JP6607054B2 - Photosensitive resin composition, cured product, black matrix, and image display device - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a cured product, a black matrix, and an image display device. In particular, the present invention relates to a photosensitive resin composition having excellent adhesion to a substrate, a cured product obtained by curing the photosensitive resin composition, a black matrix made of the cured product, and an image display device having the black matrix.

  A color filter usually forms a black black matrix (hereinafter sometimes abbreviated as “BM”) on the surface of a transparent substrate such as glass or plastic, and then three types such as red, green, and blue. The above different pixels are sequentially formed in a striped pattern or a mosaic pattern.

  A pigment dispersion method is currently used as a representative method for producing a color filter. In this method, first, a photosensitive resin composition containing a black pigment is applied on a transparent substrate, dried, further exposed to an image, developed, and then cured by high-temperature treatment at 200 ° C. or higher to form a BM. A color filter is formed by repeating this for each color such as red, green, and blue.

  The BM is generally arranged in a grid, stripe, or mosaic between pixels such as red, green, and blue, and has a role of preventing contrast improvement or light leakage by suppressing color mixture between pixels. Yes. For this reason, the BM is required to have high light shielding properties.

  Further, since the edge portions of the red, green, and blue pixels formed after the BM overlap with the BM, a step is formed at the overlapping portion due to the influence of the BM film thickness. In this overlapping portion, the flatness of the pixel is impaired, and the liquid crystal cell gap becomes nonuniform or the alignment of the liquid crystal is disturbed, resulting in a decrease in display capability.

  Therefore, in recent years, particularly BM thinning has been demanded, and the pigment content in the photosensitive resin composition tends to be higher in order to develop sufficient light-shielding properties even when thinned. However, since the pigment does not contribute to crosslinking, an increase in the pigment component leads to a decrease in the adhesion between the BM and the substrate.

  Also, in recent years, when assembling the manufactured color filter on a panel, conventionally, a frame portion was separately formed, and a sealant was applied to the panel to attach it to the array substrate. A method of forming a frame portion at the same time and applying a sealant to the frame portion and bonding the frame portion has come to be performed. For this reason, an improvement in the adhesion between the color filter substrate and the BM is required more than ever. In addition, production panels are being transported overseas, and it has become important that the substrate adhesion of the BM does not deteriorate even when exposed to a high temperature and high humidity environment during transportation.

  As described above, as the required characteristics of BM are increasing as BM becomes thinner, an adhesion improver is added to the photosensitive resin composition as a method for improving adhesion of pixels and BM to the substrate. For example, Patent Document 1 describes that the adhesion of BM is improved by using a silane coupling agent such as epoxy, (meth) acryl, and vinyl. Patent Document 2 describes that development adhesion is improved by using a secondary, tertiary amine, ketimine-based, or isocyanate-based silane coupling agent. Patent Document 3 describes that sensitivity and adhesion are improved by using a silane coupling agent having a photopolymerizable vinyl group.

JP-A-10-133370 JP 2008-129463 A Korean Registered Patent No. 10-1308246

As a result of intensive studies by the present inventors, in the photosensitive resin composition described in Patent Documents 1 and 2, the substrate adhesion after heat curing is not practically sufficient in the case of a high pigment concentration. Furthermore, it has been found that the substrate adhesion after exposure to a high temperature and high humidity environment is greatly reduced. Further, it has been found that the photosensitive resin composition described in Patent Document 3 does not have practically sufficient substrate adhesion after exposure to a high temperature and high humidity environment.
Then, an object of this invention is to provide the photosensitive resin composition from which the board | substrate adhesiveness after heat curing and high-temperature, high-humidity environment exposure becomes favorable.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by including a photosensitive resin composition containing an organosilicon compound having a specific structure and a surfactant exhibiting specific physical properties. . That is, the gist of the present invention is as follows.

[1] Alkali-soluble resin (a), photopolymerizable monomer (b), photopolymerization initiator (c), colorant (d), dispersant (e), organosilicon compound (f) and surfactant (g A photosensitive resin composition comprising:
The organosilicon compound (f) contains at least an organosilicon compound (f-1) having a structure represented by the following general formula (1),
A surfactant (g) contains a surfactant (g-1) that satisfies the following general formula (I): A photosensitive resin composition.

(In the above formula, R ^{1 to} R ³ are each independently a hydrogen atom or an alkyl group optionally having a substituent. ^Ra is a group represented by the following formula (1-1). * Is a bond.)

(In the above formula, R ⁴ and R ⁵ are each independently an alkylene group which may have a substituent, R ⁶ is a hydrogen atom or a methyl group. * Is a bond with a Si atom. .)

Δγ (toluene)> Δγ (propylene glycol monomethyl ether) (I)
(However, Δγ (toluene) is derived from the surface tension of toluene (mN / m, 25 ° C.) to the surface tension of 0.1% by weight toluene solution of surfactant (g-1) (mN / m, 25 ° C.). Similarly, Δγ (propylene glycol monomethyl ether) is 0.1 mass of surfactant (g-1) from the surface tension (mN / m, 25 ° C.) of propylene glycol monomethyl ether. (It means a value obtained by reducing the surface tension (mN / m, 25 ° C.) of a% propylene glycol monomethyl ether solution.)

[2] The photosensitive resin composition according to [1], wherein the surfactant (g-1) is a fluorosurfactant.
[3] The photosensitive resin composition according to [1] or [2], wherein the photopolymerization initiator (c) is an oxime ester compound.
[4] The photosensitive resin composition according to [3], wherein the oxime ester-based compound has an optionally substituted carbazolyl group.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the color material (d) is a black color material.

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the content ratio of the coloring material (d) is 40% by mass or more based on the total solid content.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the dispersant (e) is a polymer dispersant having a basic functional group.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the alkali-soluble resin (a) contains an epoxy (meth) acrylate resin having a carboxyl group.

[9] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [8].
[10] A black matrix comprising the cured product according to [9].
[11] The black matrix according to [10], wherein the optical density per 1 μm film thickness is 4.0 or more.
[12] An image display device having the black matrix according to [10] or [11].

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition from which the board | substrate adhesiveness after heat-curing and high-temperature, high-humidity environment exposure becomes favorable can be provided.

It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the color filter of this invention.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.

In the present invention, the “total solid content” means all components other than the solvent contained in the photosensitive resin composition or in the ink described later.
In the present invention, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
Further, in the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises an alkali-soluble resin (a), a photopolymerizable monomer (b), a photopolymerization initiator (c), a colorant (d), a dispersant (e), an organosilicon compound (f ) And a surfactant (g), wherein the organosilicon compound (f) is an organosilicon compound (f-1) having a structure represented by at least the following general formula (1): And the surfactant (g) contains a surfactant (g-1) that satisfies the following general formula (I).

In said formula, R < ¹ > -R < ³ > is a hydrogen atom or the alkyl group which may have a substituent each independently. R ^a is a group represented by the following formula (1-1). * Is a bond.

In the above formula, R ⁴ and R ⁵ are each independently an alkylene group which may have a substituent, and R ⁶ is a hydrogen atom or a methyl group. * Is a bond with a Si atom.

Δγ (toluene)> Δγ (propylene glycol monomethyl ether) (I)
However, Δγ (toluene) is the surface tension (mN / m, 25 ° C) of a 0.1% by weight toluene solution of the surfactant (g-1) from the surface tension of toluene (mN / m, 25 ° C). Means a reduced value. Similarly, Δγ (propylene glycol monomethyl ether) is determined from the surface tension of propylene glycol monomethyl ether (mN / m, 25 ° C.), and the surface of a 0.1 mass% propylene glycol monomethyl ether solution of surfactant (g-1). It means a value obtained by reducing the tension (mN / m, 25 ° C.). )

The photosensitive resin composition of the present invention may further contain a dispersion aid and a polyfunctional thiol compound, and if necessary, other adhesion improvers, coatability improvers, development improvers, ultraviolet absorptions. Other compounding components such as an agent and an antioxidant may be contained, and each compounding component is usually used in a state dissolved or dispersed in an organic solvent.
The feature of the present invention is that the photosensitive resin composition contains the surfactant (g-1) together with the organosilicon compound (f-1). First, the organosilicon compound (f) will be described.

<Organic silicon compound (f)>
The organosilicon compound (f) in the present invention contains at least an organosilicon compound (f-1) having a structure represented by the following general formula (1).

In said formula, R < ¹ > -R < ³ > is a hydrogen atom or the alkyl group which may have a substituent each independently. R ^a is a group represented by the following formula (1-1). * Is a bond.

In the above formula, R ⁴ and R ⁵ are each independently an alkylene group which may have a substituent, and R ⁶ is a hydrogen atom or a methyl group. * Is a bond with a Si atom.

The alkyl group in R ^{1 to} R ³ in the general formula (1) may be linear, branched or cyclic, but is preferably linear from the viewpoint of reactivity. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 8 or less, more preferably 6 or less, further preferably 4 or less, particularly preferably 3 or less, most preferably 2 or less, and usually 1 or more. By setting it to the lower limit value or less, the handleability and reactivity tend to be good.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopentyl group, and a cyclohexyl group. Among these, from the viewpoint of reactivity, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, and a methyl group or an ethyl group is more preferable.
Examples of the substituent that the alkyl group may have include a halogen atom, an alkoxy group, an aryl group, a hydroxyl group, a thiol group, and an alkylthio group. From the viewpoint of storage stability, a halogen atom or an alkoxy group is preferable. . Further, from the viewpoint of reaction rate, it is preferably unsubstituted.

