JP5361441B2 - Photosensitive resin composition and method for producing the same, light-shielding color filter and method for producing the same, and solid-state imaging device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition from which a light-shielding color filter superior in light-shielding ability can be manufactured and which suppresses generation of coating defects when applied on a support, and to provide a method of manufacturing the composition. <P>SOLUTION: The photosensitive resin composition contains titanium black, a dispersant, a resin, a polymerizable compound, a photopolymerization initiator, at least one kind selected from propylene glycol alkylether solvents and propylene glycol alkylether acetate solvents, and at least one kind selected from aromatic solvents and ketone solvents. In the process of manufacturing the composition, a mixture liquid containing titanium black and a dispersant is subjected to a dispersion treatment until changes in the volume average particle size of the titanium black are decreased to 10 nm/pass or lower to obtain a dispersion liquid, to which a dispersant is further added to carry out a dispersion treatment. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a photosensitive resin composition and a manufacturing method thereof, a light-shielding color filter and a manufacturing method thereof, and a solid-state imaging device.

A color filter used in a liquid crystal display device includes a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast. A solid-state image sensor is also provided with a light-shielding color filter for the purpose of preventing noise and improving image quality.
A photosensitive resin composition containing a black color material such as carbon black or titanium black is known as a composition for forming a black matrix for a liquid crystal display device or a light-shielding color filter for a solid-state imaging device. .

Specifically, as a photosensitive resin composition mainly used for liquid crystal display devices, a photosensitive resin composition containing titanium black having a specific X-ray diffraction peak intensity ratio (for example, for the purpose of improving optical density) (for example, Patent Documents 1 and 2) and photosensitive resin compositions containing titanium black having a specific nitrogen concentration and a specific crystallite diameter (for example, see Patent Documents 3 to 5) have been studied.
In addition, as a photosensitive resin composition for a solid-state imaging device, a photosensitive resin composition containing titanium black and a resin component has been studied for the purpose of obtaining a high light-shielding property with a thin film (for example, Patent Documents). 6).

Japanese Patent No. 3724269 International Publication No. 2005/037926 Pamphlet JP 2006-182627 A JP 2006-206871 A JP 2006-209102 A JP 2007-115921 A

  However, when the photosensitive resin composition containing titanium black described in Patent Documents 1 to 6 is applied on the support, it is smaller than when the photosensitive resin composition containing carbon black is applied on the support. It became clear that coating defects such as foreign matter and bubbles are likely to occur.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a photosensitive resin composition capable of producing a light-shielding color filter having excellent light-shielding ability, and capable of suppressing the occurrence of coating defects when coated on a support, and a method for producing the same. To do.
Another object of the present invention is to provide a light-shielding color filter having excellent light-shielding ability and few defects, and a method for producing the same.
It is another object of the present invention to provide a solid-state imaging device with little noise and excellent color reproducibility.

Specific means for solving the above-described problems are as follows.
<1> Titanium black, a dispersant, a resin, a polymerizable compound, a photopolymerization initiator, at least one selected from a propylene glycol alkyl ether solvent and a propylene glycol alkyl ether acetate solvent, and aromatic In the process of producing a photosensitive resin composition containing at least one selected from a system solvent and a ketone system solvent,
For the mixed liquid containing titanium black and a dispersant, a dispersion treatment is performed until the change in volume average particle diameter of the titanium black is 10 nm / pass or less,
In the method for producing a photosensitive resin composition, a dispersing agent is further added to the dispersion obtained by the dispersion treatment, and the dispersion treatment is carried out until the change in volume average particle diameter of the titanium black is 10 nm / pass or less. is there.

<2> The method for producing a photosensitive resin composition according to <1>, wherein the mixed solution contains at least one selected from a propylene glycol alkyl ether solvent and a propylene glycol alkyl ether acetate solvent.
<3> The photosensitive resin composition according to <1> or <2>, wherein at least one selected from the aromatic solvent and the ketone solvent is at least one selected from an aliphatic ketone solvent. It is a manufacturing method.
<4> The method for producing a photosensitive resin composition according to any one of <1> to <3>, wherein the photopolymerization initiator is an oxime photopolymerization initiator.

<5> A photosensitive resin composition produced by the method for producing a photosensitive resin composition according to any one of <1> to <4>.
<6> The photosensitive resin composition according to <5>, which is used for forming a light-shielding color filter for a solid-state imaging device.

<7> On the support, a step of applying the photosensitive resin composition according to <5> or <6> to form a photosensitive layer, a step of exposing the photosensitive layer in a pattern, and an exposure And a step of developing the photosensitive layer later to form a colored pattern.

