferably 50 ° to 90 °, and particularly preferably 60 ° to 90 °. If the substrate crossing angle θ is smaller than this, it is disadvantageous for the enlargement of the aperture ratio, which is the purpose of COA and BOA, and if it is larger than this, the risk of short circuit increases.
As shown in FIG. 1, the substrate crossing angle θ refers to the plate surface 1 </ b> A of the substrate 1 and the resin black matrix in a cross section perpendicular to the plate surface 1 </ b> A of the substrate 1 of the resin black matrix 2 formed on the substrate 1. The angle θ formed by the side surface 2A of the two.

The method for forming the resin black matrix of the present invention is not particularly limited, but preferably contains an alkali-soluble resin, a photopolymerization initiator, an ethylenically unsaturated compound, and a light-shielding pigment. The light-shielding photosensitive resin composition of the present invention having a content of 30% to 50% by weight based on the total solid content and 2% to 20% by weight of carbon black as a light-shielding pigment based on the total solid content It is formed by.
Here, “total solid content” indicates the total of all components other than the solvent contained in the light-shielding photosensitive resin composition of the present invention.

[Light-shielding photosensitive resin composition]
The light-shielding photosensitive resin composition of the present invention is a light-shielding photosensitive resin composition for forming the resin black matrix of the present invention, comprising an alkali-soluble resin, a photopolymerization initiator, an ethylenically unsaturated compound, and Contains light-shielding pigment.
Hereinafter, each component which comprises the photosensitive resin composition of this invention is demonstrated.

[1] Alkali-soluble resin The alkali-soluble resin used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group. For example, an epoxy acrylate resin, a novolac resin, a polyvinylphenol resin, an acrylic resin, Examples include carboxyl group-containing epoxy resins and carboxyl group-containing urethane resins. Among these, epoxy acrylate resins, novolac resins, and acrylic resins are preferable, and resins having an aromatic ring structure are particularly preferable. This is particularly preferable in terms of providing a dielectric constant.

[1-1] Epoxy Acrylate Resin For example, the above-mentioned epoxy acrylate resin is obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin. Furthermore, it is obtained by a method of imparting alkali solubility by reacting with a polybasic acid anhydride. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As the raw material epoxy resin, (o, m, p-) cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy Resin, naphthalene novolac type epoxy resin, epoxy resin which is a reaction product of polyaddition reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin, epoxy resin represented by the following formula (1), etc. are preferably used (See Japanese Patent No. 2878486).

  Further, the phenolic epoxy resin described above does not require that all of the phenolic hydroxyl groups are substituted with epoxy groups, and some hydroxyl groups may remain, and it is preferable to leave some hydroxyl groups as in the present invention. In photosensitive resin compositions with high pigment content and high light-shielding properties, it is easy to reduce the difference in the polymerization rate between the surface and the bottom during exposure, and avoid the bottoming out and reverse taper shape during development. In some cases, it is possible to obtain an advantageous effect for shape formation.

The molecular weight of the epoxy resin is usually in the range of 200 to 200,000, preferably 300 to 100,000 as a weight average molecular weight in terms of polystyrene (hereinafter referred to as “MW”) as measured by gel permeation chromatography (GPC). When the MW is less than the above range, there are many cases where a problem is caused in the film-forming property. Conversely, in the case of a resin exceeding the above range, gelation easily occurs during the addition reaction of α, β-unsaturated monocarboxylic acid, and the production is difficult. There is a risk of becoming.
An epoxy resin may be used individually by 1 type, and may mix and use 2 or more types.

Examples of the α, β-unsaturated monocarboxylic acid to be added to the epoxy resin include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, particularly acrylic acid. Is preferable because of its high reactivity. In addition, α, β-unsaturated monocarboxylic acid esters having a carboxyl group in the ester moiety include acrylic acid-2-succinoyloxyethyl, acrylic acid-2-maleinoyloxyethyl, and acrylic acid-2-phthaloyloxy. Ethyl, acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexa Hydrophthaloyloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like can be mentioned. Preferred are acrylic acid-2-malenoyloxyethyl and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2. -Maleoyloxyethyl is preferred.
These may be used alone or in combination of two or more.

A known method can be used for the addition reaction of α, β-unsaturated monocarboxylic acid or an ester thereof with an epoxy resin, for example, the reaction can be performed at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. .
Examples of the esterification catalyst used in the reaction include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride. More than seeds can be used.

  The amount of α, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. Equivalent range. If the amount of α, β-unsaturated monocarboxylic acid or ester thereof used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with the polybasic acid anhydride becomes insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β-unsaturated monocarboxylic acid or ester thereof remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  In the present invention, even if the production process does not go through an epoxy resin, if the final resin structure is the same, it is defined as a category of the epoxy acrylate resin. Examples thereof include a method of reacting, for example, a novolac resin and an unsaturated group-containing epoxy compound.

In this case, the unsaturated group-containing epoxy compound includes glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, glycidyloxy (poly) alkylene glycol (meth) acrylate, and methyl glycidyl (meth) acrylate. , (3,4-epoxycyclohexyl) vinyl and the like.
Of these, glycidyl methacrylate and (3,4-epoxycyclohexyl) methyl (meth) acrylate are particularly preferable.

  A known method can be used for the reaction of the novolak resin and the unsaturated group-containing epoxy compound. For example, tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, and benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc. in an organic solvent. By reacting at a reaction temperature of 50 to 150 ° C. for several to several tens of hours, an unsaturated group-containing epoxy compound can be added to the novolak resin.

  The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture (the total of the novolak resin and the unsaturated group-containing epoxy compound). In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, dibutylhydroxytoluene, phenothiazine). The amount used is preferably 0.01 to 10% by weight, particularly preferably 0.03 to 5% by weight, based on the reaction raw material mixture.

  In addition, it is not necessary to add an unsaturated group-containing epoxy compound to the novolak hydroxyl group, and the addition of the hydroxyl group to a certain extent has a higher pigment content and a light-shielding property as in the present invention. In the composition, it is easy to reduce the difference in polymerization rate between the surface and the bottom during exposure, and there are cases where it is advantageous for forming a shape in order to avoid the bottom of the surface during development and the reverse taper shape.

As a polybasic acid anhydride to be further added to an epoxy resin to which an α, β-unsaturated carboxylic acid or an ester thereof is added, or a resin such as the above obtained by reacting an epoxy compound containing an unsaturated group with a novolak resin, anhydrous Maleic acid, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, methyl hexahydrophthalic anhydride , Endmethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc., preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, anhydrous Tetrahydrophthalic acid, hexahydrophthalic anhydride, none Water pyromellitic acid, trimellitic anhydride and biphenyltetracarboxylic dianhydride are particularly preferred, and tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride are particularly preferred.
These may be used alone or in combination of two or more.

A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be obtained by continuing the reaction under the same conditions as in the addition reaction of α, β-unsaturated carboxylic acid or ester thereof.
The addition amount of the polybasic acid anhydride is preferably an amount such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mg-KOH / g, and more preferably 20 to 140 mg-KOH / g. It is particularly preferred. When the resin acid value is less than or equal to the above range, the alkali developability is poor, and when it exceeds the above range, a tendency to be inferior in curing performance is recognized.

[1-2] Novolak-based resin The novolak-based resin used in the present invention includes, for example, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4,4′-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, At least one of phenols such as 1,2,4-benzenetriol, benzoic acid, 4-hydroxyphenylacetic acid, salicylic acid, phloroglucinol and the like is reacted with an acid catalyst, for example, formaldehyde, paraformaldehyde, acetaldehyde, paraalkaline. Hydrate, propionaldehyde, benzaldehyde, salicylaldehyde, aldehyde furfural compound, or ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, a resin having engaged at least one and polycondensation of.

  The reaction between phenols and aldehydes is carried out without solvent or in a solvent. A resole resin that has been polycondensed in the same manner except that an alkali catalyst is used in place of the acid catalyst in the polycondensation of the novolak resin can also be used. Furthermore, the phenols may be substituted as necessary, and for example, aromatic compounds other than phenols may be mixed and polycondensed. Further, the production method is not limited to polycondensation as long as the finished skeletons are the same.

  In order to enhance alkali solubility in the novolak resin, a carboxylic acid may be added to a part of the phenolic hydroxyl group. In this case, examples of the added carboxylic acid include oxalic acid, maleic acid, and itaconic acid. Phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4 -1 type (s) or 2 or more types, such as methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, and those anhydrides, are mentioned.

  In addition to this, it is possible to substitute a part of the phenol group for the novolac resin to have various functions. For example, glycidyl methacrylate can be added to the side chain as an example. For example, giving a double bond.

  The MW of the novolac resin is usually 1,000 to 20,000, preferably 1,000 to 10,000, and more preferably 1,000 to 8,000. When the MW is less than 1,000, the sensitivity is lowered, and when it exceeds 10,000, the developability is lowered.

  The novolak resin is disadvantageous in terms of sensitivity because it traps radicals, but only on the surface, which tends to be found in a photosensitive resin composition having a high pigment content and high light shielding properties as in the present invention. It is effective in avoiding a situation where the base portion is hardened and the bottom portion becomes a hollow shape, or the shape of the taper is reverse because the heat does not easily flow.