The alkylene group in R ⁴ and R ⁵ in the general formula (1-1) may be linear, branched or cyclic. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 10 or less, more preferably 8 or less. When it is at least the above lower limit value, the handleability and storage stability tend to be good, and when it is at most the above upper limit value, the compatibility with the resist tends to be good.
Specific examples of the alkylene group include methylene group, ethylene group, 1,3-propylene group, 1,2-propylene group, 1,4-butylene group, 1,2-butylene group, 1,5-pentylene group, 1 , 6-hexylene group, cyclohexylene group, methylenecyclohexylene group, 2-ethyl-2methylbutane-1,4-diyl group and the like. Among these, methylene group, ethylene group, 1,3-propylene group, 1,2-propylene group, 1,4-butylene group, or 1,2-butylene group from the viewpoint of easy handling and compatibility with resist 2-ethyl-2methylbutane-1,4-diyl group is preferred, ethylene group, 1,3-propylene group, 1,2-propylene group, 2-ethyl-2methylbutane-1,4-diyl group is more preferred. preferable.
Examples of the substituent that the alkylene group may have include a halogen atom, an alkoxy group, an aryl group, a hydroxyl group, a thiol group, an alkylthio group, a group represented by the following general formula (1-2), and a general formula (1 -3) and the like. From the viewpoint of storage stability, a halogen atom or an alkoxy group is preferable. Further, from the viewpoint of reaction rate, it is preferably unsubstituted.

In the above formula, R ⁸ and R ⁹ are each independently an alkylene group which may have a substituent, and R ⁷ and R ¹⁰ are each independently a hydrogen atom or a methyl group. * Is a bond. In addition, as an alkylene group which may have a substituent, what was described as R < ⁵ > can be applied preferably.

  Examples of the organosilicon compound having the structure represented by the general formula (1) include the following.

  The organosilicon compound (f-1) is an organosilane compound having an isocyanate group represented by the following general formula (1-4) and a (meth) acryloyl group having a hydroxyl group represented by the following general formula (1-5) It can be obtained by a known method in which an oxy compound is urethanated in the presence of a catalyst.

In said formula, R < ¹ > -R < ⁴ > is synonymous with the said General formula (1) and (1-1).

In said formula, R < ⁵ > and R < ⁶ > are synonymous with the said General formula (1-1).

Examples of the catalyst used in this reaction include organotin compounds such as dibutyltin malate, tributyltin acetate, dimethyltin dichloride, dibutyltin diacetate, and dibutyltin dilaurate; N-methylmorpholine, triethylamine, N-methylpiperidine, N, N-dimethyl Tertiary amines such as cyclohexylamine and pyridine are useful, and the addition amount thereof is 0.001 to 1% by mass, particularly 0.01 to 0. 0% with respect to the silane compound of the general formula (2-1). 1% by mass is preferred. 0-50 degreeC is preferable and, as for reaction temperature, 20-40 degreeC is more preferable. The reaction time can be appropriately selected from 1 to 24 hours. The above reaction may usually be performed without a solvent, but an organic solvent such as hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, or acetonitrile may be used as necessary. The end point of the reaction can be confirmed by measuring the infrared absorption spectrum of the reaction product and not having absorption of 2266.1 cm ⁻¹ of the isocyanate group.

The organosilicon compound (f) may contain an organosilicon compound other than the organosilicon compound (f-1), for example, a multimer of the organosilicon compound (f-1).
Specific examples of the organosilicon compound other than the organosilicon compound (f-1) include the following vinyl group, epoxy group, styryl group, methacryl group, acrylic group, primary, secondary, tertiary amino group, Examples thereof include those having a ureido group, a mercapto group, an isocyanate group and the like.

The content ratio of the organosilicon compound (f) in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more in the total solid content. 0.5% by mass or more is more preferable, 1% by mass or more is particularly preferable, 25% by mass or less is preferable, 20% by mass or less is more preferable, and 10% by mass or less is preferable. More preferably, it is more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the amount is not less than the lower limit, there is a tendency that adhesion to the substrate can be improved, and when the amount is not more than the upper limit, there is a tendency that it is possible to suppress residue from remaining on the substrate during alkali development.
Further, the content ratio of the organosilicon compound (f-1) in the organosilicon compound (f) is not particularly limited, but is preferably 20% by mass or more, more preferably 50% by mass or more, and 70% by mass. % Or more, more preferably 100% by mass or less. There exists a tendency which can make favorable contact | adherence with a board | substrate by setting it as the said lower limit or more.

Next, the surfactant (g) will be described.
<Surfactant (g)>
The surfactant (g) in the present invention contains a surfactant (g-1) that satisfies the following general formula (I).

Δγ (toluene)> Δγ (propylene glycol monomethyl ether) (I)
However, Δγ (toluene) is the surface tension (mN / m, 25 ° C) of a 0.1% by weight toluene solution of the surfactant (g-1) from the surface tension of toluene (mN / m, 25 ° C). Means a reduced value. Similarly, Δγ (propylene glycol monomethyl ether) is determined from the surface tension of propylene glycol monomethyl ether (mN / m, 25 ° C.), and the surface of a 0.1 mass% propylene glycol monomethyl ether solution of surfactant (g-1). It means a value obtained by reducing the tension (mN / m, 25 ° C.).

  The surfactant (g-1) is not particularly limited as long as it satisfies the general formula (I), but various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, it is preferable to use a nonionic surfactant from the viewpoint of influence on the voltage holding ratio when applied to a liquid crystal panel. Further, from the viewpoint of resist film uniformity, a fluorine-based or silicon-based surfactant is preferable, and a fluorine-based surfactant is more preferable.

  Further, the value of Δγ (toluene) of the surfactant (g-1) is not particularly limited, but is preferably 1.8 or more, more preferably 2.0 or more, further preferably 2.2 or more, and 3. 0 or less is preferable, 2.8 or less is more preferable, and 2.6 or less is more preferable. When it is at least the lower limit value, the coating film uniformity tends to be good, and when it is at most the upper limit value, the pigment dispersion stability in the resist tends to be good.

Further, the value of Δγ (propylene glycol monomethyl ether) of the surfactant (g-1) is not particularly limited, but is preferably 1.5 or more, more preferably 1.7 or more, further preferably 1.9 or more, 2.7 or less is preferable, 2.5 or less is more preferable, and 2.3 or less is more preferable. By setting it as the said lower limit or more, there exists a tendency for coating-film uniformity to become favorable, and there exists a tendency for the board | substrate adhesion fall after exposure to high temperature and high humidity to be suppressed by setting it as the said upper limit or less.
For example, a surface tension meter DY-700 or DY-500 manufactured by Kyowa Interface Science Co., Ltd. can be used for measuring the surface tension.

  Examples of such a surfactant (g-1) include F-554 (manufactured by DIC). The surfactant (g) may contain other surfactants other than the surfactant (g-1). Examples of other surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), KP340 ( Shin-Etsu Silicone), F-470, F-475, F-478, F-559 (DIC), SH7PA (Toray Dow Corning), DS-401 (Daikin), L-77 ( Nippon Unicar Co., Ltd.), FC4430 (manufactured by 3M Japan), and the like.

The content ratio of the surfactant (g) in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more in the total solid content. Further, it is preferably 1.0% by mass or less, more preferably 0.7% by mass or less, further preferably 0.5% by mass or less, and 0.3% by mass or less. Is particularly preferred. When the lower limit value is set, the resist coating uniformity tends to be improved, and when the upper limit value is set, the resist sensitivity tends not to decrease.
Further, the content ratio of the surfactant (g-1) in the surfactant (g) is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass. % Or more, more preferably 100% by mass or less. By setting it as the said lower limit or more, there exists a tendency for the adhesive force fall after exposure of a cured film to high temperature, high humidity to be suppressed.

As described above, in the formula (I), Δγ (toluene) represents the surface tension (mN / m, 25 ° C.) of toluene from the surface tension (0.1% by mass) of a 0.1% by mass toluene solution of the surfactant (g-1). mN / m, 25 ° C.). This is an index of how much the surfactant exerted the surfactant action in the solvent. The same applies to Δγ (propylene glycol monomethyl ether).
Therefore, the surfactant which functions in toluene which is a nonpolar solvent rather than propylene glycol monomethyl ether which is a polar solvent is selected according to the formula (I). (Since many fluorine-based surfactants are insoluble in water, we use propylene glycol monomethyl ether, a polar solvent that dissolves widely.)
From the viewpoint of the hydrophilic / hydrophobic balance of the surfactant, the surfactant that functions effectively in the polar solvent tends to have a higher hydrophilicity. Conversely, surfactants that function effectively in nonpolar solvents tend to be relatively hydrophilic. In formula (I), a relatively low hydrophilic surfactant is selected.

<Board adhesion effect>
The organosilicon compound (f-1) has the effect of improving the adhesion between the substrate and the cured film due to the structure of the general formula (1), and its action is considered as follows.

First, by having a silane site, the silanol group is adsorbed by an interaction such as hydrogen bonding with the polar group of the substrate. Alkoxy groups bonded to Si are heated to high temperatures after being hydrolyzed to become silanol groups under the action of moisture in the film before curing (derived from environmental humidity or taken up when processed with an aqueous alkaline developer). It is considered that the treatment causes dehydration condensation with the hydroxyl group on the substrate surface to form a strong chemical bond with the substrate.
Such a strong bond is also formed at the time of coating / drying processing at the time of manufacturing a color filter, at the time of processing with an alkaline developer, or at a high temperature heat treatment at 200 ° C. or higher.

Moreover, the urethane bond part in the said General formula (1-1) is a carboxyl group, ester group, an epoxy acrylate group, etc. which are contained in alkali-soluble resin in a photosensitive resin composition, a photopolymerizable monomer, a dispersing agent, etc. It is considered that the photosensitive resin composition and the substrate are more firmly adhered to each other through the organosilicon compound (f-1) by bonding with the polar group through hydrogen bonding or charge interaction.
This effect is synergistically improved especially when the photopolymerizable monomer has an ester bond or the dispersant has a urethane bond.