<8> A light-shielding color filter produced by the method for producing a light-shielding color filter according to <7>.
<9> A solid-state imaging device including the light-shielding color filter according to <8>.

ADVANTAGE OF THE INVENTION According to this invention, the light-shielding color filter excellent in light-shielding ability can be produced, and the photosensitive resin composition which can suppress generation | occurrence | production of the coating defect when apply | coating on a support body, and its manufacturing method can be provided.
Moreover, according to the present invention, it is possible to provide a light-shielding color filter having excellent light-shielding ability and few defects, and a method for producing the same.
In addition, according to the present invention, it is possible to provide a solid-state imaging device with less noise and excellent color reproducibility.

<< Photosensitive resin composition and method for producing the same >>
The photosensitive resin composition of the present invention is selected from titanium black, a dispersant, a resin, a polymerizable compound, a photopolymerization initiator, a propylene glycol alkyl ether solvent, and a propylene glycol alkyl ether acetate solvent. In the course of producing a photosensitive resin composition containing at least one selected from an aromatic solvent and a ketone solvent, the titanium is added to the mixed liquid containing titanium black and a dispersant. Dispersion treatment is performed until the change in the volume average particle size of black is 10 nm / pass or less (hereinafter, the dispersion treatment up to this point is also referred to as “first-stage dispersion treatment”), and the dispersion obtained by the dispersion treatment is performed. A dispersing agent is further added to the liquid for dispersion treatment (hereinafter also referred to as “second-stage dispersion treatment”).
In the present invention, the distribution method including the first-stage distributed processing and the second-stage distributed processing as described above may be referred to as “multi-stage distributed processing”. In addition, the manufacturing method of the photosensitive resin composition of this invention may be the form which adds a dispersing agent after the said 2nd stage dispersion process, and performs the dispersion process after the 3rd stage. Such a form is also included in the “multistage distributed processing”.
Moreover, the photosensitive resin composition of this invention is manufactured by the manufacturing method of the said photosensitive resin composition of this invention.

Titanium black is a black pigment with excellent light-shielding ability, but when a photosensitive resin composition containing titanium black as a black pigment is applied on a support, the photosensitive resin composition containing carbon black as a black pigment is applied on the support. As a result of studies by the present inventors, it has been clarified that coating defects such as fine foreign matters and bubbles are likely to occur compared to the case where the coating is applied to the coating.
Therefore, by setting the photosensitive resin composition and the manufacturing method thereof to the configuration of the present invention, the occurrence of coating defects, which is a problem of the photosensitive resin composition containing titanium black, is suppressed.
The reason why the above effect can be obtained is presumed to be because the dispersibility of titanium black is improved by the above configuration, but the present invention is not limited to this reason.
Surprisingly, the composition described above improves the temporal stability of the composition. Further, peeling when the light-shielding color filter is formed (particularly peeling when formed on a substrate having a structure) is suppressed.

In the photosensitive resin composition and production method thereof of the present invention, titanium black, a dispersant, a resin (a resin other than the dispersant), a polymerizable compound, a photopolymerization initiator, and a specific solvent component (propylene glycol alkyl ether type) A solvent component comprising at least one selected from a solvent and a propylene glycol alkyl ether acetate solvent and at least one selected from an aromatic solvent and a ketone solvent, hereinafter also simply referred to as a “solvent component”. As long as the first-stage dispersion process and the second-stage dispersion process are performed, there is no particular limitation on the timing of adding each component.
The photosensitive resin composition and the method for producing the same according to the present invention include, for example, a dispersion containing titanium black, a dispersant, and, if necessary, a part of a solvent component by the first-stage dispersion treatment and the second-stage dispersion treatment. After the composition is manufactured, the remaining components of the photosensitive resin composition (resin, polymerizable compound, photopolymerization initiator, and remaining solvent component) are added to the manufactured dispersion composition. Can do.
Further, in the step of producing a dispersion composition containing titanium black, a dispersant, and optionally a part of the solvent component by the first stage dispersion treatment and the second stage dispersion treatment, a resin, a polymerizable compound, At least a part of the photopolymerization initiator and the solvent component may be added in advance, and the remaining components of the photosensitive resin composition may be added to the produced dispersion composition.
Further, in the step of producing a dispersion composition containing titanium black, a dispersant, and, if necessary, a part of the solvent component by the first-stage dispersion treatment and the second-stage dispersion treatment, the photosensitive resin composition All components (resin, polymerizable compound, photopolymerization initiator, solvent component, etc.) may be added in advance, and a photosensitive resin composition may be prepared as a dispersion composition.

  Hereinafter, the first-stage dispersion treatment and the second-stage dispersion treatment in the present invention will be described, and then each component contained in the photosensitive resin composition of the present invention will be described.