[1-3] Acrylic Resin The acrylic resin needs to contain a monomer having a carboxyl group or a phenolic hydroxyl group in the side chain or main chain in order to ensure alkali solubility. Among them, an acrylic resin having a carboxyl group that can be developed with a highly alkaline solution, such as an acrylic acid (co) polymer, a styrene-maleic anhydride resin, an acid anhydride-modified resin of novolak epoxy acrylate, etc. It is. Among them, particularly preferred are (co) polymers containing (meth) acrylic acid or (co) polymers containing (meth) acrylic acid ester having a carboxyl group. A (co) polymer containing a monomer having is more preferable. These acrylic resins are excellent in developability, transparency, and the like, and have advantages in that copolymers having different performances can be obtained in combination with various monomers, and the production method can be easily controlled.

  The acrylic resin according to the present invention is, for example, a (co) polymer mainly composed of the following monomers.

That is, examples of the monomer include a compound obtained by adding an acid (anhydride) to hydroxyalkyl (meth) acrylate.
Examples of the hydroxyalkyl (meth) acrylate include (meth) acrylic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- (meth) acryloyloxyethyl) ester, and adipic acid (2-acrylic acid). Leuoxyethyl) ester, phthalic acid (2- (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ) Ester, succinic acid (2- (meth) acryloyloxypropyl) ester, adipic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxypropyl) ester, Phthalic acid (2- (meth) acryloyloxypropyl) ester, maleic acid ( -(Meth) acryloyloxypropyl) ester, succinic acid (2- (meth) acryloyloxybutyl) ester, adipic acid (2- (meth) acryloyloxybutyl) ester, hexahydrophthalic acid (2- (meta ) Acryloyloxybutyl) ester, phthalic acid (2- (meth) acryloyloxybutyl) ester, maleic acid (2- (meth) acryloyloxybutyl) ester, etc., and the acid (anhydride) (Anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid and the like.
Any of these hydroxyalkyl (meth) acrylates and acids (anhydrides) may be used alone or in combination of two or more.

  Monomers that can be copolymerized with the above monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, cinnamic acid, maleic acid, fumaric acid, maleic anhydride, itacone. Unsaturated group-containing carboxylic acids such as acids, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl Esters of (meth) acrylic acid such as (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, and (meth) acrylic acid Caprolactone, β-propiolac , Γ-butyrolactone, δ-valerolactone and other lactones, acrylonitrile, methacrylonitrile and other acrylonitriles, (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloyl Acrylamides such as morpholine, N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminoethylacrylamide, vinyl acids such as vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate and vinyl pivalate Etc. These may be used alone or in combination of two or more.

  In particular, as a preferred acrylic resin for improving the strength of the coating film on the substrate, at least one of the following monomers (a) and at least one of the following monomers (b) are used in combination. A polymerized acrylic resin is exemplified.

Monomer (a): styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl (meth) acrylsulfamide, etc. Monomer (b): (meth) acrylic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2- (meth) acryloyloxyethyl) ester, phthalic acid (2- (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- Has a carboxyl group such as (meth) acryloyloxyethyl) ester That (meth) acrylic acid ester

  In the production of the acrylic resin, the monomer (a) is usually from 10 to 98 mol%, preferably from 20 to 80 mol%, more preferably from 30 to 70 mol%, and the monomer (b) is usually from 2 to 2 mol%. It is used in a proportion of 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%.

  The acrylic resin preferably includes an acrylic resin having an ethylenic double bond in the side chain. By using such an acrylic resin, the photocurability of the photosensitive resin composition of the present invention is improved, so that the adhesion to the substrate can be further improved.

As a method for introducing an ethylenic double bond into the side chain of an acrylic resin, for example, the method described in Japanese Patent Publication No. 50-34443, Japanese Patent Publication No. 50-34444, etc.,
(1) A method of reacting a carboxyl group of an acrylic resin with a compound having both a glycidyl group, an epoxycyclohexyl group and a (meth) acryloyl group
(2) A method of reacting acrylic acid chloride or the like with the hydroxyl group of the acrylic resin may be mentioned.

  Specifically, an acrylic resin having a carboxyl group or a hydroxyl group is added to glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, (meth) acrylic acid chloride, (meth) allyl chloride, etc., by reacting one or more compounds, it has an ethylenic double bond group in the side chain. An acrylic resin can be obtained. Especially, what made the alicyclic epoxy compound like (3,4-epoxycyclohexyl) methyl (meth) acrylate react with acrylic resin which has a carboxyl group and a hydroxyl group is preferable.

  As described above, the method of introducing an ethylenic double bond into an acrylic resin having a carboxyl group or a hydroxyl group in advance is usually 2 to 50 with respect to the carboxyl group or hydroxyl group of the acrylic resin having a carboxyl group or a hydroxyl group. A method of bonding a compound having an ethylenic double bond of 5 mol%, preferably 5 to 40 mol% is preferable. The carboxyl group content is preferably in the range of 5 to 200 mg-KOH / g as the acid value. When the acid value is less than 5 mg-KOH / g, it becomes insoluble in an alkaline developer, and when it exceeds 200 mg-KOH / g, the development sensitivity may be lowered.

  In addition, when the acrylic resin used for this invention contains a phenolic hydroxyl group, the effect close | similar to said novolak resin is acquired. In particular, vinyl monomers having an aromatic hydroxyl group in the side chain, specifically o, m, p-hydroxyphenylmethacrylamide, o, m, p-hydroxystyrene, o, m, p-hydroxyphenylmaleimide, etc. It is effective to use an acrylic resin used as a part of the copolymer component. Although the resin containing such components is disadvantageous in terms of sensitivity as a photosensitive resin composition, in the light-sensitive photosensitive resin composition as in the present invention, only the surface is cured and the substrate is developed by development. An effect of preventing the photosensitive resin composition in a portion close to that from being easily in a hollow shape can be obtained.

  The MW of the acrylic resin is preferably in the range of 1,000 to 100,000. When the MW is less than 1,000, it is difficult to obtain a uniform coating film, and when it exceeds 100,000, the developability tends to decrease.

[1-4] Polyvinylphenol resin Examples of the polyvinylphenol resin include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, o- Hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, 2- (p- (Hydroxyphenyl) Hydroxystyrenes such as propylene (note that these may have a halogen atom such as chlorine, bromine, iodine or fluorine, or an alkyl group having 1 to 4 carbon atoms as a substituent on the benzene ring. 1) or 2 or more And styrenes such as styrene and α-methylstyrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, tricyclo [5.2. 1.0] Start radical polymerization of one or more comonomers such as acrylic acid derivatives such as decan-8-yl (meth) acrylate, glycidyl (meth) acrylate, and hydroxyphenyl (meth) acrylamide. And homopolymers or copolymers of hydroxystyrenes polymerized in the presence of an agent or a cationic polymerization initiator.

  In order to increase the alkali solubility in the polyvinyl phenol resin, carboxylic acid may be added to a part of the phenolic hydroxyl group. In this case, examples of the carboxylic acid to be added include oxalic acid, maleic acid, itacone. Acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, Examples include 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, and anhydrides thereof.

  The MW of the polyvinylphenol resin is usually 2,000 to 50,000, preferably 2,000 to 20,000. When the MW is less than 2,000, the sensitivity is lowered, and when it exceeds 20,000, the developability is lowered.

  The above-mentioned alkali-soluble resins may be used alone or in combination of two or more.

  In the present invention, as described above, as the alkali-soluble resin, use of a resin having an aromatic ring structure, in particular, a resin having a phenolic hydroxyl group reduces the difference in polymerization rate between the surface and the bottom during exposure. It is preferable for forming a resin black matrix having a good shape.

  The ratio of the alkali-soluble resin to the total solid content in the light-shielding photosensitive resin composition of the present invention is usually 10 to 70% by weight, preferably 15 to 50% by weight. If the proportion of the alkali-soluble resin is too much above this range, sufficient sensitivity cannot be ensured, and the necessary light-shielding property cannot be ensured. On the other hand, if it is too small, the preferred shape of the resin black matrix cannot be formed.

[2] Photopolymerization initiator The photopolymerization initiator according to the present invention is a compound capable of generating radicals that polymerize ethylenically unsaturated groups by ultraviolet rays or heat.

  Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.

  2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;

  Halomethylated oxadiazole derivatives;

  2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) ) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. An imidazole derivative of

  Benzoin, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;

  Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;

  Benzanthrone derivatives;

  Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;

  2,2, -dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p- Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- Acetophenone derivatives such as (p-butylphenyl) ketone;

  Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

  benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

  Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;

  Phenazine derivatives such as 9,10-dimethylbenzphenazine;

  Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny -1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-di-fluoro Feni-1-i , Di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl;

  2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as

  As the photopolymerization initiator, oxime derivatives (oxime compounds) are particularly effective in terms of sensitivity, and in the case of increasing the light shielding property or using an alkali-soluble resin containing a phenolic hydroxyl group, In particular, such oxime derivatives (oxime compounds) having excellent sensitivity are useful.

  Examples of the oxime compound include a compound containing a structural moiety represented by the following general formula (2), and preferably include an oxime ester compound represented by the following general formula (3).