  Furthermore, the unsaturated group in the general formula (1-1) is cross-linked to the alkali-soluble resin in the photosensitive resin composition or the unsaturated group in the photopolymerizable monomer, and to ultraviolet irradiation or high heat treatment during color filter production. I think that. In particular, when the photopolymerization initiator in the photosensitive resin composition contains a highly sensitive material such as an oxime ester, the effect is considered to be synergistically improved.

  Thus, due to the synergistic effect of the silane moiety in the general formula (1), the urethane bond site in the general formula (1-1), and the unsaturated group moiety, the substrate and the photosensitive resin composition It is considered that the adhesion is greatly improved. Further, if there is a non-uniform portion in the coating film, it may cause a decrease in substrate adhesion, but the surfactant (g-1) contributes to the formation of a uniform coating film by satisfying the general formula (I).

<Inhibition effect on decrease in substrate adhesion after exposure to high temperature and high humidity>
Usually, surfactants are added to improve coatability such as repellency control, but remain in the coating after forming the coating. Therefore, selection according to the application is necessary so as not to adversely affect the subsequent steps. .
The surfactant (g-1) has the effect of suppressing the decrease in adhesion of the substrate after exposure to high temperature and high humidity by satisfying the general formula (I), and the action is considered as follows.

Curing when exposed to high temperatures and high humidity by selecting from surfactants with a higher hydrophilic / hydrophobic balance while maintaining the coatability improvement effect that is the basic performance of surfactants. It is thought that moisture absorption to the whole film is suppressed.
In addition, at the interface between the substrate and the cured film, the surfactant gathers with the hydrophilic portion facing the substrate side such as glass, but by reducing the hydrophilicity of the surfactant, the amount of moisture gathered at this interface can be suppressed. Conceivable.
Furthermore, by using a fluorosurfactant, the surface is covered with a fluorinated group that protrudes toward the gas phase when the coating is formed. It is thought that.
The moisture absorption of the cured film expands the cured film and generates stress between the substrate and the substrate. Since such stress causes micro cracks in the cured film, it leads to a decrease in substrate adhesion. Suppressing moisture permeation and moisture absorption under high temperature and high humidity is effective in suppressing decrease in substrate adhesion.

<Alkali-soluble resin (a)>
The photosensitive resin composition of this invention contains alkali-soluble resin (a). The alkali-soluble resin (a) is particularly limited as long as the solubility of the exposed portion and the non-exposed portion in alkali development changes after exposure of the cured film obtained by applying and drying the photosensitive resin composition. Although not made, it is preferably an alkali-soluble resin having a carboxyl group. Moreover, what has an ethylenically unsaturated group is preferable, and alkali-soluble resin which has an ethylenically unsaturated group and a carboxyl group is still more preferable. Specific examples include an epoxy (meth) acrylate resin and an acrylic copolymer resin having a carboxyl group, and more preferable examples are (A1-1), (A1-2), (A2- Examples include 1), (A2-2), (A2-3) and (A2-4), and these may be used alone or in combination of two or more. Among the above, epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxyl group are particularly desirable.

  When creating a color filter, a polymer resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphoric acid group, or a sulfonic acid group is applied as a polymer resin so that the non-exposed portion is dissolved in an alkaline developer. The Among these, from the viewpoint of solubility in an alkaline developer, a polymer resin having a carboxyl group is preferable. In addition, although phosphoric acid groups and sulfonic acid groups have higher acidity than carboxyl groups, they easily react with initiators, monomers, dispersants and other additives having basic groups in the photosensitive resin composition. , Storage stability may deteriorate.

  In addition, the organosilicon compound (f-1) having a urethane bond site represented by the general formula (1) is bonded to a polar group such as a carboxyl group in an alkali-soluble resin by a hydrogen bond or a charge interaction. The adhesion between the photosensitive resin composition and the substrate tends to be further improved.

  Furthermore, the organosilicon compound (f-1) having an unsaturated group represented by the general formula (1) includes an ethylenically unsaturated group in an alkali-soluble resin, ultraviolet irradiation at the time of manufacturing a color filter, and high heat treatment. Sometimes they tend to crosslink with each other and further improve adhesion to the substrate.

  In addition, when an epoxy (meth) acrylate resin is used as an alkali-soluble resin having a carboxyl group and an ethylenically unsaturated group, it becomes possible to add more unsaturated bonds and carboxyl groups in the resin. It is possible to include a large amount of an aromatic ring structure or a sterically bulky alicyclic structure, and the interaction with the organosilicon compound (f-1) is further increased, and the substrate is in close contact with the substrate. There is a tendency for the property to be further improved.

  Examples of the epoxy (meth) acrylate resin having a carboxyl group include the following epoxy (meth) acrylate resin (A1-1) and / or epoxy (meth) acrylate resin (A1-2).

<Epoxy (meth) acrylate resin (A1-1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Epoxy (meth) acrylate resin (A1-2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.

(Epoxy (meth) acrylate resin (A1-1) having carboxyl group and ethylenically unsaturated group bond)
As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat (registered trademark; the same applies hereinafter) 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004” manufactured by Mitsubishi Chemical Corporation, etc. ), Epoxy obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, “NER-1302” manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76 ° C.)), bisphenol F type resin ( For example, “Epicoat 807”, “EP-4001”, “EP-4002”, “EP-4004 etc.” manufactured by Mitsubishi Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (For example, “NER-7 manufactured by Nippon Kayaku Co., Ltd. 06 ”(epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg“ YX-4000 ”manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (eg Nippon Kayaku Co., Ltd.) "EPPN-201" manufactured by Mitsubishi Chemical Corporation, "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o, m, p-) cresol novolac type epoxy resin (For example, “EOCN (registered trademark) manufactured by Nippon Kayaku Co., Ltd.”) “102S”, “EOCN-1020”, “EOCN-104S”), triglycidyl isocyanurate (for example, “TEPIC manufactured by Nissan Chemical Co., Ltd.) (Registered trademark) ”), trisphenolmethane type epoxy resin (for example,“ EPPN (registered trademark) manufactured by Nippon Kayaku Co., Ltd. ) -501 "," EPN-502 "," EPPN-503 "), cycloaliphatic epoxy resin (" Celoxide (registered trademark; the same applies hereinafter) 2021P "," Celoxide EHPE "manufactured by Daicel Corporation), Di Epoxy resins obtained by glycidylation of a phenol resin by reaction of cyclopentadiene and phenol (for example, “EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), the following general formulas (a1) to (a4) The epoxy resin etc. which are represented by these can be used suitably. Specifically, “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (a1) and “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (a2) NC-3000 ”,“ ESF-300 ”manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and the like can be given as epoxy resins represented by the following general formula (a4).

In the said general formula (a1), b11 shows an average value and shows the number of 0-10. R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. A plurality of R ¹¹ present in one molecule may be the same as or different from each other.

In the said general formula (a2), b12 shows an average value and shows the number of 0-10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. A plurality of R ²¹ present in one molecule may be the same as or different from each other.

  In the general formula (a3), X represents a linking group represented by the following general formula (a3-1) or (a3-2). However, one or more adamantane structures are included in the molecular structure. b13 represents an integer of 2 or 3.

In the general formulas (a3-1) and (a3-2), R ^{31 to} R ³⁴ and R ^{35 to} R ³⁷ are each independently an adamantyl group, a hydrogen atom, or a substituent which may have a substituent. The alkyl group of C1-C12 which may have this, or the phenyl group which may have a substituent is shown. Moreover, * mark in a formula represents the binding site in (a3).

In the general formula (a4), p and q each independently represent an integer of 0 to 4, and R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom. R ⁴³ and R ⁴⁴ each independently represents an alkylene group. x and y each independently represents an integer of 0 or more.
Among these, it is preferable to use an epoxy resin represented by any one of the general formulas (a1) to (a4).

Examples of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) a Acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyl Loxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid,
The (meth) acrylic acid ester is a single monomer having one hydroxyl group at the terminal by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to (meth) acrylic acid. Body,
Alternatively, a monomer having one hydroxyl group at the end, such as hydroxyalkyl (meth) acrylate, or a compound having one hydroxyl group at the end, such as pentaerythritol tri (meth) acrylate, is added to (anhydrous) succinic acid, (Meth) acrylic acid ester having one or more ethylenically unsaturated groups and one carboxyl group at the end by adding an acid (anhydride) such as (anhydrous) phthalic acid or (anhydrous) maleic acid . Moreover, (meth) acrylic acid dimer etc. are also mentioned.

Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
As a method of adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin, a known method can be used. For example, reacting an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group with an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. it can. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used. .

In addition, the epoxy resin, the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two types. You may use the above together.
The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents.
If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid and / or anhydride thereof The reaction with is also insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  Polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthal Examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

  Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or their anhydrides. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

  A known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid having carboxyl group to epoxy resin. The target product can be obtained by continuing the reaction under the same conditions as in the ester addition reaction. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mg KOH / g, and further 20 It is preferable that it is a grade which becomes the range of -140 mgKOH / g. There exists a tendency for alkali developability to become favorable by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to become favorable by setting it as the said upper limit or less.

((A1-1) Synthesis of Resin and (A1-1) Synthesis of Resin with Addition of Polyhydric Alcohol to Resin and Introduced Branch Structure)
In the addition reaction synthesis of the polybasic acid and / or anhydride thereof of the (A1-1) resin, polyhydric alcohol such as trimethylolpropane, pentaerythritol, dipentaerythritol is added, and a multi-branched structure is introduced. Also good.
The carboxyl group-containing epoxy (meth) acrylate resin is usually a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. Or after mixing the anhydride, or a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group with a polybasic acid and / or Or it is obtained by heating after mixing the anhydride and polyhydric alcohol. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyhydric alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyhydric alcohol by heating. To the polybasic acid and / or its anhydride.