<First-stage distributed processing>
The first-stage dispersion treatment in the present invention is a dispersion treatment performed on a mixed solution containing titanium black and a dispersant until the change in volume average particle diameter of the titanium black becomes 10 nm / pass or less.

Here, “10 nm / pass or less” means that the amount of change in the volume average particle diameter for each pass in the dispersion apparatus is 10 nm or less.
Examples of “10 nm / pass or less” include the following states.
That is, in the system in which the volume average particle diameter is decreased for each pass at the beginning of the dispersion treatment for the mixed liquid, and the change in the volume average particle diameter for each pass is decreased as the dispersion proceeds, 1 The state in which the change amount of the volume average particle diameter for each pass is 10 nm or less is “10 nm / pass or less”.

In addition, “pass” refers to the number of times that the entire amount of the dispersion liquid passes through the dispersion apparatus in the dispersion apparatus.
For example, in a dispersion apparatus, when 25 L (liter) of mixed liquid is dispersed at a flow rate of 5 L / h, the dispersion process for 5 h is “one pass”.
The number of passes is determined by the following formula A.

  Number of passes = (flow rate [L / h] × processing time [h]) / processing liquid amount [L] Formula A

The volume average particle diameter of titanium black in the present invention is measured using a dynamic light scattering method for a diluted liquid obtained by diluting a mixture or dispersion containing titanium black 80 times with propylene glycol monomethyl ether acetate. The value obtained by doing.
This measurement can be performed using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd.

The dispersion apparatus used for the dispersion treatment in the present invention is not particularly limited as long as it is a dispersion apparatus that repeatedly performs dispersion treatment on the mixed liquid (that is, a dispersion apparatus that can define the “pass”). A known dispersion device that is commercially available can be used.
Examples of the dispersing device include Ultra Apex Mill manufactured by Kotobuki Kogyo Co., Ltd., Dino Mill ECM Series manufactured by Shinmaru Enterprises Co., Ltd., and the like.

Moreover, there is no limitation in particular as temperature at the time of a dispersion process, However, 5 to 60 degreeC is preferable from a viewpoint of dispersion stability, and 20 to 40 degreeC is more preferable.
The dispersion treatment is preferably performed using beads.
There are no particular limitations on the composition of the beads and the diameter of the beads, and known compositions and diameters can be applied.
For example, a bead having a diameter of 0.01 mm to 0.10 mm can be suitably used.

  In the mixed solution in the first stage dispersion treatment, the mass ratio of the dispersant to the titanium black [dispersant / titanium black] is preferably 0.05 to 1.00, more preferably 0.05 to 0.50. If the mass ratio is too high, it is difficult to proceed with dispersion, which is not preferable. On the other hand, if the mass ratio is too low, it is difficult to obtain dispersion stability.

Moreover, it is preferable that the liquid mixture in the said 1st dispersion process contains a solvent.
The solvent in the mixed solution is not particularly limited, but the solvent component of the photosensitive resin composition of the present invention (at least one selected from a propylene glycol alkyl ether solvent and a propylene glycol alkyl ether acetate solvent; It is preferable to use at least one selected from among solvent components comprising at least one selected from group solvents and ketone solvents.
In particular, from the viewpoint of more effectively obtaining the effects of the present invention, the solvent in the mixed solution is at least selected from at least one selected from propylene glycol alkyl ether solvents and propylene glycol alkyl ether acetate solvents. It is more preferable that 1 type is included.
In the mixed solution in the first stage dispersion treatment, the mass ratio of the solvent to titanium black [solvent / titanium black] is preferably 1.0 to 9.0, and preferably 1.0 to 5 from the viewpoint of ease of dispersion. 0.0 is more preferable.

  Moreover, the liquid mixture in the said 1st dispersion | distribution process may contain the component (For example, resin, a photoinitiator, a polymeric compound, etc.) of the photosensitive resin composition mentioned later.

<Second-stage distributed processing>
The second-stage dispersion treatment in the present invention is a dispersion treatment performed by further adding a dispersant to the dispersion obtained by the first-stage dispersion treatment.
The dispersant added in the second stage dispersion treatment (hereinafter also referred to as “second stage dispersant”) is the same as the dispersant added in the first stage dispersion treatment (hereinafter also referred to as “first stage dispersant”). One kind may be sufficient and a different kind may be sufficient.

The amount of the second stage dispersant added in the second stage dispersion treatment is preferably 0.05 to 1.00 in terms of mass ratio [second stage dispersant / titanium black] with respect to titanium black in the dispersion. 0.05 to 0.50 is more preferable.
Further, the timing of adding the second stage dispersant is not particularly limited as long as it is after the time point when the change in the volume average particle diameter of titanium black becomes 10 nm / pass or less.
Further, the second stage dispersant may be added only once, or may be added in two or more times.