(In Formula (2), R ² is a C1-C20 heteroaryl group, a C2-C12 alkanoyl group, a C1-C20 heteroarylalkanoyl group, carbon which may be respectively substituted. C3-C25 alkenoyl group, C3-C8 cycloalkanoyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 heteroaryloxyoxy A carbonylalkanoyl group, an aminocarbonyl group having 2 to 10 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a 7 to 20 carbon atom Represents a phenoxycarbonyl group.)

(In formula (3), R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, Phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, amino group having 0 to 20 carbon atoms, aminoalkyl group having 1 to 20 carbon atoms, carbon C2-C12 alkanoyl group, C3-C25 alkenoyl group, C3-C8 cycloalkanoyl group, C7-C20 benzoyl group, C1-C20 heteroaryloyl group, C2 -10 alkoxycarbonyl groups and C7-20 phenoxycarbonyl groups.
R ^1b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ^1a may form a ring together with R ^1b , and the linking group thereof may have an optionally substituted alkylene group having 1 to 10 carbon atoms, a polyethylene group (— (CH═CH) _r. -), A polyethynylene group (-(C≡C) _r- ) or a group formed by a combination thereof (where r is an integer of 0 to 3).
R ^2a is an optionally substituted heteroaryl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and an alkenoyl group having 3 to 25 carbon atoms. C3-C8 cycloalkanoyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 heteroaryloxyoxycarbonylalkanoyl group, C2-C2 A C10-20 aminocarbonyl group, a C7-20 benzoyl group, a C1-20 heteroaryloyl group, a C2-10 alkoxycarbonyl group, or a C7-20 phenoxycarbonyl group. )

R ² in the general formula (2) and R ^1a and R ^2a in the general formula (3) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and a carbon number. 3-8 cycloalkanoyl groups are mentioned.

In addition, R ^1b in the general formula (3) is preferably a carbazoyl group which may be substituted, a thioxanthonyl group which may be substituted, or a phenyl sulfide group which may be substituted.

  Specific examples of the oxime ester-based compound suitable for the present invention include the compounds exemplified below, but the oxime ester-based compound is not limited to these compounds.

  These oxime ester compounds are known per se, and are, for example, one of a series of compounds described in JP-A No. 2000-80068 and JP-A No. 2006-36750.

  The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.

  The ratio of the photopolymerization initiator in the light-shielding photosensitive resin composition of the present invention is usually 0.4 to 15% by weight, preferably 0.5 to 10% by weight, based on the total solid content. If the ratio of the photopolymerization initiator is too much within this range, the developing speed will be too slow, while if it is too low, sufficient sensitivity will not be obtained, and a preferable resin black matrix shape will not be formed.

[3] Ethylenically unsaturated compound The photopolymerization initiator is used together with an ethylenically unsaturated compound.
As used herein, an ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and a developer for exposed and non-exposed areas associated therewith. From the viewpoint that the difference in solubility can be expanded, the compound is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth) acryloyloxy group (meta ) Acrylate compounds are more preferred.
Furthermore, the use of a compound having three or more ethylenically unsaturated bonds in the molecule is preferable for electrical characteristics such as volume resistivity and relative dielectric constant.

  Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.

  Typically, compounds having two or more ethylenically unsaturated bonds include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, and hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

Specific examples of esters of an unsaturated carboxylic acid and a polyhydroxy compound include the following compounds.
Reaction product of unsaturated carboxylic acid and sugar alcohol; specifically, sugar alcohol includes ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.
Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol; sugar alcohol is the same as above. Specific examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
Reaction product of unsaturated carboxylic acid and alcohol amine; specific examples of alcohol amines include diethanolamine and triethanolamine.

Specific esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, etc.

  In addition, as esters of unsaturated carboxylic acid and polyhydroxy compound, unsaturated carboxylic acid and aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts These reactants can be mentioned. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc., and the unsaturated carboxylic acid as described above A reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate, tri (meth) acrylate, etc. of tris (2-hydroxyethyl) isocyanurate, Reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, for example, condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol , (Meth) acrylic acid, terephthalic acid and pentae Condensates of Suritoru include condensates of (meth) acrylic acid and adipic acid and butane diol and glycerol.

  As the (meth) acryloyloxy group-containing phosphates, those represented by the following general formulas (4), (5) and (6) are preferable.

（式（４），（５）及び（６）中、Ｒ^１０は水素原子又はメチル基を示し、ｐ及びｐ’は１〜２５の整数、ｑは１、２、又は３である。）

(In the formulas (4), (5) and (6), R ¹⁰ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is 1, 2 or 3.)

  Here, it is preferable that p and p ′ are 1 to 10, particularly 1 to 4, and specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (Meth) acryloyloxyethylene glycol phosphate and the like may be mentioned, and these may be used alone or as a mixture.

Examples of urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound include hydroxy (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylolethane tri (meth) acrylate. ) Acrylate compound, aliphatic polyisocyanate such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptanetri Cycloaliphatic polyisocyanates such as isocyanate, 4,4-diphenylmethane diisocyanate, tris Aromatic polyisocyanates such as isocyanate phenyl) thiophosphate, heterocyclic polyisocyanates such as isocyanurate, a reaction product of a polyisocyanate compounds and the like.
Examples of such products include trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

  Among these, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly A compound obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, or ethylene glycol As a compound having two or more hydroxyl groups in one molecule, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 18H-70B”, etc. manufactured by Asahi Kasei Corporation Biuret type, same A compound having three or more isocyanate groups in one molecule such as adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T” and “Duranate E-405-80T” is reacted. The compound obtained, or a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like, a compound having 4 or more, preferably 6 or more isocyanate groups in one molecule, such as Asahi Kasei Kogyo “Duranate ME20-100”, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. 1 or more hydroxyl groups and 2 in one molecule Above, can preferably be obtained by a compound having three or more (meth) acryloyloxy group, it is reacted.

  Examples of epoxy (meth) acrylates of (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound include (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, and (poly) Ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene Glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Aliphatic polyepoxy compounds, phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, etc. Aromatic polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, heterocyclic polyepoxy compounds such as triglycidyl tris (2-hydroxyethyl) isocyanurate, and reactants with polyepoxy compounds such as .

  Other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, ether bonds Thioether bond-containing compounds whose crosslinking rate has been improved by sulfurizing the ether bonds of the ethylenically unsaturated compound with phosphorous pentasulfide and changing to thioether bonds, and for example, Japanese Patent No. 3164407 and JP-A-9- The polyfunctional (meth) acrylate compound and silica sol having a particle diameter of 5 to 30 nm (for example, isopropanol-dispersed organosilica sol (“IPA-ST” manufactured by Nissan Chemical Co., Ltd.)), methyl ethyl ketone-dispersed organosilica sol (Nissan Chemical) "MEK-S" ”), Methyl isobutyl ketone-dispersed organosilica sol (“ MIBK-ST ”manufactured by Nissan Chemical Co., Ltd.), etc.] and the like, and the like, and the like, by using an isocyanate group or a mercapto group-containing silane coupling agent. Examples thereof include compounds in which the strength and heat resistance as a cured product are improved by reacting and bonding silica sol through a silane coupling agent.

  In the present invention, as the ethylenically unsaturated compound, ester (meth) acrylates or urethane (meth) acrylates are preferable, and among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. Those having 5 or more functional groups are particularly preferred.

  The above ethylenically unsaturated compounds may be used alone or in combination of two or more.

  The ratio of the ethylenically unsaturated compound in the light-shielding photosensitive resin composition of the present invention is usually 1 to 20% by weight, preferably 4 to 18% by weight, particularly preferably 5 to 15% by weight, based on the total solid content. It is. If the ratio of the ethylenically unsaturated compound is too much above this range, the bottom tends to have a shape due to the difference in polymerization rate between the surface and the bottom during exposure, while if it is too small, sufficient sensitivity cannot be obtained. In addition, electrical characteristics such as volume resistivity and relative dielectric constant are deteriorated.

[4] Light-shielding component (coloring material)
In the light-shielding photosensitive resin composition of the present invention, a single black color material or a black color material obtained by mixing red, green, blue and the like can be used. These black color materials can be appropriately selected from inorganic or organic pigments and dyes such as carbon black and titanium black, and can be used alone or in combination.

[4-1] Carbon black Examples of commercially available carbon black include the following brands.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.

Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, Sck, 350, S350, 250, 350

Manufactured by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACKPEARLS480, PEARLS480.

Made by Colombian Carbon: Raven11, Raven15, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040 and the like.

[4-2] Titanium black Titanium black is produced by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere and reducing it (Japanese Patent Laid-Open No. 49-5432), high-temperature hydrolysis of titanium tetrachloride. The method of reducing ultrafine titanium dioxide obtained in the above in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), and the method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-60). -65069, JP-A-61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide, and performing high-temperature reduction in the presence of ammonia (JP-A-61-201610). However, it is not limited to these.

  Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

[4-3] Organic pigments Organic pigments are not limited to black, but can be shaded by mixing blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, etc. Is preferable. The structure includes organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene.
Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  The average particle diameter of these light-shielding pigments is usually 1 μm, preferably 0.5 μm or less, for example, 0.01 to 0.4 μm. The smaller the particle size of the light-shielding pigment, the greater the light-shielding property.