The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or as a mixture of two or more resins.
If the amount of polyhydric alcohol is too small, the effect is thin, and if it is too large, there is a possibility of thickening or gelation. Therefore, a carboxyl group is added to the epoxy resin component and the α, β-unsaturated monocarboxylic acid or ester moiety. It is about 0.01-0.5 mass times normally with respect to the reaction material with the (alpha), (beta)-unsaturated monocarboxylic acid ester component which has, Preferably it is about 0.02-0.2 mass times.

  The acid value of the epoxy (meth) acrylate resin (A1-1, A1-2) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more, and preferably 200 mgKOH / g or less. More preferably, it is 150 mgKOH / g or less. There exists a tendency for developability to become favorable by setting it as the said lower limit or more, and there exists a tendency which can make alkali resistance favorable by setting it as the said upper limit or less.

  The weight average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resin (A1-1, A1-2) is preferably 1,000 or more, and 1,500. More preferably. Further, it is preferably 10,000 or less, more preferably 8,000 or less, and still more preferably 6,000 or less. Sensitivity, coating film strength and alkali resistance tend to be good when the lower limit value is exceeded, and developability and re-dissolvability tend to be good when the upper limit value or less. .

(Acrylic copolymer resin (A2-1) (A2-2) (A2-3) (A2-4))
Examples of the acrylic copolymer resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, and JP-A-2000-56118. Various polymer compounds described in JP-A-2003-233179, JP-A-2007-270147, and the like can be used. Preferably, the following (A2-1) to (A2-) 4) resin etc. are mentioned, Among these, (A2-1) resin is particularly preferable.

(A2-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin obtained by addition, or resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction (A2-2): linear alkali-soluble containing a carboxyl group in the main chain Resin (A2-3): Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the (A2-2) resin (A2-4): (Meth) acrylic resin

  From the viewpoint of sensitivity, the photosensitive resin composition of the present invention is (A1-1), (A1-2), (A2-1), (A2-3) as an alkali-soluble resin containing an ethylenically unsaturated group. It is more preferable that at least one of these is included. The photosensitive resin composition of the present invention is an epoxy (meth) acrylate resin as an alkali-soluble resin containing an ethylenically unsaturated group from the viewpoint of surface curability, and is at least one of (A1-1) and (A1-2). It is particularly preferable to include any of them.

The photosensitive resin composition of the present invention may be used in combination with other alkali-soluble resins.
There is no restriction | limiting in other alkali-soluble resin, What is necessary is just to select from resin normally used for the photosensitive resin composition for color filters. Examples thereof include alkali-soluble resins described in JP2007-271727A, JP2007-316620A, JP2007-334290A, and the like.

Content of alkali-soluble resin (a) is 5 mass% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 10 mass% or more, More preferably, it is 15 mass% or more, Usually, it is 90 mass% or less, Preferably it is 70 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 30 mass% or less. By setting the lower limit value or more, there is a tendency that the solubility of the unexposed portion in the developer tends to be good, and by setting the upper limit value or less, excessive penetration of the developer into the exposed portion can be suppressed. And there is a tendency for the image to be sharp and to have good adhesion.
In addition, as above-mentioned, the photosensitive resin composition of this invention is the above-mentioned (A1-1), (A1-2), (A2-1), (A2-2) as alkali-soluble resin (a). , (A2-3) and (A2-4) are preferably included, and when other alkali-soluble resin is included, the content ratio is 20 mass with respect to the total of the alkali-soluble resin (a). % Or less, preferably 10% by mass or less.

<Photopolymerizable monomer (b)>
The photosensitive resin composition of this invention contains a photopolymerizable monomer (b) from points, such as a sensitivity.
Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as “ethylenic monomer”). Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. Can be mentioned.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is usually 2 or more, preferably 3 or more, more preferably 4 or more, further preferably 5 or more, particularly preferably 6 or more, and usually 10 or less, preferably 8 or less. When the amount is not less than the lower limit, the resist tends to have high sensitivity, and when the amount is not more than the upper limit, curing shrinkage during polymerization tends to be small.
Examples of the polyfunctional ethylenic monomer include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, and an aromatic polyhydroxy compound. Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester instead of itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. Etc.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol, and glycerin.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.
These may be used alone or in combination of two or more.

  The proportion of the photopolymerizable monomer (b) is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and further preferably 30% by mass with respect to the total solid content of the photosensitive resin composition. % Or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. When the content of the photopolymerizable monomer is not more than the above upper limit, the permeability of the developer into the exposed area becomes appropriate, and a good image tends to be obtained. The lower limit of the content of the photopolymerizable monomer (b) is usually 1% by mass or more, preferably 5% by mass or more. By being more than the said minimum, it exists in the tendency for the photocuring by ultraviolet irradiation to improve, and for alkali developability to also become favorable.

<Photopolymerization initiator (c)>
The photopolymerization initiator is a component having a function of directly absorbing light and causing a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. If necessary, an additive such as a sensitizing dye may be added and used.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbi compounds described in JP-A-2000-56118. Imidazole derivatives; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503, N-aryl-α-amino acid salts, Radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A, JP 2006-36750 A, and the like. .

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-difluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxy) Phenyl) -4,5-diphenylimidazole dimer and the like.

  Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

  Examples of α-aminoalkylphenone derivatives include 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-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like It is.

As photopolymerization initiators, oxime derivatives (oxime ester compounds and ketoxime ester compounds) are particularly effective in terms of sensitivity, and when using an alkali-soluble resin containing a phenolic hydroxyl group, sensitivity is particularly high. In particular, such oxime derivatives (oxime ester compounds and ketoxime compounds) excellent in sensitivity are useful. Among oxime derivatives, an oxime ester compound is preferable from the viewpoint of adhesion to a substrate.
Photopolymerization initiators of oxime ester compounds have both a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals. Therefore, it is possible to design a photosensitive resin composition that is stable and sensitive in a small amount. In particular, in the case of an oxime ester-based compound containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring) from the viewpoint of light absorption with respect to i-line (365 nm) of an exposure light source, This structural characteristic is favorably expressed and more preferable. Currently, the market demands a high degree of shading, a thin BM (black matrix), and the pigment concentration is also increasing. In such a situation, it is particularly effective.

  As described above, the organosilicon compound (f-1) has an unsaturated group of (meth) acryloyloxy group, which is unsaturated in an alkali-soluble resin or photopolymerizable monomer contained in the photosensitive resin composition. It is considered that the adhesion with the substrate can be greatly improved by crosslinking with the group at the time of ultraviolet irradiation at the time of manufacturing the color filter or at the time of high heat treatment. In particular, when the initiator in the photosensitive resin composition contains an oxime ester having the above characteristics, the effect is considered to be synergistically improved.

  Examples of the oxime ester compound include a compound containing a structural moiety represented by the following general formula (22), and preferably include an oxime ester compound represented by the following general formula (23).

In the above formula (22), R ²² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number. 3 to 8 cycloalkanoyl group, 3 to 20 alkoxycarbonylalkanoyl group, 8 to 20 phenoxycarbonylalkanoyl group, 3 to 20 heteroaryloxycarbonylalkanoyl group, 2 to 10 carbon atoms An aminoalkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroarylloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms is shown.

(In formula (23), R ^21a is hydrogen or an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroarylalkyl group having 1 to 20 carbon atoms. , C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, C1-C20 aminoalkyl Group, alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, heteroarylloyl group having 1 to 20 carbon atoms, C2-C10 alkoxycarbonyl group, C7-C20 aryloxycarbonyl group, or C1-C10 A chloroalkylalkyl group is shown.
R ^21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.

R ^21a may form a ring together with R ^21b , and each of the linking groups thereof may have a substituent, an 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 ^22a represents the same group as R ²² in the above formula (22).
R ²² in the general formula (22) and R ^22a in the general formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Of the cycloalkanoyl group.

R ^21a in the general formula (23) is preferably substituted with a linear alkyl group such as an unsubstituted methyl group, ethyl group or propyl group or a cycloalkylalkyl group, or an N-acetyl-N-acetoxyamino group. And propyl group.
In addition, R ^21b in the general formula (23) is preferably an optionally substituted carbazole group, an optionally substituted thioxanthonyl group, or an optionally substituted phenyl sulfide group.

As the oxime ester photopolymerization initiator (c), those containing a carbazole group which may be substituted as R ^21b are more preferable for the reasons described above. Furthermore, an aryl group having 6 to 25 carbon atoms which may be substituted, an arylcarbonyl group having 7 to 25 carbon atoms which may be substituted, a heteroaryl group having 5 to 25 carbon atoms which may be substituted, and substitution A carbazole group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms and a nitro group which may be used is preferable. In particular, a carbazole group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group, and a nitro group is preferable. These groups are preferably bonded to the 3-position of the carbazole group.

  Commercially available products of such oxime ester photopolymerization initiator (c) include OXE-02 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power Electronics.

  Specific examples of the oxime ester photopolymerization initiator (c) include compounds exemplified below as oxime ester compounds suitable for the present invention, but the oxime ester photopolymerization initiator (c) is not limited to these compounds. .

  Examples of the ketoxime ester compound include a compound containing a structural portion represented by the following general formula (24), and preferably an oxime ester compound represented by the following general formula (25).

(In the general formula (24), R ²⁴ has the same meaning as R ²² in the general formula (22).)

(In the above general formula (25), each R ^23a may be a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroaryl having 1 to 20 carbon atoms. An alkyl group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms, or heteroary Ruthioalkyl group, C1-C20 aminoalkyl group, C2-C12 alkanoyl group, C3-C25 alkenoyl group, C3-C8 cycloalkanoyl group, C7-C20 aryloyl group , A C1-C20 heteroaryloyl group, a C2-C10 alkoxycarbonyl group, a C7-C2 0 aryloxycarbonyl group or a C1-C10 cycloalkylalkyl group is shown.