In the second stage dispersion treatment, a solvent may be added together with the second stage dispersant.
The solvent to be added may be the same type of solvent that may be used in the mixed liquid in the first stage dispersion treatment, or may be a different type of solvent.
For example, a part of the solvent component of the photosensitive resin composition is included in the mixed solution in the first stage dispersion treatment, and the remaining part of the solvent component of the photosensitive resin composition is added in the second stage dispersion treatment. Alternatively, all may be added.
Furthermore, in the second stage dispersion treatment, in addition to the second stage dispersant and the solvent, the components of the photosensitive resin composition described later (for example, resin, photopolymerization initiator, polymerizable compound, etc.) are added. It may be added.

  The other preferable conditions for the second-stage distributed processing are the same as the preferable conditions for the first-stage distributed processing. However, the condition of the first stage distributed process and the condition of the second stage distributed process may be the same condition or different conditions.

In the present invention, the dispersion composition (hereinafter also referred to as “final dispersion composition”) that has undergone the first-stage dispersion treatment and the second-stage dispersion treatment described above (with further treatment as necessary) is obtained. Is manufactured.
The total mass of the solvent in the total mass of the obtained final dispersion composition is preferably 30% by mass to 95% by mass, more preferably 40% by mass to 90% by mass, and particularly preferably 50% by mass to 80% by mass. .

  Further, in the obtained final dispersion composition, the mass ratio of the total dispersant to the titanium black [(first stage dispersant + second stage dispersant) / titanium black] is preferably 0.10 to 2.00, 0 .10 to 1.00 is more preferable.

  The total mass of titanium black in the total mass of the obtained final dispersion composition is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 50% by mass, and particularly preferably 5% by mass to 30% by mass. preferable.

<Titanium Black>
The photosensitive resin composition of the present invention contains titanium black as a black color material (black pigment).
Thereby, the light-shielding ability when this composition is made into a light-shielding color filter improves. In particular, a light-shielding color filter for a solid-state imaging device may require a light-shielding ability in the infrared region in addition to a light-shielding ability in the visible region. The photosensitive resin composition of the present invention containing titanium black is used as a light-shielding color filter. When used as a filter, it is excellent in light shielding ability in the visible region and in light shielding ability in the infrared region.

Titanium black in the present invention is black particles (black pigment) having titanium atoms.
The titanium black in the present invention is preferably low-order titanium oxide or titanium oxynitride represented by TiN _x O _y (x and y are real numbers less than 2).
The surface of titanium black in the present invention can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. Specifically, it can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and a water-repellent substance as disclosed in Japanese Patent Application Laid-Open No. 2007-302836. Processing is also possible.

  The titanium black can be produced by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere for reduction (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not a thing.

  The average primary particle diameter of titanium black in the present invention is not particularly limited, but is preferably 3 nm to 2000 nm, more preferably 10 nm to 500 nm, and more preferably 10 nm to 100 nm from the viewpoint of dispersibility and colorability. It is particularly preferred.

The specific surface area of the titanium black is not particularly limited. However, since the water repellency after the surface treatment of the titanium black with a water repellent agent has a predetermined performance, the value measured by the BET method is usually 5 m ^2. / 150 m ² / g approximately, inter alia ^20m 2 / ^g~100m about ² / g are preferred.

Examples of commercially available titanium black products include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, manufactured by Mitsubishi Materials Corporation (Gemco Co., Ltd.), Alacka Chemical Co., Ltd. ) D and the like.
In this invention, titanium black may be used individually by 1 type, and may use 2 or more types together.

  Further, extender pigments may be added to the titanium black in the present invention as necessary. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more. The amount of the extender is usually 0 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of titanium black. In the present invention, the titanium black and extender pigment can be used by modifying the surface with a polymer in some cases.

Moreover, you may mix and use things other than titanium black as a pigment for light shielding in the photosensitive resin composition of this invention.
Such a light-shielding pigment that can be mixed is not particularly limited as long as it has absorbance in the visible light region, and the above-mentioned extender pigment, carbon black, C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, C.I. I. Pigment Brown 25, 28, C.I. I. And organic pigments such as Pigment Black 1 and 7.
Examples of using a mixture of light shielding pigments other than titanium black include a mixture of titanium black and carbon black in a ratio of 6: 1, a mixture of titanium black and titanium oxide in a ratio of 3: 1, and the like.
The light-shielding pigment other than titanium black used by mixing can be used in the range of 0.01 to 99.99 parts by mass with respect to 100 parts by mass of titanium black. Preferably, it is the range of 20-70 mass parts.