[4-4] Pigment blending amount The ratio of the light-shielding pigment in the light-sensitive photosensitive resin composition of the present invention is 30% to 50% by weight, preferably 30% to 45% by weight, based on the total solid content. More preferably, it is 30 to 42% by weight. If there are too many light-shielding pigments within this range, the sharpness of the edge shape of a necessary pattern will be significantly reduced in the case of a high-definition display. On the other hand, if the amount is too small, sufficient light shielding properties as a resin black matrix cannot be secured.
Further, if the amount of the pigment is too small, the substrate crossing angle θ tends to be small. That is, as described above, the resin black matrix of the present invention can be suitably used for the COA or BOA system which can take a wide opening, but the substrate crossing angle θ is small, and the shape of the slanted shape is the opening. The substrate crossing angle θ is preferably 40 ° to 90 °. In order to secure the substrate crossing angle θ, it is not preferable to reduce the amount of the light-shielding pigment from the above range.

  Furthermore, the light-shielding photosensitive resin composition of the present invention is 2 to 20% by weight, preferably 2 to 10% by weight, of carbon black in the light-shielding pigment, based on the total solid content. Features. When the content of carbon black exceeds this range, the volume resistance value of the resin black matrix to be formed becomes small, and the relative dielectric constant further increases. On the other hand, if the amount is too small, sufficient light-shielding properties as a resin black matrix cannot be secured, and it is necessary to increase the content of organic pigments to compensate for this, and as a result, the proportion of the entire light-shielding pigment must be increased. Disadvantageous and disadvantageous.

  In the present invention, when increasing the carbon black content in the light-shielding photosensitive resin composition, it is preferable to use porous carbon black in order to lower the relative dielectric constant. In addition, in order to increase the volume resistance value while increasing the carbon black content, it is also one measure to use coated carbon black. The coated carbon black is described in JP-A-9-071733, JP-A-9-095625, and JP-A-9-124969. Regarding the coating method with the resin, the methods described therein can also be used.

[4-5] Pigment derivative A pigment derivative or the like may be used in combination with the light-shielding pigment used in the present invention in order to improve dispersibility and dispersion stability.
As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as quinophthalone are preferable, among which quinophthalone is preferable. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.

Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives.
These pigment derivatives can be used alone or in combination of two or more.

  When a pigment derivative is used, the amount used is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably, based on the light-shielding pigment. 0.1 to 5% by weight.

[5] Dispersant / dispersion aid The light-shielding photosensitive resin composition of the present invention is used in combination with a pigment dispersant and / or a dispersion aid in order to improve the dispersibility and dispersion stability of the light-shielding pigment. It is preferable to do. Among them, it is particularly preferable to use a polymer dispersant as the pigment dispersant because it is excellent in dispersion stability with time. Here, the dispersant is a polymer having a completely different structure from the pigment for ensuring the dispersion stability of the pigment, and the dispersion aid means a pigment derivative for enhancing the dispersibility of the pigment.

Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. And the like, and the like. Specific examples of these dispersants are trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbik (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by GENECA), Examples thereof include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.
These dispersants can be used singly or in combination of two or more.
Among these, urethane-based dispersants and polyethyleneimine-based dispersants are preferable for electrical characteristics such as volume resistivity and relative dielectric constant.

[5-1] Urethane-based dispersant As the urethane-based dispersant, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule, and active in the same molecule A dispersion resin obtained by reacting hydrogen with a compound having a tertiary amino group is preferred.

  Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

  Examples of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.

  Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. .

  Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.

  These may be used alone or in combination of two or more.

  The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
The tertiary amino group is not particularly limited, and examples of the tertiary amino group include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is a nitrogen-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. . Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.

  These may be used alone or in combination of two or more.

  The preferable blending ratio of the raw materials when producing the urethane-based dispersant is 10 to 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 200 parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, 0.2 to 25 parts by weight of a compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3 to 24 parts by weight.

  Production of such a urethane-based dispersant is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl One or more of aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

  In the production, a usual urethanization reaction catalyst is used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. 1 type, or 2 or more types, such as a secondary amine type | system | group, are mentioned.

  The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mg-KOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mg-KOH / g. The amine value is a value obtained by neutralizing and titrating a basic group with an acid and representing the acid value in mg of KOH. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.

  In addition, when an isocyanate group remains in the dispersion resin obtained by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability with time of the product becomes high.

  The MW of such a urethane-based dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor.

[5-2] Acrylic dispersant Examples of the acrylic dispersant include a graft polymer containing a nitrogen atom and an acrylic block copolymer. As the acrylic dispersant, a polymer obtained by polymerizing a monomer component having a specific compound described below as an essential component can also be used.

  In the graft polymer and acrylic block copolymer containing nitrogen atoms used in the present invention, the nitrogen atoms contained therein have an affinity for the pigment surface, and portions other than the nitrogen atoms have an affinity for the medium. By increasing it, it is estimated that it contributes to the improvement of dispersion stability as a whole.

The performance of a dispersant is its adsorption behavior on the solid surface. Regarding the relationship between the molecular architecture and the adsorption behavior, it is known that when the same unit is used, the adsorption behavior is excellent in the order of random copolymerization <graft copolymer <block copolymer. (For example, Jones and Richards, “Polymers at Surfaces and Interfaces” p281). Although the detailed mechanism is unknown, the following can be inferred.
That is, in the case of a normal random copolymer, it is highly likely that the monomer constituting the copolymer is stably arranged in the copolymer sterically and / or electrically during the copolymerization. . The portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, and therefore may be an obstacle when adsorbed on the pigment. On the other hand, in a resin whose molecular arrangement is controlled, such as a graft or block copolymer, a portion that prevents adsorption of the dispersant can be disposed at a position away from the adsorption portion of the pigment and the dispersant. That is, an optimum portion for adsorption can be arranged in the adsorption portion between the pigment and the dispersant, and a portion suitable for it can be arranged in the portion requiring solvent affinity. In particular, the dispersion of a coloring material containing a pigment having a small crystallite size is presumed that this molecular arrangement affects the good dispersibility.

[5-2-1] Graft copolymer containing a nitrogen atom A graft copolymer containing a nitrogen atom is preferred in that the light-shielding pigment used in the present invention can be dispersed extremely efficiently. The reason for this is not clear, but the part (molecule) that obstructs the adsorption of the pigment and the dispersant has a structure that can be positively excluded from the arrangement around the adsorption part to the pigment. It is assumed that there is.
Furthermore, the present dispersant is preferable for achieving a substrate crossing angle θ = 40 to 90 ° with respect to the substrate of the black matrix.

  As the graft copolymer containing a nitrogen atom, those having a repeating unit containing a nitrogen atom in the main chain are preferred. Especially, it is preferable to have a repeating unit represented by the following formula (I) and / or a repeating unit represented by the following formula (II).

(In the above formula (I), R ¹¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably. An ethylene group, A represents a hydrogen atom or any one of the following formulas (III) to (V), preferably formula (III).

(In the formula ^{(II), R 11,} A has the same meaning as ^{R 11,} A of formula (I).)

(In the above formula (III), W ¹ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, hexylene and the like is preferable. Represents an integer of 1 to 20, preferably an integer of 5 to 10.)

(In the above formula (IV), Y ¹ represents a divalent linking group, among which an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. preferably .W ² represents ethylene, propylene, a linear or branched alkylene group having 2 to 10 carbon atoms butylene, among which ethylene, an alkylene group having 2 to 3 carbon atoms such as propylene preferred .Y ² Represents a hydrogen atom or CO-R ¹² (R ¹² represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among them, those having 2 to 5 carbon atoms such as ethyl, propyl, butyl, pentyl, etc. An alkyl group is preferred.) T represents an integer of 1 to 20, preferably an integer of 5 to 10.)

(In the above formula (V), W ³ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups, and in particular, an alkyl group having 10 to 20 carbon atoms such as stearyl. C1-C20 hydroxyalkyl groups having 1-2 hydroxyl groups such as monohydroxystearyl are preferred.)

The content of the repeating unit represented by the formula (I) and / or (II) in the graft copolymer containing a nitrogen atom used in the present invention is preferably higher, usually 50 mol% or more, preferably It is 70 mol% or more. The repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) may both be present, and the content thereof is not particularly limited. It is preferable to contain a larger number of repeating units.
The total number of repeating units represented by the formula (I) and / or the formula (II) in one molecule is usually 1 to 100, preferably 10 to 70, more preferably 20 to 50.
Moreover, repeating units other than formula (I) and formula (II) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group.
The graft copolymer, the end -NH ₂ and ^-R 11 _-NH 2 ^{(R 11} is, ^{R 11} as defined in the formula (I)) that are preferred.

  In addition, if the graft copolymer containing this nitrogen atom is a graft copolymer, the main chain may be linear or branched.

  The amine value of the graft copolymer containing a nitrogen atom according to the present invention is usually 5 to 100 mg-KOH / g, preferably 10 to 70 mg-KOH / g, and more preferably 15 to 40 mg-KOH / g. g or less. If the amine value is too low, the dispersion stability may decrease and the viscosity may become unstable. Conversely, if the amine value is too high, the residue may increase or the electrical characteristics after the liquid crystal panel is formed may deteriorate.