R ^23b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ^23a may form a ring together with R ^23b , and the linking group thereof may have an optionally substituted alkylene group having 1 to 10 carbon atoms or 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 ^24a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, carbon Heteroaryloyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylamino having 2 to 20 carbon atoms Represents a carbonyl group. )
R ²⁴ in the general formula (24) and R ^24a in the general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. And a cycloalkanoyl group and an aryloyl group having 7 to 20 carbon atoms.

R ^23a in the general formula (25) is preferably an unsubstituted ethyl group, propyl group, butyl group, or an ethyl group or propyl group substituted with a methoxycarbonyl group.
In addition, R ^23b in the general formula (25) is preferably an optionally substituted carbazoyl group or an optionally substituted phenyl sulfide group.
Specific examples of the ketoxime ester-based compound suitable for the present invention include compounds exemplified below, but the ketoxime ester-based compound is not limited to these compounds.

  Commercially available products of such oxime ester photopolymerization initiator (c) include OXE-01 manufactured by BASF, TR-PBG-305 manufactured by Changzhou Strong Electronic Co., Ltd.

These oxime and ketoxime ester compounds are known compounds 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.

Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p- Methoxyph Yl) acridine derivatives acridine like; 9,10-dimethyl-benz phenazine phenazine derivatives such as; anthrone derivatives such as benzanthrone etc. may be mentioned.
Among these photopolymerization initiators, oxime ester derivatives are particularly preferable for the reasons described above.

<Sensitizing dye>
If necessary, the photopolymerization initiator can be used in combination with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-diethyl Aminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p -Dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. and p-dialkylaminophenyl group-containing compounds.
Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

Content of a photoinitiator (c) is 0.1 mass% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 0.5 mass% or more, More preferably, it is 1 mass. More preferably, it is 5% by mass or more, usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. When it is at least the lower limit, there is a tendency that it is possible to suppress a decrease in sensitivity, and when it is at most the upper limit, there is a tendency that the solubility of the unexposed portion in the developing solution can be improved.
In particular, the proportion of the oxime ester compound in the photopolymerization initiator (c) is usually 10% by mass or more, preferably 50% by mass or more, more preferably 90% by mass or more. By setting it to the above lower limit or more, when the organosilicon compound (f-1) of the present invention and an alkali-soluble resin are combined as the photosensitive resin composition of the present invention, the adhesion to the substrate is further increased after irradiation with ultraviolet rays. There is a tendency to improve.

  When using an accelerator with a photoinitiator (c), content of an accelerator is 0 mass% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 0.02 mass%. In the above, it is usually 10% by mass or less, preferably 5% by mass or less, and the accelerator is a proportion of 0.1 to 50% by mass, particularly 0.1 to 10% by mass with respect to the photopolymerization initiator (c). It is preferable to use in. There exists a tendency which can suppress a sensitivity fall by setting it as the said lower limit or more, and there exists a tendency which can improve the solubility with respect to the developing solution of an unexposed part by setting it as the said upper limit or less.

  Moreover, when using a sensitizing dye, the compounding ratio of the sensitizing dye in the photosensitive resin composition of this invention is 0-20 mass% normally in the total solid in the photosensitive resin composition, Preferably it is 0-0. It is 15 mass%, More preferably, it is 0-10 mass%.

<Coloring material (d)>
The photosensitive resin composition of the present invention contains a coloring material when used for forming a pixel of a color filter, a black matrix, or the like. A coloring material means what colors the photosensitive resin composition of this invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.

  As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is.

Hereinafter, specific examples of pigments that can be used in the present invention are shown by pigment numbers. Note that terms such as “CI Pigment Red 2” mentioned below mean a 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. Pigment Green 7, 36, 58.

  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.

Moreover, when the photosensitive resin composition of this invention is the photosensitive resin composition for resin black matrices of a color filter, a black coloring material can be used as a coloring material (d). The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes.
Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  Further, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.
Among these color materials (d), when a black color material is used as the photosensitive resin composition, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

  Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350 # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Made by Degussa: Printex (registered trademark; The same.) 3, Printex3OP, Printex30, Printex30OP, Print x40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color black FW200, Color Black S160, Color Black S170 Cabot: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1, Monarch1100, Monarch1100, Monarch1100, Monarch1100, Monarch1100 The same shall apply hereinafter.) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8

Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890, Raven1000, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

Carbon black coated with a resin may be used. Use of carbon black coated with a resin has the effect of improving adhesion to a glass substrate and volume resistance. As carbon black coated with resin, for example, carbon black described in JP-A No. 09-71733 can be suitably used.
As carbon black to be coated, the total content of Na and Ca is preferably 100 ppm or less. Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al, Fe, etc. Is contained in the order of percent. Of these, Na and Ca are generally contained in a few hundred ppm or more, but if many of these are present, they penetrate into the transparent electrode (ITO) and other electrodes, causing electrical shorts. This is because there is a case.

  As a method for reducing the content of ash containing these Na and Ca, carefully select those with as little content as possible as raw oil, fuel oil (or gas) and reaction stop water when producing carbon black. This is possible by reducing the addition amount of the alkaline substance for adjusting the structure as much as possible. As another method, carbon black produced from the furnace is washed with water, hydrochloric acid or the like, and Na or Ca is dissolved and removed.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment. These various pigments can be used in combination. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

<Particle particle size>
The average particle diameter of the pigment used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a colored layer of a color filter, and varies depending on the type of pigment used. It is preferably in the range of ˜100 nm, more preferably in the range of 10 to 70 nm. When the average particle diameter of the pigment is within the above range, the color characteristics of the liquid crystal display device produced using the photosensitive resin composition of the present invention can be made high quality.
In addition, when the pigment is carbon black, the average particle diameter of the pigment is preferably 60 nm or less, and more preferably 50 nm or less. Further, when the pigment is carbon black, the average particle diameter of the pigment is preferably 20 nm or more. If the pigment becomes too large, scattering increases and color characteristics such as light shielding properties and contrast tend to deteriorate. On the other hand, if the pigment particle size is too small, a large amount of dispersant is required, and the dispersibility tends to decrease.
In addition, the average particle diameter of the pigment can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (mass) of each particle is obtained by approximating a cuboid with the obtained particle size, and the volume average particle size is obtained and used as the average particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

  Moreover, although it is preferable that the photosensitive resin composition of this invention contains a pigment at least, you may use together a dye in the range which does not affect the effect of this invention besides. Examples of dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  The content rate of a coloring material (d) can be normally selected in 1-70 mass% with respect to the total amount of solids in the photosensitive resin composition. In this range, 20 mass% or more is more preferable, 40 mass% or more is more preferable, and 60 mass% or less is more preferable.

  The photosensitive resin composition of the present invention can be used for various applications as described above, but excellent image forming properties are particularly effective when used for forming a black matrix for a color filter. . When using it for forming a black matrix, use a black color material such as carbon black or titanium black described above as the color material (d), or mix several types of color materials other than black and adjust to black. It ’s fine. Among these, it is particularly preferable to use carbon black from the viewpoint of dispersion stability.

  The present invention is particularly effective in the region where the pigment concentration of the black pigment increases. Particularly in recent years, it is necessary to increase the black pigment concentration in order to increase the degree of light shielding. The content of the black pigment in the region where the effect is large is a region of 40% by mass or more with respect to the total solid content of the photosensitive resin composition. The effect is greater when it is 45% by mass or more, and the effect can be further enhanced when it is 50% by mass or more.

  In the photosensitive resin composition, when the black pigment is contained within the above content range, a photosensitive resin composition having high light shielding properties (optical density, OD value) can be obtained. Specifically, by setting the black pigment content to 45% by mass or more, the optical density when the black matrix having a thickness of 1 μm is formed using the photosensitive resin composition of the present invention is 4.0 or more. Can be a value. The optical density is more preferably 4.2 or more. In regions with high light shielding properties, ultraviolet rays are difficult to penetrate deeply, and crosslinking due to photopolymerization is weak particularly in the area where the substrate and fine wires are in close contact, but particularly when the photosensitive resin composition of the present invention is used, the pigment concentration When the value is large, the effect of the present invention can be confirmed well. A pigment concentration of 40 to 65% by mass is particularly effective. When it is at least the lower limit, there is a tendency that the film thickness with respect to the color density is prevented from becoming too large, and when it is at most the upper limit, there is a tendency that sufficient image formability is easily secured.

  In the photosensitive resin composition, the content ratio of the coloring material (d) is usually 20 to 500 parts by mass, preferably 30 to 300 parts by mass, more preferably 40 to 200, per 100 parts by mass of the alkali-soluble resin (a). It is the range of mass parts. By setting it to the lower limit value or more, there is a tendency that it is easy to suppress a decrease in the solubility of the unexposed portion in the developer, and by setting the upper limit value or less, a desired image thickness tends to be obtained.

<Dispersant (e)>
In the present invention, it is important to finely disperse the color material and stabilize the dispersion state, so that it is important to ensure the stability of the quality.
As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino group. A quaternary ammonium base; a polymer dispersant having a functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine and pyrazine, is preferable. Among these, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, pyrazine, or the like is particularly preferable. By using the polymer dispersant having these basic functional groups, there is a tendency that the dispersibility can be improved and a high light-shielding property can be achieved.

  Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include a dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

Specific examples of such a dispersant are trade names of EFKA (registered trademark, manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (registered trademark, manufactured by BYK Chemie), and Disparon (registered trademark, Enomoto Kasei). , SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Florene (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Fine Techno Co., Ltd.) Etc.).
These polymer dispersants may be used alone or in combination of two or more.

  Among these, it is particularly preferable that the dispersant (e) contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a basic functional group in terms of adhesion and linearity. In particular, a urethane-based polymer dispersant is preferable in terms of adhesion. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester and / or polyether bond is preferred.