<Dispersant>
The photosensitive resin composition of the present invention contains a dispersant.
The dispersant is used for at least the first stage dispersion process and the second stage dispersion process. In the present invention, as described above, the dispersant in the first stage dispersion treatment (hereinafter, also referred to as “first stage dispersant”) and the dispersant in the second stage dispersion treatment (hereinafter referred to as “second stage dispersant”). May be the same species or different species.
Further, each of the first stage dispersant and the second stage dispersant may be only one kind or two or more kinds.

As the dispersant in the present invention (first-stage dispersant or second-stage dispersant, the same shall apply hereinafter), a polymer dispersant [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, Modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment Derivatives and the like can be mentioned.
The dispersant in the present invention can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

The dispersant in the present invention acts to adsorb on the surface of titanium black and, if desired, the pigment used in combination, and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface can be cited as preferred structures.
On the other hand, the dispersant in the present invention has an effect of promoting the adsorption of the dispersed resin by modifying the pigment surface.

Specific examples of the dispersant that can be used in the present invention include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. 161, 162, 163, 164, 165, 166, 170, 180 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010 ”manufactured by EFKA. 4165 (polyurethane series), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 ( Phthalocyanine derivatives), 6750 (a) "Zo pigment derivative)", "Ajisper PB821, PB822" manufactured by Ajinomoto Fine Techno Co., Ltd., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., Ltd. “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725”, Kao, manufactured by Enomoto Kasei Co., Ltd. “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)”, “Ace Min 86 (stearylamine acetate), Lubrizol "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end) , 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical.
These dispersants may be used alone or in combination of two or more.

  The acid value of the dispersant is preferably in the range of 5.0 mgKOH / g to 200 mgKOH / g, more preferably in the range of 10 mgKOH / g to 150 mgKOH / g, and still more preferably in the range of 15 mgKOH / g to 100 mgKOH / g. The following range is preferable. If the acid value is 200 mgKOH / g or less, pattern peeling during development can be suppressed, and if it is 5.0 mgKOH / g or more, alkali developability is good.

  In the present invention, the acid value of the dispersant can be calculated from, for example, the average content of acid groups in the dispersant. Moreover, the resin which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which comprises a dispersing agent.

  The weight average molecular weight of the dispersant in the present invention is preferably 10,000 or more and 300,000 or less, and preferably 15,000 or more and 200,000 or less, from the viewpoint of pattern peeling inhibition during development and developability. More preferably, it is 20,000 or more and 100,000 or less, and particularly preferably 25,000 or more and 50,000 or less. In addition, the weight average molecular weight of a dispersing agent can be measured by GPC, for example.

(Graft copolymer)
In the present invention, it is also preferable to use a graft copolymer (hereinafter also referred to as “specific resin”) as a dispersant.
Dispersibility and storage stability can be further improved by using a graft copolymer as a dispersant.

The graft copolymer preferably has a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000. In this case, the graft chain refers to the main chain from the base of the copolymer. From the chain to the end of the branched group.
In the dispersion composition, this specific resin is a dispersion resin that imparts dispersibility to titanium black, and has excellent dispersibility and affinity with a solvent due to a graft chain. Excellent dispersion stability after aging. Moreover, when it is set as the photosensitive resin composition, since it has affinity with the polymerizable compound or other resin that can be used in combination with the graft chain, it becomes difficult to produce a residue by alkali development.

  Further, by introducing an alkali-soluble partial structure such as a carboxylic acid group into this specific resin, a function as a resin imparting developability can be imparted for pattern formation by alkali development. Therefore, by introducing an alkali-soluble partial structure into the graft copolymer, the photosensitive resin composition of the present invention has an alkali-soluble dispersion resin itself, which is essential for the dispersion of titanium black. Such a photosensitive resin composition is preferable because it is excellent in the light shielding property of the exposed portion and the alkali developability of the unexposed portion is improved.

  When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility is improved. On the other hand, when the graft chain is too long, the adsorptive power to titanium black is lowered and the dispersibility is lowered. For this reason, as the graft copolymer used in the present invention, the number of atoms excluding hydrogen atoms per graft chain is preferably 40 to 10,000, and the hydrogen atoms per graft chain are excluded. The number of atoms is more preferably 50 to 2,000, and the number of atoms excluding hydrogen atoms per graft chain is more preferably 60 to 500.

  As the polymer structure of the graft chain, poly (meth) acryl, polyester, polyurethane, polyurea, polyamide, polyether, etc. can be used, but it improves the interaction between the graft site and the solvent, thereby improving dispersibility. In order to enhance, a poly (meth) acrylic structure, or a graft chain having poly (meth) acrylic, polyester, or polyether is preferable, and polyester or polyether is more preferable.