  In addition, the MW of the graft copolymer containing a nitrogen atom is preferably 3000 to 100,000, particularly preferably 5000 to 50000. If the MW is less than 3000, the aggregation of the pigment cannot be prevented and the viscosity or gelation may occur. If it exceeds 100,000, the viscosity itself becomes high and the solubility in an organic solvent is insufficient. Therefore, it is not preferable.

As a method for synthesizing the graft copolymer containing a nitrogen atom, a known method can be adopted, and for example, a method described in JP-B-63-30057 can be used.
In the present invention, a commercially available graft copolymer having the same structure as described above can also be applied.

[5-2-2] Acrylic Block Copolymer An acrylic block copolymer is preferable in that it can disperse the light-shielding pigment used in the present invention very efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed on the pigment. As an acrylic block copolymer, an AB block comprising an A block having a quaternary ammonium base and / or amino group in a side chain and a B block having no quaternary ammonium base and / or amino group. Copolymers and / or B-A-B block copolymers are preferred.

  The A block constituting the block copolymer of the acrylic block copolymer has a quaternary ammonium base and / or an amino group.

The quaternary ammonium base is preferably —N ⁺ R ²¹ R ²² R ²³ .M ⁻ (wherein R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, or an optionally substituted cyclic or chain) Or two or more of R ²¹ , R ²² and R ²³ may be bonded to each other to form a cyclic structure, and M ⁻ represents a counter anion). It has the quaternary ammonium base represented. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R ²¹ R ²² R ²³ , as a cyclic structure formed by combining two or more of R ²¹ , R ²² and R ²³ with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following. These cyclic structures may further have a substituent.

（上記式中、ＲはＲ^２１〜Ｒ^２３のうち何れかの基を表す。）

(In the above formula, R represents any group of R ^{21 to} R ^23. )

As ^R 21 ^{to R 23} in ^{-N + R 21 R 22 R 23} , more preferably it may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a phenyl group or a benzyl group which may have a substituent.

  As the A block, those containing a partial structure represented by the following general formula (VI) are particularly preferable.

(In the above formula (VI), R ²¹ , R ²² and R ²³ each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ²¹ , R ²² and Two or more of R ²³ may be bonded to each other to form a cyclic structure, R ²⁴ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and M ⁻ represents Represents a counter anion.)

In the general formula (VI), the hydrocarbon groups of R ²¹ , R ²² and R ²³ are each independently a substituent having an alkyl group having 1 to 10 carbon atoms and an aromatic group having 6 to 20 carbon atoms. preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.

In the general formula (VI), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ²⁵ —, —COO—R ²⁶ — (provided that R ²⁵ and R ²⁶ represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ²⁷ —O—R ²⁸ —: R ²⁷ and R ²⁸ are each independently an alkylene group). And the like, and preferably —COO—R ²⁶ —.

Examples of the counter anion M ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

The amino group is preferably —NR ³¹ R ³² (wherein R ³¹ and R ³² each independently have a cyclic or chain-like alkyl group which may have a substituent, or a substituent. A preferable allyl group or an aralkyl group which may have a substituent.), And an amino group represented by the following formula (VII) is more preferable.

^{(However, R 31} and ^{R 32} has the same meaning as above ^{R 31} and ^{R 32, R 33} represents one or more alkylene groups having a carbon ^{number, R 34} represents a hydrogen atom or a methyl group.)

Among them, R ³¹ and R ³² are preferably methyl groups, R ³³ is preferably a methylene group and an ethylene group, and R ³⁴ is preferably a hydrogen atom. Examples of such a compound include a substituent represented by the following formula (VII-a).

  Two or more kinds of partial structures containing the specific quaternary ammonium base and / or amino group as described above may be contained in one A block. In that case, two or more quaternary ammonium bases and / or amino group-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base and / or amino group may be contained in A block, As an example of this partial structure, it is derived from the below-mentioned (meth) acrylic acid ester monomer. Examples include partial structures.

  The content of such a quaternary ammonium base and / or a partial structure not containing an amino group in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the amino group-free partial structure is not contained in the A block.

  On the other hand, as the B block constituting the acrylic block copolymer, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, Isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethyl (Meth) acrylic acid ester monomers such as glycidyl acrylate and N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- Methylolacrylamide, , N-dimethylacrylamide, (meth) acrylamide monomers such as N, N-dimethylaminoethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine Examples include polymer structures.

  The B block is preferably a partial structure derived from a (meth) acrylate monomer represented by the following formula (VIII).

(In the above formula (VIII), R ⁴¹ represents a hydrogen atom or a methyl group. R ⁴² may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents an allyl group or an aralkyl group which may have a substituent.)

  Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be.

  When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 99% by weight, more preferably 0 to 85% by weight.

  The acrylic dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block, and such a block copolymer. Is prepared, for example, by the living polymerization method shown below.

  The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

  In synthesizing such an acrylic block copolymer, JP-A-60-89452, JP-A-9-62002, p. Lutz, P.A. Masson et al, Polym. Bull. 12, 79 (1984), B.R. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K.A. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J.A. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W. R. Hertler et al, Macromolecules, 20, 1473 (1987), K. Matyaszewski et al, Chem. Known methods described in Rev. 2001, 101, 2921-2990, etc. can be employed.

In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer according to the present invention is preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.
Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of a basic amino group with an acid.

The acid value of such an acrylic block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably lower and is usually 100 mg-KOH / g or less.
The MW of the acrylic block copolymer is usually in the range of 1000 or more and 100,000 or less. When the molecular weight of the acrylic block copolymer is too small, the dispersion stability decreases, and when it is too large, the developability and resolution tend to decrease.

  In the present invention, a commercially available acrylic block copolymer having the same structure as described above can also be applied.

[5-2-3] Polymer formed by polymerizing monomer component essential to specific compound The polymer formed by polymerizing monomer component essential to a specific compound is represented by the following formula (X). It refers to a polymer obtained by polymerizing a monomer component essentially comprising the represented compound (hereinafter referred to as “polymer (X)”).
Hereinafter, the polymer (X) will be described.

(In formula (X), R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

In the general formula (X) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ⁵¹ and R ⁵² is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl , Alicyclic groups such as t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ⁵¹ and R ⁵² may be the same type of substituent or different substituents.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like. Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds.

  The proportion of the ether dimer in the monomer component in obtaining the polymer (X) is not particularly limited, but is 2 to 60% by weight, preferably 5 to 55% by weight, more preferably, in all monomer components. It should be 5 to 50% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, the transparency, heat resistance, etc. There is a possibility that the performance of the coating film becomes insufficient.

  The polymer (X) is preferably a polymer having an acid group. Thus, the resulting photosensitive resin composition is a curable resin capable of a crosslinking reaction (hereinafter abbreviated as “acid-epoxy curing”) utilizing the fact that an ester bond is formed by the reaction of an acid group and an epoxy group. A composition or a composition in which an uncured part can be visualized with an alkali developer can be used. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more.

  In order to introduce an acid group into the polymer (X), for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter referred to as “monomer for introducing an acid group”). May be polymerized as a monomer component. In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

Examples of the monomer having an acid group include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.
These monomers for introducing an acid group may be only one type or two or more types.

When the monomer component for obtaining the polymer (X) also includes a monomer for introducing the acid group, the content ratio is not particularly limited, but is 5 to 70% by weight in the total monomer components. %, Preferably 10 to 60% by weight.
The polymer (X) may be a polymer having a radical polymerizable double bond.

In order to introduce a radical polymerizable double bond into the polymer (X), for example, a monomer capable of imparting a radical polymerizable double bond after polymerization (hereinafter referred to as “monomer for introducing a radical polymerizable double bond”). )) As a monomer component, and then a treatment for imparting a radical polymerizable double bond as described later may be performed.
Examples of the monomer for introducing the radical polymerizable double bond include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; and a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride. A monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

  When the monomer component in obtaining the polymer (X) also includes a monomer for introducing the radical polymerizable double bond, the content ratio is not particularly limited, 5 to 70% by weight, preferably 10 to 60% by weight.

The polymer (X) is preferably a polymer having an epoxy group.
In order to introduce an epoxy group into the polymer (X), for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) is polymerized as a monomer component. do it.

Examples of the monomer for introducing the epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. Is mentioned. These monomers for introducing an epoxy group may be only one kind or two or more kinds.
When the monomer component for obtaining the polymer (X) also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but is 5 to 70% by weight in the total monomer components. %, Preferably 10 to 60% by weight.

The monomer component for obtaining the polymer (X) includes the ether dimer represented by the general formula (X), which is an essential component, the monomer for introducing the acid group described above, and a radically polymerizable monomer. In addition to the monomer for introducing a heavy bond and the monomer for introducing an epoxy group, other copolymerizable monomers may be included as required.
Examples of the other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy (meth) acrylate (Meth) acrylic acid esters such as ethyl; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene Or substituted butadiene compounds; ethylene, propylene, vinyl chloride Le, ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.

  In particular, when the polymer (X) is used as a dispersant, it is preferable to use benzyl (meth) acrylate as another monomer. In this case, the proportion of benzyl (meth) acrylate gives the polymer (X). 1 to 70% by weight, preferably 5 to 60% by weight, based on all monomer components.