  As described above, the organosilicon compound (f-1) of the present invention has a synergistic action of its organosilane site, urethane bond site, and ethylenically unsaturated group site, so that it can be used at high temperature and high humidity or at room temperature. Improves adhesion between the cured product and the substrate. It is considered that the urethane bond site of the organosilicon compound (f-1) can form a bond with the urethane bond site of the urethane-based polymer dispersant with an affinity such as hydrogen bond, and can further improve the adhesion to the substrate. It is done. Therefore, urethane polymer dispersants are particularly preferred in the present invention.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less. By setting it to the upper limit or less, the alkali developability tends to be good even when the pigment concentration is high.
Examples of urethane-based and acrylic polymer dispersants include Disperbyk 160 to 167, 182 series (both are urethane-based), Disperbyk 2000, 2001, etc. (both are acrylic-based) (all manufactured by Big Chemie). Disperbyk 167, 182 and the like are preferable as a urethane polymer dispersant having a basic functional group and having a polyester and / or polyether bond and having a weight average molecular weight of 30,000 or less.

(Urethane polymer dispersant)
If a chemical structure preferable as a urethane polymer dispersant is specifically exemplified, for example, the same as a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule Examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule.

  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, , 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 initiated with an alcohol having 1 to 25 carbon atoms.

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 usually 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. The hydrogen atom of the amino group is preferable.

The tertiary amino group is not particularly limited, and examples thereof 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, when the tertiary amino group is a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo N-containing hetero 5-membered ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., nitrogen-containing hetero 6-membered ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned. Among these nitrogen-containing heterocycles, preferred are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and an 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 preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 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 mass of the polyisocyanate compound. To 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3. -24 parts by mass.

  Manufacture of a urethane type polymer dispersing agent is performed in accordance with the well-known method of polyurethane resin manufacture. 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 Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of two or more.

  In the above production, a urethanization reaction catalyst is usually 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.

<Method of measuring amine value>
The tertiary amine value of the dispersant is represented by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and can be measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ (perchloric acid) acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]
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 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino 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 polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.
The weight average molecular weight (Mw) of the urethane-based polymer 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. In particular, 30,000 or less is preferable. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility tends to be low and the dispersibility is poor, and at the same time, the reaction tends to be difficult to control. When the molecular weight is 30,000 or less, alkali developability tends to be good even when the pigment concentration is particularly high. Examples of such a particularly preferred commercially available urethane dispersant include Disperbyk 167 and 182 (Bic Chemie).

  The content of the dispersant is usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, usually 1% by mass or more, preferably 3% by mass in the total solid content of the photosensitive resin composition. As mentioned above, More preferably, it is 5 mass% or more, More preferably, it is 7 mass% or more. Further, the content of the dispersant is usually 5% by mass or more, particularly 10% by mass or more, and usually 200% by mass or less, and particularly preferably 80% by mass or less, with respect to the coloring material (d). There is a tendency to ensure sufficient dispersibility by setting the lower limit value or more, and by reducing the ratio of other components by setting the upper limit value or less, the color density, sensitivity, film formability, etc. There is a tendency to be sufficient.

  In particular, it is preferable to use a polymer dispersant and a pigment derivative in combination as the dispersant. In this case, the blending ratio of the pigment derivative is usually 0 with respect to the total solid content of the photosensitive resin composition of the present invention. .1% by mass or more, usually 10% by mass or less, preferably 5% by mass or less.

<Thiols>
It is preferable to add thiols to the photosensitive resin composition of the present invention in order to increase sensitivity and improve adhesion to the substrate. Types of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate , Butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate); (PGMB for short), Diol (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane; (trade name; Karenz MT BD1, manufactured by Showa Denko KK), butanediol trimethylolpropane tris (3-mercapto) Butyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz MT PE1, Showa Denko KK), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoiso) (Butyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptobutyrate); (TPMB for short) trimethylolpropane tris (2 Mercaptoisobutyrate); (TPMIB for short), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Trade name; Karenz MT NR1, manufactured by Showa Denko Co., Ltd.) and the like, and various of these may be used alone or in combination of two or more. Preferred are polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1, among which Karenz MT BD1, Karenz MT PE1 and Karenz MT NR1 are more preferable, and Karenz MT PE1 is preferable. Particularly preferred.

  When a thiol compound is used, the content of the thiol compound is usually 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0%, based on the total solid content of the photosensitive resin composition of the present invention. 0.5 mass or more, usually 10 mass% or less, preferably 5 mass% or less. There exists a tendency which can suppress a sensitivity fall by setting it as the said lower limit or more, and there exists a tendency which is easy to make a storage stability favorable by setting it as the said upper limit or less.

<Solvent>
The photosensitive resin composition of the present invention usually contains an alkali-soluble resin (a) containing an ethylenically unsaturated group, a photopolymerizable monomer (b), a photopolymerization initiator (c), a color material (d), a dispersion. The agent (e), the organosilicon compound (f), the surfactant (g), and various materials used as necessary are used in a state of being dissolved or dispersed in an organic solvent.
As an organic solvent, it is preferable to select an organic solvent having a boiling point (under a pressure of 101.25 [hPa], hereinafter the same for boiling points) in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.
Examples of such organic solvents include the following.

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;

  Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxy Tyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol mono Glycol alkyl ether acetates such as ethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

  Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, Ethers such as dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone , Methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Mono ketones such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol Aliphatic alcohols such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane; alicyclic rings such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl Formula hydrocarbons;

  Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, Propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-methoxy Linear or cyclic esters such as ethyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and gamma-butyrolactone; alkoxy groups such as 3-methoxypropionic acid and 3-ethoxypropionic acid Bonn acids;

  Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile, etc .: Examples of commercially available solvents corresponding to the above include mineral spirits and valsols # 2, Apco # 18 Solvent, Apco Thinner, Soak Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cerosolve" is a registered trademark, the same shall apply hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name).

These organic solvents may be used alone or in combination of two or more.
When forming a pixel or black matrix of a color filter by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120 to 170 ° C.
Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability tends to decrease such as the viscosity of the photosensitive resin composition obtained later increases. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

  It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent together, the photosensitive resin composition becomes difficult to dry, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation or solidification of a color material or the like at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such high effects.

  The content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. If the amount of the high boiling point solvent is too small, for example, a coloring material may precipitate and solidify at the tip of the slit nozzle to cause a foreign matter defect, and if it is too much, the drying temperature of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is not separately contained. It doesn't matter.
Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

  In the photosensitive resin composition of the present invention, the content of the organic solvent is not particularly limited, but from the viewpoint of easy application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, More preferably 8% by mass or more, further preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less. .

<Other ingredients of the photosensitive resin composition>
In addition to the above-described components, the photosensitive resin composition of the present invention can be appropriately mixed with an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a pigment derivative, and the like.

(Adhesion improver)
In order to improve the adhesion to the substrate, an adhesion improver other than the organosilicon compound (f) may be included in the photosensitive resin composition of the present invention. For example, a phosphate adhesion improver, other adhesion enhancement Agents and the like.

  As the phosphate-based adhesion improver, (meth) acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2), and (g3) are particularly preferable.

In the general formulas (g1), (g2), and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l ′ are integers of 1 to 10, and m is 1, 2, or 3.
Other examples of the adhesion improver include TEGO ^* Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesives may be used alone or in combination of two or more.

(Pigment derivative)
The photosensitive resin composition of the present invention may contain a pigment derivative for improving dispersibility and storage stability. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Among them, derivatives such as phthalocyanines and quinophthalones are 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 may be used alone or in combination of two or more.

<Method for producing photosensitive resin composition>
The photosensitive resin composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.
Usually, it is preferable to disperse the color material (d) in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the color material (d) is finely divided by the dispersion treatment, the resist coating characteristics are improved. Further, when a black color material is used as the color material (d), it contributes to an improvement in light shielding ability.

In general, the dispersion treatment is preferably performed in a system in which a coloring material (d), a dispersing agent (e), an organic solvent, and, if necessary, a part or all of the alkali-soluble resin (a) are used in combination. (Hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”.) In particular, when a polymer dispersant is used as the dispersant, the mixture is obtained. In addition, it is preferable because thickening of the ink and resist over time is suppressed (excellent dispersion stability).
In addition, when a dispersion treatment is performed on a liquid containing all components to be blended in the photosensitive resin composition, a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.

  When the color material (d) is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 100 to 200. When the glossiness of the resist is low, the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

  Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.

[Cured product]
A cured product can be obtained by curing the photosensitive resin composition of the present invention. A cured product obtained by curing the photosensitive resin composition can be suitably used as a member constituting a color filter such as a pixel, a black matrix, or a colored spacer.

[Black Matrix]
Next, the black matrix using the photosensitive resin composition of the present invention will be described in accordance with its production method.

(1) Support The support for forming the black matrix is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy resins. And thermosetting resin sheets such as unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.

For the support, to improve surface properties such as adhesiveness, corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agents, and thin film formation treatment of various resins such as urethane resins, etc. May be performed.
The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) Black matrix In order to form the black matrix of the present invention by the above-described photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is applied on a transparent substrate and dried, and then the sample is coated. A black mask is formed by placing a photomask on the substrate and exposing the image through the photomask, developing, and thermosetting or photocuring as necessary.

(3) Formation of black matrix (3-1) Application of photosensitive resin composition Application of a photosensitive resin composition for a black matrix onto a transparent substrate is performed by a spinner method, a wire bar method, a flow coating method, or a die coating method. , Roll coating method or spray coating method. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming process. May become impossible. The thickness of the coating is usually preferably in the range of 0.2 to 10 μm as the film thickness after drying, more preferably in the range of 0.5 to 6 μm, and still more preferably in the range of 1 to 4 μm. is there.