  The structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited as long as it has a substituent capable of reacting with the polymer main chain portion and satisfies the requirements of the present invention. A macromonomer having a reactive double bond group can be preferably used.

  Commercially available macromonomers suitably used for the synthesis of specific resins include AA-6 (manufactured by Toa Gosei Co., Ltd.), AA-10 (manufactured by Toa Gosei Co., Ltd.), AB-6 (manufactured by Toa Gosei Co., Ltd.), AS-6 (Toa Gosei Co., Ltd.) Synthesizer), AN-6 (Toa Gosei), AW-6 (Toa Gosei), AA-714 (Toa Gosei), AY-707 (Toa Gosei), AY-714 (Toa) Synthetic Co., Ltd.), AK-5 (Toagosei Co., Ltd.), AK-30 (Toagosei Co., Ltd.), AK-32 (Toagosei Co., Ltd.), Blemmer PP-100 (manufactured by NOF Corporation), Blemmer PP-500 (Manufactured by NOF Corporation), BLEMMER PP-800 (manufactured by NOF Corporation), BLEMMER PP-1000 (manufactured by NOF Corporation), BLEMMER 55-PET-800 (manufactured by NOF Corporation), Blemmer PME-4000 (manufactured by NOF Corporation) Manufactured), Blemmer PSE-400 (manufactured by NOF Corporation), BREMMER PSE-1300 (manufactured by NOF Corporation), Renma 43PAPE-600B (NOF Co., Ltd.), is used like. Among these, AA-6 (manufactured by Toa Gosei), AA-10 (manufactured by Toa Gosei), AB-6 (manufactured by Toa Gosei), AS-6 (manufactured by Toa Gosei), AN-6 (Manufactured by Toa Gosei Co., Ltd.), Blemmer PME-4000 (manufactured by NOF Corporation), etc.

  The graft site in the specific resin used in the present invention preferably contains at least a structural unit represented by any of the following formulas (1) to (5).

In Formula (1) to Formula (5), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthesis restrictions, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
In the formulas (1) to (5), Y ¹ , Y ² , Y ³ , Y ⁴ , and Y ⁵ are each independently a divalent linking group and are not particularly limited in structure. Specific examples include the following (Y-1) to (Y-20) linking groups. In the following structures, A and B each represent a bond with the left terminal group and the right terminal group in Formulas (1) to (5). Of the structures shown below, (Y-2) and (Y-13) are more preferable from the viewpoint of ease of synthesis.

In Formula (1) to Formula (5), Z ¹ , Z ² , Z ³ , Z ⁴ , and Z ⁵ are each independently a monovalent organic group, and the structure is not particularly limited. Includes a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group, and the like. Among these, particularly from the viewpoint of improving dispersibility, it is preferable to have a steric repulsion effect, and an alkyl group having 5 to 24 carbon atoms is preferable, and among these, a branched alkyl group having 5 to 24 carbon atoms or 5 to 24 carbon atoms is particularly preferable. The cyclic alkyl group is preferable.
In the formulas (1) to (5), n, m, p, q, and r are each an integer of 1 to 500.

  In the specific resin used in the present invention, the structural units represented by the formulas (1) to (5) are preferably included in a range of 10% to 90% in terms of mass with respect to the total mass of the specific resin. More preferably, it is contained in the range of 30% to 70%. Within this range, the dispersibility of titanium black is high, and the developability when a resist is formed is good. Moreover, the specific resin used for this invention can contain the graft copolymer from which 2 or more types of structures differ.

  In formula (5), R represents a monovalent organic group and is not particularly limited in terms of structure, but is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom, an alkyl group. It is a group. Further, as R, two or more types of R having different structures may be mixed and used in the specific resin.

  As the specific resin of the present invention, a functional group capable of forming an interaction with titanium black can be introduced in addition to the graft site. Among them, for example, a structural unit having an acid group, a structural unit having a basic group, a structural unit having a coordinating group, a structural unit having reactivity, and the like can be given.

Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and a particularly preferable one is a carboxylic acid group that has a good adsorptive power to titanium black and a high dispersibility. It is. One or more of these can be used.
By introducing such an acid group, there is also an advantage that the alkali developability of the specific resin is improved.
The content of these copolymer components suitably used for the specific resin of the present invention is 0.1 mol% or more and 50 mol% or less, and particularly preferably, from the viewpoint of suppressing damage of image strength due to alkali development, 1 It is mol% or more and 30 mol% or less.

  Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. Is a tertiary amino group having good dispersibility. One or more of these can be used. The content of these copolymerization components preferably used in the specific resin of the present invention is 0.01 mol% or more and 50 mol% or less, and particularly preferably 0.01 mol% from the viewpoint of inhibiting developability inhibition. More than 30 mol%.