When the monomer component for obtaining the polymer (X) includes the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by weight or less in the total monomer component, and 85% by weight. % Or less is more preferable.
The polymer (X) can be easily obtained by polymerizing the monomer component having at least the ether dimer represented by the general formula (X). At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydrofuran ring structure.

  The method for the polymerization reaction of the monomer component in obtaining the polymer (X) is not particularly limited, and various conventionally known polymerization methods can be adopted, but it is particularly preferable to use a solution polymerization method. . The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. Depending on the molecular weight of the target polymer, the polymerization temperature is preferably 40 to 150 ° C. and the polymerization concentration is 5 to 50%, and more preferably, the polymerization temperature is 60 to 130 ° C. and the polymerization concentration is 10 to 40%. It is good to do.

  When a solvent is used in the polymerization of the monomer component when obtaining the polymer (X), a solvent used in a normal radical polymerization reaction may be used as the solvent. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide; Etc. These solvents may be used alone or in combination of two or more.

  When the monomer component for obtaining the polymer (X) is polymerized, a commonly used polymerization initiator may be added as necessary. Although it does not specifically limit as a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo compounds such as dimethyl 2,2′-azobis (2-methylpropionate), and the like. These polymerization initiators may be used alone or in combination of two or more. The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight without gelation. From the standpoint that several thousand to several tens of thousands of polymers can be obtained, the content is 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on all monomer components.

  Moreover, when polymerizing the monomer component for obtaining the polymer (X), a chain transfer agent that is usually used may be added as necessary for adjusting the molecular weight. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and α-methylstyrene dimer. Preferred are n-dodecyl mercaptan and mercaptoacetic acid, which can be reduced and easily obtained. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but without gelation In terms of being able to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, it is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight based on all monomer components. .

  In the polymerization reaction, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously, but the cyclization rate of the ether dimer does not necessarily need to be 100 mol%.

When obtaining the polymer (X), as a monomer component, the monomer that can give an acid group after polymerization described above is used, and when an acid group is introduced thereby, a treatment for adding an acid group after polymerization is performed. There is a need to do.
The treatment for imparting an acid group varies depending on the type of monomer that can impart an acid group to be used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, for example, What is necessary is just to make it add acid anhydrides, such as a succinic anhydride, a tetrahydrophthalic anhydride, and a maleic anhydride, When using the monomer which has epoxy groups, such as glycidyl (meth) acrylate, Hydroxyl group formed after adding a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol, or after adding an acid such as (meth) acrylic acid For example, an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride may be added. , In the case of using a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate may be, for example, so as to be added with a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid.

When the polymer (X) is obtained, a monomer capable of imparting a radical polymerizable double bond after the above-described polymerization is used as a monomer component. It is necessary to perform a treatment for imparting a polymerizable double bond.
The treatment for imparting the radical polymerizable double bond varies depending on the type of monomer that can impart the radical polymerizable double bond to be used. For example, a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used. When used, epoxy groups such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether and radical polymerizable double bonds In the case of using a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride, a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a radical are added. A compound having a polymerizable double bond may be added, and glycidyl (meth) a When a monomer having an epoxy group such as relate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzylglycidyl ether is used, (meth) acrylic acid, etc. A compound having an acid group and a radical polymerizable double bond may be added.

  The MW of the polymer (X) is not particularly limited, but is preferably 2,000 to 200,000, more preferably 5,000 to 100,000. When the MW exceeds 200,000, the viscosity becomes too high to form a coating film, and when it is less than 2000, sufficient heat resistance tends to be hardly exhibited.

  When the polymer (X) has an acid group, the acid value is preferably 30 to 500 mg-KOH / g, more preferably 50 to 400 mg-KOH / g. When the acid value of the polymer (X) is less than 30 mg-KOH / g, it becomes difficult to apply to alkali development, and when it exceeds 500 mg-KOH / g, the viscosity tends to be too high to form a coating film. .

  The polymer (X) is a compound known per se, and examples thereof include compounds described in JP-A-2004-300203 and JP-A-2004-300204.

[5-3] Content of dispersant and / or dispersion aid In the present invention, the content of the dispersant and / or dispersion aid is the total content in the total solid content of the light-sensitive photosensitive resin composition. The amount is usually 1 to 30% by weight, preferably 2 to 25% by weight. If the content of the dispersing agent and / or dispersing aid is too small, sufficient dispersibility cannot be obtained, and if it is too large, the proportion of other components is relatively reduced and the optical density, sensitivity, film formability, etc. are decreased. To do.

[6] Other components In addition to the components listed above, the light-shielding photosensitive resin composition of the present invention further includes a polymerization accelerator, a sensitizing dye, a surfactant, a photoacid generator, a crosslinking agent, An adhesion improver, a plasticizer, a storage stabilizer, a surface protective agent, an organic carboxylic acid, an organic carboxylic acid anhydride, a development improver, a thermal polymerization inhibitor and the like may be included.

[6-1] Photoacid generator The photoacid generator is a compound capable of generating an acid by ultraviolet rays, and there is a crosslinking agent such as a melamine compound by the action of the acid generated upon exposure. As a result, the crosslinking reaction proceeds. Among such photoacid generators, those having high solubility, particularly solubility in a solvent are preferable. For example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium. Bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p-isopropylphenyl (p-tolyl) iodonium, etc. Diaryliodonium or triarylsulfonium chloride, bromide, borofluoride, hexafluorophosphate salt, hexafluoroarsenate salt, aromatic sulfonate salt, Sulfonium organic boron complexes such as kiss (pentafluorophenyl) borate salt, diphenylphenacylsulfonium (n-butyl) triphenyl borate, 2-methyl-4,6-bistrichloromethyltriazine, 2- (4 Examples include triazine compounds such as -methoxyphenyl) -4,6-bistrichloromethyltriazine, but are not limited thereto.

[6-2] Crosslinking agent A crosslinking agent can be further added to the light-shielding photosensitive resin composition of the present invention. For example, a melamine or guanamine-based compound can be used. Examples of these crosslinking agents include melamine or guanamine compounds represented by the following general formula (XI).

(Wherein R ⁶¹ represents a group —NR ⁶⁶ R ⁶⁷ or aryl, and when R ⁶¹ is a group —NR ⁶⁶ R ⁶⁷ , one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ ). And when R ⁶¹ is aryl, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents the group —CH ₂ OR ⁶⁸ , and R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ The rest, independently of one another, represent hydrogen or the group —CH ₂ OR ⁶⁸ , where R ⁶⁸ represents hydrogen or alkyl.)

Here, the aryl is typically phenyl, 1-naphthyl or 2-naphthyl, and a substituent such as alkyl, alkoxy or halogen may be bonded to the phenyl or naphthyl. Alkyl and alkoxy can each have about 1 to 6 carbon atoms. Among the above, alkyl represented by R ⁶⁸ is generally methyl or ethyl, especially methyl.

  Melamine compounds corresponding to the general formula (XI), that is, compounds of the following general formula (XI-1) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy Methyl melamine, hexaethoxymethyl melamine and the like are included.

(Wherein one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is aryl, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents the group —CH ₂ OR ⁶⁸ . , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and the rest of R ⁶⁷ independently of one another represent hydrogen or the group —CH ₂ OR ⁶⁸ , where R ⁶⁸ represents hydrogen or alkyl.)

Further, guanamine compounds corresponding to the general formula (XI), that is, compounds in which R ⁶¹ in the general formula (XI) is aryl include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine. Etc. are included.

Furthermore, the following compounds are also included in the crosslinking agent having a methylol group or a methylol alkyl ether group, and these can also be used. Examples are given below.
2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.

In addition, these crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type.
The amount of the crosslinking agent used is preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight, based on the total solid content of the light-shielding photosensitive resin composition.

[5-3] Adhesion improver The light-shielding photosensitive resin composition of the present invention may contain an adhesion improver in order to sufficiently adhere fine lines and dots.

As the adhesion improver, a compound containing a nitrogen atom, a phosphoric acid group-containing compound, a silane coupling agent or the like is preferable. Examples of the compound containing a nitrogen atom include diamines (adhesion enhancers described in JP-A No. 11-184080) And others) and azoles are preferred. Of these, azoles are preferred, and imidazoles (adhesion improvers described in JP-A-9-236923, etc.), benzimidazoles, and benzotriazoles (adhesion improvers described in JP-A 2000-171968, etc.) are particularly preferred. And benzimidazoles are most preferred. Among these, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2 are less likely to cause fogging and greatly improve adhesion. -Aminoimidazole is preferable, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferable. Various types of silane coupling agents such as epoxy, methacrylic, amino and the like can be used, and epoxy silane coupling agents are particularly preferable.
These can be used alone or in combination of two or more.

  When blending these adhesion improvers, the blending ratio varies depending on the type of the adhesion improver used, but is 0.01 to 5% by weight, particularly 0, based on the total solid content of the light-shielding photosensitive resin composition. It is preferable to set it as 0.05 to 3 weight%. If it is less than this, sufficient adhesion improving effect cannot be obtained, and if it is too much, developability is lowered.