(3-2) Drying of the coating film The drying of the coating film after applying the photosensitive resin composition to the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the alkali-soluble resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
(3-3) Exposure Image exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive resin composition and irradiating an ultraviolet light source or a visible light source through the mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. As the light source, 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, a lamp light source, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

(3-4) Development The black matrix according to the present invention is an aqueous solution containing an organic solvent or a surfactant and an alkaline compound after image-exposing the coating film of the photosensitive resin composition with the above light source. An image can be formed on a substrate by development using a film. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.
The development processing conditions are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., particularly 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

(3-5) Thermosetting treatment The substrate after development is subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes.
The black matrix formed as described above has a bottom width of usually 3 to 50 μm, preferably 4 to 30 μm, particularly 4 to 8 μm in the case of a high fine wire, and a height of usually 0.5 to 5 μm, preferably Is 1 to 4 μm. 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 (OD) per 1 μm thickness is 3.0 or more, preferably 3.5 or more, more preferably 4.0 or more, and particularly preferably 4.2 or more.

[Formation of other color filter images]
On a transparent substrate provided with a black matrix, a photosensitive resin composition containing a color material of one color of red, green, and blue is applied by the same process as (3-1) to (3-5) above and dried. After that, a photomask is overlaid on the coating film, and a pixel image is formed through image exposure, development, and thermosetting or photocuring as necessary through this photomask to form a colored layer. A color filter image can be formed by performing this operation for each of the three color photosensitive resin compositions of red, green, and blue. The order of these is not limited to the above.

[Coloring spacer]
The photosensitive resin composition of the present invention can be used as a resist for colored spacers in addition to the black matrix. When a spacer is used in a TFT type LCD, the TFT may malfunction as a switching element due to light incident on the TFT, and a colored spacer is used to prevent this, for example, Japanese Patent Laid-Open No. 8-234212. Describes that the spacer is light-shielding. The colored spacer can be formed in the same manner as the black matrix described above except that a mask for the colored spacer is used.

(3-6) Formation of transparent electrode In this state, the color filter forms a transparent electrode such as ITO on the image and is used as a part of components such as a color display and a liquid crystal display device. In order to enhance the property and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[Image display device]
The image display device of the present invention is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display described later.
[Liquid Crystal Display]
The liquid crystal display device of the present invention has the above-described black matrix of the present invention, and is not particularly limited in terms of the formation order and formation position of the color pixels and the black matrix.

  A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to a counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and usually a spacer having a size of 2 to 8 μm is preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

[Organic EL display]
The organic EL display of the present invention is produced using the color filter of the present invention.

  When producing an organic EL display using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern (that is, the pixel 20 and the adjacent region) formed on the transparent support substrate 10 by the photosensitive resin composition. A color filter in which a resin black matrix (not shown) provided between the pixels 20 to be formed is formed, and the organic light-emitting body 500 is formed on the color filter via the organic protective layer 30 and the inorganic oxide film 40. The organic EL element 100 can be manufactured by stacking layers. In addition, at least one of the pixel 20 and the resin black matrix is manufactured using the photosensitive resin composition of the present invention. As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, Inc., August 20, 2004, light emission, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 manufactured in this manner, etc. Thus, an organic EL display can be produced.

  The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

  Next, although a synthesis example, 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.

<Preparation of carbon black ink>
A carbon black ink was prepared by preparing a pigment, a dispersant, a dispersion aid, and a solvent by the following composition and method.
Specifically, first, the solid content of the pigment, the dispersant, and the dispersion aid and the solvent were prepared so as to have the following quantitative ratio.
Pigment: R1060 (carbon black manufactured by Columbia); 100 parts by mass Dispersant: BYK167 (basic urethane dispersant manufactured by Big Chemie); 20 parts by mass (in terms of solid content)
Dispersing aid (pigment derivative): S12000 (manufactured by Lubrizol, phthalocyanine pigment derivative having an acidic group); 2.0 parts by mass; solvent; propylene glycol monomethyl ether acetate (PGMEA): 226.6 parts by mass

These were sufficiently stirred and mixed to obtain a dispersion.
Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, zirconia beads having a diameter of 0.5 mm were used and added at a ratio of 180 parts by mass of beads to 60 parts by mass of the dispersion. After the dispersion, the beads and the dispersion were separated by a filter to prepare a carbon black ink having a solid content of 35% by mass.

<Synthesis Example 1: Synthesis of alkali-soluble resin (1)>

50 g of epoxy compound having the above structure (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were attached to a thermometer, a stirrer and a cooling pipe. The reaction was continued at 90 ° C. with stirring until the acid value was 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the above epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 3.5 parts by mass of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution became transparent, it was diluted with 3-methoxybutyl acetate (MBA) to prepare a solid content of 50% by mass, an acid value of 115 mg KOH / g, and a polystyrene-reduced weight average molecular weight (Mw) measured by GPC. ) 2600 alkali-soluble resin (1) was obtained.

<Synthesis Example 2: Synthesis of Photopolymerization Initiator (1)>

(Diketone body)
Ethylcarbazole (5 g, 25.61 mmol) and o-naphthoyl chloride (5.13 g, 26.89 mmol) are dissolved in 30 ml of dichloromethane, cooled to 2 ° C. with an ice-water bath and stirred, and then AlCl ₃ (3. 41 g, 25.61 mmol) was added. Further, after stirring at room temperature for 3 hours, a 15 ml dichloromethane solution of crotonoyl chloride (2.81 g, 26.89 mmol) was added to the reaction solution, then AlCl ₃ (4.1 g, 30.73 mmol) was added, and another 1 hour 30 hours. Stir for minutes. The reaction solution was poured into 200 ml of ice water, 200 ml of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a diketone body as a white solid (10 g).

(Oxime body)
Diketone (3.00 g, 7.19 mmol), NH ₂ OH · HCl (1.09 g, 15.81 mmol), and sodium acetate (1.23 g, 15.08 mmol) were mixed with 30 ml of isopropanol and refluxed for 3 hours. .
After completion of the reaction, the reaction mixture was concentrated, 30 ml of ethyl acetate was added to the resulting residue, washed with 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 1.82 g of a solid. This was purified by column chromatography to obtain 2.22 g of an oxime compound as a pale yellow solid.

(Oxime ester)
The oxime (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane, and the mixture was ice-cooled. Triethylamine (1.77 g, 17.5 mmol) was added dropwise, and 1 Reacted for hours. After confirming disappearance of the raw material by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of saturated aqueous sodium hydrogen carbonate solution and twice with 5 ml of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (ethyl acetate / hexane = 2/1) to obtain 0.79 g of a light yellow solid photopolymerization initiator (1). Obtained. The chemical shift of ¹ H-NMR of the photopolymerization initiator (1) is shown below.

¹ H-NMR (CDCl ₃ ): σ 1.17 (d, 3H), 1.48 (t, 3H), 1.53 (s, 3H), 1.81 (s, 3H), 2.16 (s 3H), 2.30 (s, 3H), 3.17-3.32 (m, 2H), 4.42 (q, 2H), 4.78-4.94 (br, 1H), 7. 45-7.59 (m, 5H), 7.65 (dd, 1H), 7.95 (m, 2H), 8.04 (m, 2H), 8.14 (dd, 1H), 8.42 (D, 1H), 8.64 (d, 1H)

  The structure of the photopolymerization initiator (1) is as follows.

<Photopolymerization initiator (2)>
In addition, the following photopolymerization initiator (2) was prepared.
Photopolymerization initiator (2): Irgacure OXE02 (manufactured by BASF)

<Organic silicon compound>
The following organosilicon compounds (1) to (5) were prepared. The organosilicon compounds (1) and (2) correspond to the organosilicon compound (f-1) and can be obtained by the method described in <Organic silicon compound (f)>.
Organosilicon compound (1):

  Organosilicon compound (2):

  Organosilicon compound (3):

  Organosilicon compound (4):

  Organosilicon compound (5):

<Photopolymerizable monomer>
Dipentaerythritol hexaacrylate (KAYARAD DPHA (manufactured by Nippon Kayaku)) was prepared as a photopolymerizable monomer.

<Surfactant>
The following surfactants (1) to (2) were prepared as surfactants.
Surfactant (1): Megafac F-554 (DIC Corporation, fluorine-based)
Surfactant (2): Megafac F-559 (manufactured by DIC, fluorine-based)
The characteristics of each surfactant are as shown in Table 1.

However, the surface tension of toluene and propylene glycol monomethyl ether (PGME) is as follows.
Surface tension of toluene: 27.9 mN / m (25 ° C.)
Propylene glycol monomethyl ether (PGME): 27.1 mN / m (25 ° C.)
Further, from Table 1, the surfactant (1) satisfies the relationship of the general formula (I).

<Example 1>
(Preparation of black resist 1)
Using the carbon black ink prepared in <Adjustment of carbon black ink>, each component was added so as to have the ratio shown in Table 2, and stirred and dissolved with a stirrer to prepare black resist 1. The solid content in the black resist is 15% by mass.

In addition, the meaning of the abbreviation in Table 2 is as follows.
DPHA: Dipentaerythritol hexaacrylate PGMEA: Propylene glycol monomethyl ether acetate MBA: 3-methoxybutyl acetate

<Example 2>
(Preparation of black resist 2)
A black resist 2 was prepared in the same manner as the black resist 1 of Example 1, except that the photopolymerization initiator (1) of Example 1 was changed to the photopolymerization initiator (2).
<Example 3>
(Preparation of black resist 3)
A black resist 3 was prepared in the same manner as the black resist 1 of Example 1, except that the organosilicon compound (1) of Example 1 was changed to the organosilicon compound (2).