  Examples of the coordinating group and the reactive group include an acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, acid chloride, and the like. It is a good and highly dispersible acetylacetoxy group. One or more of these can be used. The content of these copolymerization components preferably used in the specific resin of the present invention is 0.5 mol% or more and 50 mol% or less, and particularly preferably 1 mol% or more and 30 or more from the viewpoint of suppressing developability inhibition. It is less than mol%.

  The structure of the functional group capable of forming an interaction with titanium black other than the graft site is not particularly limited as long as it contains a functional group capable of forming an interaction with titanium black other than the above graft site. It preferably has at least one repeating unit obtained from the monomer represented by any one of the following general formulas (i) to (iii).

In the above formulas (i) to (iii), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or a carbon atom number of 1 to 6 An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
R ¹ , R ² , and R ³ are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. R ² and R ³ are particularly preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene groups), divalent heterocyclic groups and their oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino groups (—NR ³¹ —, where R ³¹ may be an aliphatic group, an aromatic group or a heterocyclic group) or a combination with a carbonyl group (—CO—).

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of the said aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

  6-20 are preferable, as for the carbon atom number of the said bivalent aromatic group, 6-15 are more preferable, and 6-10 are the most preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocycle. The heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) _n —, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

  In the above formulas (i) to (iii), Z represents a functional group capable of forming an interaction with titanium black in addition to the graft site, and is preferably a carboxylic acid or a tertiary amino group, and is a carboxylic acid. It is more preferable. Y represents a methine group or a nitrogen atom.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms ( For example, a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ is represented. Here, L and Z are as defined above. As R < ⁴ >, R < ⁵ > and R < ⁶ >, a hydrogen atom or a C1-C3 alkyl group is preferable, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ² , and R ³ are a hydrogen atom or a methyl group, and L includes an alkylene group or an oxyalkylene structure 2 A compound in which X is an oxygen atom or an imino group and Z is a carboxylic acid is preferable.
Further, as the monomer represented by the general formula (ii), R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, Z is a carboxylic acid, and Y is a methine group. Certain compounds are preferred. Further, as the monomer represented by the general formula (iii), R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z is a carboxyl group. Compounds that are acids are preferred.

Examples of typical compounds represented by formulas (i) to (iii) are shown below.
Methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride, addition polymerizable double in the molecule A reaction product of a compound having a bond and a hydroxyl group and a phthalic anhydride, an addition polymerizable double bond in the molecule, a reaction product of a compound having a hydroxyl group and a tetrahydroxyphthalic anhydride, an addition polymerizable double bond in the molecule Reaction product of hydroxyl group-containing compound and trimellitic anhydride, addition-polymerizable double bond and hydroxyl group-containing compound and pyromellitic anhydride in the molecule, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid , Itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenylmethacrylamide and the like.

  The content of a functional group capable of forming an interaction with titanium black such as a monomer having an acidic group in a specific resin is from the viewpoint of interaction with titanium black, dispersion stability, and permeability to a developer. The specific resin is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and still more preferably 10 to 70% by mass.

  Furthermore, the specific resin contained in the dispersion composition of titanium black according to the present invention is not limited to the structural unit having the graft site and titanium as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength. In addition to the functional group capable of forming an interaction with black, another structural unit having various functions, for example, a functional unit having an affinity for the dispersion medium used in the dispersion is shared. It can be included as a polymerization component.

  Examples of the copolymerizable component copolymerizable with the specific resin according to the present invention include radical polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes, acrylonitriles, methacrylonitriles, and the like. .

  These can be used singly or in combination of two or more. The content of these copolymerization components in the specific resin is preferably 0 mol% or more and 90 mol% or less, particularly preferably 0 mol% or more. 60 mol% or less. When the content is in the above range, sufficient pattern formation can be obtained.

  Examples of the solvent used for synthesizing the specific resin of the present invention include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl. Examples include acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. . These solvents may be used alone or in combination of two or more.

  Specific examples of such a specific resin include the following exemplary compounds 1 to 53. In addition, the suffix of each structural unit (main chain part) is mass%.

<Solvent component>
The photosensitive resin composition of the present invention has at least one selected from a propylene glycol alkyl ether solvent and a propylene glycol alkyl ether acetate solvent as a solvent component, and at least selected from an aromatic solvent and a ketone solvent. 1 type.
From the viewpoint of obtaining the effect of the present invention more effectively, it is preferable that at least a part of the solvent component of the photosensitive resin composition is contained in the mixed liquid in the first dispersion treatment. Furthermore, the solvent to be contained in the mixed solution is more preferably at least one selected from propylene glycol alkyl ether acetate solvents. When a part of the solvent component is contained in the mixed solution, the remainder of the solvent component of the photosensitive resin composition is added during the second dispersion treatment or after the second dispersion treatment.