[6-4] Sensitizing dye Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703, and JP-A-5-289335. Coumarin dyes having the heterocyclic ring described above, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A-47. -2528, JP 54-155292, JP-B 45-37377, JP 48-84183, JP 52-112681, JP 58-15503, JP 60-88005 JP, 59-56403, JP, 2-69, JP, 57-168088, JP, 5-107761, JP, 5-210240, JP, Examples thereof include a dye having a dialkylaminobenzene skeleton described in JP-A-4-288818.
These can be used alone or in combination of two or more.

  When blending the sensitizing dye, the content of the sensitizing dye in the total solid content in the light-shielding photosensitive resin composition is 0.01 to 5% by weight, preferably 0.05 to 3% by weight. If it is less than this, the sensitizing effect will not be obtained, and if it is too much, the developability will be lowered.

[6-5] Surfactant As the surfactant, one or more of anionic, cationic, nonionic, amphoteric surfactants and the like can be used, but they adversely affect various properties. In view of low possibility, it is preferable to use a nonionic surfactant. In addition, fluorine-based and silicon-based materials are effective in terms of coating properties.

  The blending ratio of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, and more preferably 0.01 to 10% by weight based on the total solid content in the light-shielding photosensitive resin composition. It is in the range of 0.5% by weight, most preferably 0.03-0.3% by weight. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film cannot be expressed, and if it is too large, the smoothness and uniformity of the coating film cannot be expressed and other characteristics may be deteriorated. .

[6-6] Organic Carboxylic Acid, Organic Carboxylic Anhydride The light-shielding photosensitive resin composition of the present invention contains an organic carboxylic acid and / or an organic carboxylic anhydride for the purpose of improving developability and improving background stains. You may go out.
Examples of the organic carboxylic acid include aliphatic carboxylic acids and / or aromatic carboxylic acids.
Specific examples of the aliphatic carboxylic acid include monoacids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid. Carboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethyl Examples thereof include dicarboxylic acids such as succinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid, and tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoric acid. Specific examples of the aromatic carboxylic acid include benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and merophanic acid. , Pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidenacetic acid, coumaric acid, umbelic acid, etc. Examples thereof include carboxylic acids in which a carboxyl group is directly bonded to a group, and carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon bond.

Among the organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferable, and malonic acid, glutaric acid, and glycolic acid are more preferable, and malonic acid is particularly preferable.
The molecular weight of the organic carboxylic acid is 1000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving the soiling is insufficient, and if it is too small, the addition amount may be reduced or process contamination may occur due to sublimation or volatilization.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and / or aromatic carboxylic acid anhydrides, and specific examples of aliphatic carboxylic acid anhydrides include acetic anhydride, trichloroacetic anhydride, and trifluoro anhydride. Acetic acid, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2, Examples include aliphatic carboxylic acid anhydrides such as 3-dicarboxylic acid. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

Among the organic carboxylic acid anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.
The molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid anhydride is too large, the effect of improving background stains is insufficient. If the molecular weight is too small, there is a possibility that the amount added may be reduced or process contamination may occur due to sublimation or volatilization.

  One of these organic carboxylic acids and organic carboxylic acid anhydrides may be used alone, or two or more thereof may be mixed and used.

  The amount of these organic carboxylic acid and organic carboxylic acid anhydride added is usually 0.01% by weight to 5% by weight, preferably 0.03% in the total solid content of the light-shielding photosensitive resin composition of the present invention. % By weight to 3% by weight. If the addition amount is too small, a sufficient addition effect cannot be obtained. If the addition amount is too large, surface smoothness and sensitivity are deteriorated, and undissolved peeling pieces may be generated.

[6-7] Thermal polymerization inhibitor Examples of the thermal polymerization inhibitor include one or two of hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol, and the like. More than seeds are used.
The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight with respect to the total solid content in the light-shielding photosensitive resin composition. Reduce sensitivity.

[6-8] Plasticizer Examples of the plasticizer include 1 such as dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. Species or two or more are used.
The blending ratio of these plasticizers is preferably in the range of 5% by weight or less with respect to the total solid content in the light-shielding photosensitive resin composition, and if it is more than this, the curing point of the resin black matrix is lowered.

[7] Solvent Each component contained in the light-shielding photosensitive resin composition of the present invention described above is usually dissolved or dispersed in a solvent and used as a light-shielding photosensitive resin composition solution.

  Examples of the solvent used here include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methyl Ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropion Acid, 3-e Methyl toxipropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, Examples include butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate. These solvents may be used alone or in combination of two or more.

  In the light-shielding photosensitive resin composition of the present invention, the solvent content is 90% by weight or less, 60% by weight or more, particularly 70% by weight, from the viewpoint of ease of coating during coating film formation and film thickness control. The above is preferable. That is, the light-shielding photosensitive resin composition of the present invention is usually prepared so that the total solid content concentration is 10% by weight or more and 40% by weight or less, particularly 30% by weight or less.

[8] Manufacturing method of light-shielding photosensitive resin composition Next, the manufacturing method of the light-shielding photosensitive resin composition of this invention is demonstrated.

  The method for producing the light-shielding photosensitive resin composition of the present invention is not particularly limited, but a pigment dispersion is prepared using a light-shielding pigment, a solvent and a dispersant, and other components are added to the pigment dispersion. A method for preparing a light-shielding photosensitive resin composition is preferred.

[8-1] Method for Producing Pigment Dispersion Various methods can be adopted as a method for producing a pigment dispersion according to the present invention. An example is shown below.

First, a predetermined amount of each of the light-shielding pigment, the solvent, and the dispersant is weighed, and in the dispersion treatment step, the pigment is dispersed to obtain a liquid pigment dispersion. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several mm or zirconia beads.
Since the pigment is formed into fine particles by this dispersion treatment, the light-shielding photosensitive resin composition using the pigment dispersion has improved coating properties.

  When dispersing the pigment, the alkali-soluble resin or the dispersion aid may be used in combination as appropriate.

  The temperature for the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the pigment dispersion (pigment, solvent, dispersant, etc.), the size of the sand grinder apparatus, and the like.

[8-2] Method for Producing Light-Sensitive Photosensitive Resin Composition Next, the pigment dispersion (ink) obtained by the above dispersion treatment and the above-described other components necessary as a light-shielding photosensitive resin composition component are added, Stir and mix to obtain a uniform light-shielding photosensitive resin composition solution. In this manufacturing process, fine dust is often mixed in the liquid, and thus the obtained light-shielding photosensitive resin composition solution is preferably filtered through a filter or the like.

[Method of forming resin black matrix]
In order to form the resin black matrix of the present invention by the light-shielding photosensitive resin composition of the present invention described above, the light-shielding photosensitive resin composition solution of the present invention is applied on a transparent substrate and dried, A photomask is placed on the sample, and a resin black matrix is formed through image exposure, development, and thermosetting or photocuring as necessary through the photomask.
The resin black matrix of the present invention is effective for forming on the TFT element substrate, but its configuration is not particularly limited in each of the COA and BOA systems, and can be applied to various configurations. is there.

  Examples of the method for applying the light-shielding photosensitive resin composition solution of the present invention on a transparent substrate include a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, and a spray coating method. According to the die coating method, the amount of coating solution used is greatly reduced, and there is no influence of mist adhering when using the spin coating method. preferable.

The film thickness of the coating after application and drying is usually 0.5 to 5 μm, preferably 1 to 4 μm.
A hot plate, IR oven, convection oven, or the like can be used for drying the coating film. Preferred drying conditions are 40 to 150 ° C., and drying time is in the range of 10 seconds to 60 minutes.

  As a light source used for exposure, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a fluorescent lamp, or a lamp light source or an argon ion laser And laser light sources such as YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. In the case where only the wavelength of specific irradiation light is used, an optical filter can also be used.

  The development treatment is not particularly limited as long as it is a solvent capable of dissolving the resist film in the unexposed area. For example, an organic solvent such as acetone, methylene chloride, trichlene, and cyclohexanone can be used. However, since many organic solvents have environmental pollution, harmfulness to human body, fire risk, etc., it is preferable to use an alkaline developer without such danger. Examples of such an alkaline developer include inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethanolamine, tetraalkylammonium hydroxide salt, etc. And an aqueous solution containing an organic alkali agent. If necessary, the alkaline developer may contain a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxyl group, and the like. In particular, it is preferable to add a surfactant since many surfactants have an improving effect on developability, resolution, and background stains.

  For example, as a surfactant for a developer, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group Can be mentioned.

  Although there is no restriction | limiting in particular about the image development processing method, Usually, it is carried out by methods, such as immersion image development, spray image development, brush image development, and ultrasonic image development, at the image development temperature of 15-40 degreeC, Preferably it is 20-30 degreeC.

After the development, usually a heat curing treatment or a light curing treatment, preferably a heat curing treatment is performed.
As for the thermosetting treatment conditions, the temperature is selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.
A higher temperature of the thermosetting treatment and a longer time are advantageous for electrical characteristics such as a high volume resistivity and a low relative dielectric constant.