<Comparative Example 1>
(Preparation of black resist 4)
The organosilicon compound was not added in Example 1 (the PGMEA solvent was added to 1.5% by mass occupied by the organosilicon compound), and the surfactant (1) was the surfactant (2). A black resist 4 was prepared in the same manner as the black resist 1 of Example 1 except that the change was changed to.
<Comparative Example 2>
(Preparation of black resist 5)
The black resist of Example 1 except that the organosilicon compound (1) was changed to the organosilicon compound (3) and the surfactant (1) was changed to the surfactant (2) in Example 1. A black resist 5 was prepared in the same manner as in 1.

<Comparative Example 3>
(Preparation of black resist 6)
A black resist 6 was prepared in the same manner as the black resist 5 of Comparative Example 2 except that the organosilicon compound (3) was changed to the organosilicon compound (4) in Comparative Example 2.
<Comparative Example 4>
(Preparation of black resist 7)
A black resist 7 was prepared in the same manner as the black resist 5 of Comparative Example 2 except that the organosilicon compound (3) was changed to the organosilicon compound (5) in Comparative Example 2.
<Comparative Example 5>
(Preparation of black resist 8)
A black resist 8 was prepared in the same manner as the black resist 1 of Example 1, except that the surfactant (1) was changed to the surfactant (2) in Example 1.
<Comparative Example 6>
(Preparation of black resist 9)
A black resist 9 was prepared in the same manner as the black resist 1 of Example 1, except that the organosilicon compound (1) was changed to the organosilicon compound (3) in Example 1.

(Evaluation of resist)
(1) Production of cured black resist film The prepared black resists 1 to 11 were applied to a glass substrate with a spin coater, dried under reduced pressure, and then dried with a hot plate at 100 ° C for 150 seconds. Subsequently, the entire surface of the obtained dried coating film was exposed with a high-pressure mercury lamp at 40 mJ without an exposure mask, and then the alkali adjusted to a 0.04 mass% KOH aqueous solution with ultrapure water at room temperature (23 ° C.). A black resist film was obtained by spray development with a developer for 1.4 times the dissolution time. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes to prepare a black resist cured film having a thickness of 1.0 μm. The dissolution time is the time when the unexposed portion of the photosensitive layer is dissolved and the entire substrate begins to be visible during the development process, and the dissolution time of each black resist is 30 to 40 seconds.

  The film thickness of the black resist cured film was measured with a step measuring device Alpha-Step-500 (KLA-Tencor) after part of the film was shaved with a cutter to provide a stepped portion. The film thickness can be adjusted by changing the rotation speed of the spin coater.

(2) Evaluation of substrate adhesion (after heat curing)
About each black resist cured film produced in (1), after returning to room temperature, a 2.5 cm square solid plate is cut out, and a thermosetting sealant Structbond XN-21-S (Mitsui Chemical Co., Ltd.) is used. Aluminum stud pins (P / N: 901106U, diameter 2.7 mm) (manufactured by Quad Group) were joined to prepare a measurement sample. The prepared sample was subjected to a tensile test at a rate of 2.0 kg / s using a thin film adhesion strength measuring device Romulus (manufactured by Quad Group), and the breaking strength when the black resist cured film and the glass substrate were broken. The substrate adhesion stress was determined from the adhesion area by the following formula.
Substrate adhesion stress (kg / cm ² ) = breaking strength (kg) / bonding area (cm ² )
From this, the substrate adhesion strength (%) was determined as a relative value (%) when the value of substrate adhesion stress (kg / cm ² ) in Comparative Example 1 was taken as 100%. The results are shown in Tables 3-1 and 3-2.

(3) Evaluation of substrate adhesion (after exposure to high temperature and high humidity environment)
After preparing a measurement sample in which aluminum stud pins were joined in the same procedure as (2), it was further exposed for 2 hours in a steam atmosphere at 120 ° C., 2 atm and relative humidity 100% (pressure cooker test, PCT ). After returning the measurement sample to room temperature, the substrate adhesion stress was measured in the same procedure as (2). Here, the substrate adhesion strength (%) was determined as a relative value (%) when the value of the substrate adhesion stress (kg / cm ² ) after heat curing in Comparative Example 1 was taken as 100%. The results are shown in Tables 3-1 and 3-2.

(Substrate adhesion evaluation criteria)
The substrate adhesion strength was expressed and compared in terms of a relative value (%) with the substrate adhesion stress of the black resist cured film (after heat curing) of Comparative Example 1 as 100%.
A: The substrate adhesion strength is 150% or more.
B: Substrate adhesion strength is less than 150% to 120% or more.
C: The substrate adhesion strength is less than 120% to 110% or more.
D: Substrate adhesion strength is less than 110%.

  As shown in Table 3-1 and Table 3-2, the photosensitive resin composition (Examples 1 to 3) of the present invention contains an organosilicon compound (f-1) and a surfactant (g-1). By containing, the substrate adhesion after heat-curing is improved and improved. Furthermore, it can be seen that even after exposure in a high temperature and high humidity environment, high substrate adhesion is exhibited and good. The results of Table 3-1 and Table 3-2 will be described below.

In Comparative Example 1, a surfactant (2) that does not contain an organosilicon compound and does not belong to the surfactant (g-1) is used, and the substrate adhesion is low.
In Comparative Examples 2 to 5, the organosilicon compound (f-1) and other various organosilicon compounds and a surfactant (2) that does not belong to the surfactant (g-1) are used in combination. Compared with Comparative Example 1 containing no organosilicon compound, an improvement in substrate adhesion is observed, but the effect is not great.
Comparative Example 2 is a surfactant (2) that does not belong to surfactant (g-1), Comparative Example 6 is a surfactant (1) that belongs to surfactant (g-1), both of which are organosilicon compounds. It is used in combination with an organosilicon compound (3) not belonging to (f-1). Although there is no significant difference in substrate adhesion, the substrate adhesion after exposure to a high-temperature and high-humidity environment is slightly higher when the surfactant (1) is used, but it is not sufficient.

  In Examples 1 to 3, an organosilicon compound belonging to the organosilicon compound (f-1) and a surfactant belonging to the surfactant (g-1) are used in combination at the same time. It can be seen that both the adhesion to the substrate after exposure to a wet environment is greatly improved. This is because the silane part of the organosilicon compound (f-1) is bonded to glass, the urethane part is improved in adhesion by the interaction with the polar part of other materials, and the unsaturated double bond It is thought that the site has increased the degree of cross-linking of the resin because the water penetration rate is reduced. In addition, when a large amount of surfactant is collected at the interface between the film and the substrate, the surfactant itself does not contribute to crosslinking or adhesion, which may cause a decrease in adhesion, but the surfactant (g-1) with reduced hydrophilicity and When combined, it is considered that the number of molecules of the surfactant covering the interface between the black resist film and the glass substrate is reduced. Thereby, the silane site | part and urethane site | part of an organosilicon compound (f-1) function effectively in the interface of a resist film and a board | substrate, and can improve the adhesive force after heat-hardening. Further, the surfactant (g-1) is concentrated on the surface of the black resist film, thereby increasing the hydrophobicity of the film surface. Thereby, it is considered that moisture permeation from the film surface is suppressed and a decrease in adhesion after exposure to a high temperature and high humidity environment is suppressed. As described above, when the organosilicon compound (f-1) and the surfactant (g-1) are used in combination, a greater improvement effect than that obtained when used alone can be obtained.

  As described above, by using the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition having good substrate adhesion after heat curing and exposure to a high temperature and high humidity environment.

Claims (12)

Including alkali-soluble resin (a), photopolymerizable monomer (b), photopolymerization initiator (c), colorant (d), dispersant (e), organosilicon compound (f) and surfactant (g) A photosensitive resin composition comprising:
The organosilicon compound (f) contains at least an organosilicon compound (f-1) having a structure represented by the following general formula (1),
A surfactant (g) contains a surfactant (g-1) that satisfies the following general formula (I): A photosensitive resin composition.

(In the above formula, R ^{1 to} R ³ are each independently a hydrogen atom or an alkyl group optionally having a substituent. ^Ra is a group represented by the following formula (1-1). * Is a bond.)

(In the above formula, R ⁴ and R ⁵ are each independently an alkylene group which may have a substituent, R ⁶ is a hydrogen atom or a methyl group. * Is a bond with a Si atom. .)
Δγ (toluene)> Δγ (propylene glycol monomethyl ether) (I)
(However, Δγ (toluene) is derived from the surface tension of toluene (mN / m, 25 ° C.) to the surface tension of 0.1% by weight toluene solution of surfactant (g-1) (mN / m, 25 ° C.). Similarly, Δγ (propylene glycol monomethyl ether) is 0.1 mass of surfactant (g-1) from the surface tension (mN / m, 25 ° C.) of propylene glycol monomethyl ether. (It means a value obtained by reducing the surface tension (mN / m, 25 ° C.) of a% propylene glycol monomethyl ether solution.)   The photosensitive resin composition of Claim 1 whose surfactant (g-1) is a fluorine-type surfactant.   The photosensitive resin composition of Claim 1 or 2 whose photoinitiator (c) is an oxime ester type compound.   The photosensitive resin composition according to claim 3, wherein the oxime ester-based compound has an optionally substituted carbazolyl group.   The photosensitive resin composition of any one of Claims 1-4 whose color material (d) is a black color material.   The photosensitive resin composition of any one of Claims 1-5 whose content rate of a coloring material (d) is 40 mass% or more with respect to the total amount of solids.   The photosensitive resin composition according to any one of claims 1 to 6, wherein the dispersant (e) is a polymer dispersant having a basic functional group.   The photosensitive resin composition of any one of Claims 1-7 in which the alkali-soluble resin (a) contains an epoxy (meth) acrylate resin having a carboxyl group.   Hardened | cured material formed by hardening the photosensitive resin composition of any one of Claims 1-8.   A black matrix comprising the cured product according to claim 9.   The black matrix according to claim 10, wherein an optical density per 1 μm of film thickness is 4.0 or more.   An image display device comprising the black matrix according to claim 10.

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