The resin black matrix formed as described above has a bottom width of usually 3 to 50 μm, preferably 5 to 30 μm, a height of usually 0.5 to 5 μm, preferably 1 to 4 μm, and a substrate crossing angle θ is As mentioned above, it is usually 40 ° to 90 °, preferably 50 ° to 90 °, particularly preferably 60 ° to 90 °. Further, the low volume efficiency is 1 × 10 ¹³ Ω · cm or more, preferably 1 × 10 ¹⁴ Ω · cm or more, and the relative dielectric constant is 6 or less, preferably 5 or less.
Furthermore, the optical density is 3 or more, preferably 3.2 or more, more preferably 3.5 or more.

[Liquid Crystal Display]
The liquid crystal display device of the present invention has the resin black matrix of the present invention as described above. For example, the resin black matrix of the present invention is provided on a TFT element substrate to form red, green, and blue pixel images. Further, after forming an alignment film on the alignment film and spraying spacers on the alignment film, a liquid crystal cell is formed by bonding to the counter substrate, liquid crystal is injected into the formed liquid crystal cell, and the counter electrode is connected. Manufactured.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the following, “part” represents “part by weight”.

<Synthesis of alkali-soluble resin-1>
"XD1000" manufactured by Nippon Kayaku Co., Ltd. (polyglycidyl ether of dicyclopentadiene / phenol polymer, MW 700, epoxy equivalent 252) 300 parts, 87 parts of acrylic acid, 0.2 parts of p-methoxyphenol, triphenylphosphine 5 Part and 255 parts of propylene glycol monomethyl ether acetate were charged in a reaction vessel and stirred at 100 ° C. until the acid value became 3.0 mg-KOH / g. It took 9 hours for the acid value to reach the target (acid value 2.5 mg-KOH / g). Subsequently, 145 parts of tetrahydrophthalic anhydride was further added and reacted at 120 ° C. for 4 hours to obtain an alkali-soluble resin-1 solution having an acid value of 100 mg-KOH / g and MW 2600.

<Synthesis of alkali-soluble resin-2>
120 parts of MW4000 metacresol novolak resin and 71 parts of glycidyl methacrylate are dissolved in 191 parts of propylene glycol monomethyl ether acetate, 0.19 parts of p-methoxyphenol and 1.9 parts of tetraethylammonium chloride are added, and the reaction is carried out at 90 ° C. for 13 hours. I let you. It was confirmed by gas chromatography analysis that glycidyl methacrylate was 1% or less, 45.6 parts of tetrahydrophthalic anhydride and 45.6 parts of propylene glycol monomethyl ether acetate were added, and the mixture was further reacted at 95 ° C. for 5 hours. . After confirming the absence of acid anhydride by IR, an alkali-soluble resin-2 solution of MW7500 was obtained.

<Synthesis of alkali-soluble resin-3>
145 parts of propylene glycol monomethyl ether acetate was stirred while the inside of the reaction vessel was purged with nitrogen, and the temperature was raised to 120 ° C. To this, 20 parts of styrene, 57 parts of glycidyl methacrylate and 82 parts of monoacrylate having a tricyclodecane skeleton ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and stirring was continued at 120 ° C for 2 hours.
Next, the inside of the reaction vessel was purged with air, 27.0 parts of acrylic acid, 0.7 part of trisdimethylaminomethylphenol and 0.12 part of hydroquinone were added, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 52.0 parts of tetrahydrophthalic anhydride (THPA) and 0.7 part of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an alkali-soluble resin-3 solution. The obtained alkali-soluble resin-3 had a MW of about 15000 and an acid value of 100 mg-KOH / g.

<Alkali-soluble resin-4>
“ZCR-1569H” manufactured by Nippon Kayaku Co., Ltd. (MW = 4000 to 5000, acid value = 100
mg-KOH / g)

<Synthesis of Dispersant-1>
50 parts by weight of polyethyleneimine having a molecular weight of about 5000 and 40 parts by weight of polycaprolactone with n = 5 were mixed with 300 parts by weight of propylene glycol monomethyl ether acetate and stirred at 150 ° C. for 3 hours in a nitrogen atmosphere. MW of the obtained Dispersant-1 was 9000.

<Dispersant-2>
"DisperBYT-161" manufactured by Big Chemie

<Dispersing aid>
“S12000” manufactured by Loop Resor Co., Ltd.

<Solvent>
PGMEA: Propylene glycol monomethyl ether acetate MBA: 3-methoxydibutyl acetate

<Photopolymerization initiator-1>

<Ethylenically unsaturated compound>
DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate U-6LPA: Shin-Nakamura Chemical Co., Ltd. PM-21: Nippon Kayaku Co., Ltd.

<Preparation of pigment dispersions-1 to 4>
A pigment, a dispersant, a dispersion aid, an alkali-soluble resin, and propylene glycol monomethyl ether acetate (PGMEA) as a solvent described in Table 1 were mixed at a weight ratio described in Table 1. Here, 3 times the total weight of these zirconia beads (average particle size 0.5 mm) was mixed, filled in a stainless steel container, and dispersed for 6 hours in a paint shaker to prepare each pigment dispersion. .

[Examples 1 to 3, Comparative Examples 1 to 5]
The pigment dispersion prepared above and the components shown in Table 2 were blended in the proportions shown in Table 2 and stirred to prepare respective light-shielding photosensitive resin composition coating solutions.

<Manufacture of sample (1)>
A 10 cm square TFT element substrate is immersed in a 1% by weight diluted solution of silane coupling agent “KBM-603” manufactured by Shin-Etsu Chemical Co., Ltd. for 3 minutes, washed with water for 10 seconds, drained with an air gun, and dried in an oven at 110 ° C. for 5 minutes. did. On this TFT element substrate, each light-shielding photosensitive resin composition coating solution prepared according to Table 2 was applied using a spin coater, vacuum-dried for 1 minute, and prebaked at 90 ° C. for 90 seconds on a hot plate, A coating film having a dry film thickness of 3.5 μm was obtained. Thereafter, image exposure was performed from the coating film side through a fine line pattern mask having a width of 15 μm using 3 kW high-pressure mercury under an exposure condition of 50 mJ / cm ² . Subsequently, using a developer composed of an aqueous solution containing 0.05% by weight of potassium hydroxide and 0.08% by weight of a nonionic surfactant (“A-60” manufactured by Kao Corporation), the water pressure at 23 ° C. After performing shower development at 0.15 MPa, development was stopped with pure water and rinsed with a water spray. The shower development time was adjusted between 10 and 120 seconds, and was 1.5 times as long as the photosensitive layer was dissolved and removed (break time).
The TFT element substrate thus imaged was post-baked at 230 ° C. for 30 minutes to obtain a sample (1) in which a resin black matrix line was formed on the TFT element substrate. The resist film thickness at this stage was about 3 μm.

<Manufacture of sample (2)>
Instead of the TFT element substrate, a glass substrate (Asahi Glass Co., Ltd. color filter glass plate “AN100”) on which a 150 nm thick ITO film was formed by sputtering was used, and the entire surface was exposed without using a mask. Except for this, a sample (2) in which a resin black matrix was formed on the entire surface of the ITO substrate was obtained in the same manner as in the production of the sample (1).

  The obtained sample (1) or sample (2) was evaluated as follows, and the results are shown in Table 2.

<Measurement of optical density>
The sample (1) was measured using a Macbeth reflection densitometer (“RD-914” manufactured by Sakata Inx Corporation).

<Measurement of substrate crossing angle θ>
For sample (1), the cross-sectional shape of the resin black matrix line was observed with an SEM (Hitachi, Ltd. “S-4500”), and the substrate crossing angle θ in contact with the TFT element substrate was measured.

<Evaluation of linearity>
The resin black matrix line of sample (1) was observed with an optical microscope. The line edge with no shakiness and good linearity was marked with ◯, and the edge with shaky edges was marked with x.

<Measurement of volume resistivity / dielectric constant>
The relative permittivity and volume resistivity of the sample (2) were measured using “LCR meter 4284A” manufactured by HP (current Agilent). The relative dielectric constant was measured at 1 KHz · 1 V, and the volume resistivity was measured at DC 5 V.

  From Table 2, it can be seen that according to the present invention, a resin black matrix having excellent light shielding properties, high volume resistivity, low relative dielectric constant, and good shape is provided.

It is typical sectional drawing which shows board | substrate crossing angle (theta).

Explanation of symbols

1 Substrate 2 Resin black matrix

Claims (4)

A resin black matrix having an optical density of 3 or more, a volume resistivity of 1 × 10 ¹³ Ω · cm or more, and a relative dielectric constant at 1 KHz of 6 or less. In the resin black matrix formed on the substrate, the optical density is 3 or more, the volume resistivity is 1 × 10 ¹³ Ω · cm or more, the relative dielectric constant at 1 KHz is 6 or less, and the plate of the substrate A resin black matrix, wherein a crossing angle θ between a side surface of the resin black matrix and a plate surface of the substrate in a cross section perpendicular to the surface is 40 ° to 90 °.   An alkali-soluble resin, a photopolymerization initiator, an ethylenically unsaturated compound, and a light-shielding pigment, wherein the content of the light-shielding pigment is 30% by weight to 50% by weight with respect to the total solid content; The light-shielding photosensitive resin composition for forming a resin black matrix according to claim 1 or 2, wherein carbon black is contained in an amount of 2 to 20% by weight based on the total solid content.   A liquid crystal display device comprising the resin black matrix according to claim 1.

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