The propylene glycol alkyl ether solvent is not particularly limited, but propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether are preferable from the viewpoint of obtaining the effect of the present invention more effectively. Among these, propylene glycol monoalkyl ether is more preferable, and propylene glycol monoalkyl ether having an alkyl group having 1 to 4 carbon atoms is particularly preferable.
Examples of the propylene glycol alkyl ether solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol dimethyl ether.

The propylene glycol alkyl ether acetate solvent is not particularly limited, but from the viewpoint of obtaining the effect of the present invention more effectively, propylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol dialkyl ether acetate. Is preferred. Among these, propylene glycol monoalkyl ether acetate is more preferable, and propylene glycol monoalkyl ether acetate having an alkyl group having 1 to 4 carbon atoms is particularly preferable.
Examples of the propylene glycol alkyl ether acetate solvent include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene A glycol dimethyl ether acetate is mentioned.

Although it does not specifically limit as said aromatic solvent, For example, toluene, o-xylene, m-xylene, p-xylene, etc. are mentioned.
Moreover, although it does not specifically limit as said ketone solvent, From a viewpoint of defect suppression, an aliphatic ketone solvent is preferable. Further, the aliphatic ketone solvent is more preferably a dialkyl ketone or an alicyclic ketone.
The dialkyl ketone is preferably a dialkyl ketone in which two alkyl groups each have 1 to 6 carbon atoms. Examples of the dialkyl ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, and methyl propyl ketone.
Examples of the alicyclic ketone include cyclopentanone and cyclohexanone.
Other ketone solvents include acetylacetone, diacetone alcohol, and the like.

  In the present invention, from the viewpoint of more effectively suppressing the occurrence of coating defects, at least one selected from an aromatic solvent and a ketone solvent in the photosensitive resin composition is selected from an aliphatic ketone solvent. It is preferable that it is at least one kind.

In the present invention, from the viewpoint of more effectively suppressing the occurrence of coating defects, at least one selected from an aromatic solvent and a ketone solvent in the photosensitive resin composition has a boiling point of 160 ° C. or less ( More preferably, the solvent type is 100 ° C. or higher and 160 ° C. or lower.
The boiling points of the aforementioned solvent species are shown below.
Toluene (boiling point 110.6 ° C), o-xylene (boiling point 144.4 ° C), m-xylene (boiling point 139.1 ° C), p-xylene (boiling point 138.4 ° C), acetone (boiling point 56.1 ° C) Methyl ethyl ketone (boiling point 79.6 ° C.), methyl isobutyl ketone (boiling point 116.2 ° C.), methyl amyl ketone (boiling point 152 ° C.), methyl isoamyl ketone (boiling point 144 ° C.), methyl propyl ketone (boiling point 101.7 ° C.), They are cyclopentanone (boiling point 130.6 ° C.), cyclohexanone (boiling point 155.7 ° C.), acetylacetone (boiling point 140 ° C.), diacetone alcohol (boiling point 166 ° C.).

In the photosensitive resin composition of the present invention, the concentration of the solid content relative to the solvent component is preferably 2 to 60% by mass.
In the present invention, at least one selected from a propylene glycol alkyl ether solvent and a propylene glycol alkyl ether acetate solvent (hereinafter also referred to as “first solvent”), an aromatic solvent, and a ketone solvent. It is preferable to adjust the mass ratio of at least one selected (hereinafter also referred to as “second solvent”).
Specifically, in the photosensitive resin composition of the present invention, the mass ratio [second solvent / (first solvent + second solvent)] is preferably 0.01 to 0.50, and preferably 0.02 to 0.00. 30 is more preferable.
A coating defect can be suppressed more as the mass ratio is 0.01 or more. When the mass ratio is 0.50 or less, a composition having excellent temporal stability can be obtained.

Moreover, the photosensitive resin composition of this invention may contain other solvents other than the above as a solvent component.
Examples of other solvents include cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether. , Ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3-methoxypropyl acetate, N, N-dimethylformamide Dimethyl sulfoxide, .gamma.-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate.

<Resin>
The photosensitive resin composition of the present invention contains a resin (a resin other than the dispersant).
It is preferable to use a linear organic polymer as the resin. As such a “linear organic polymer”, a known one can be arbitrarily used.
As the resin in the present invention, a linear organic polymer that is soluble or swellable in water or weak alkaline water is preferably selected to enable water development or weak alkaline water development.
The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible.
Examples of the linear organic polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, Those described in Kaisho 54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins having a carboxyl group alone or copolymerized, having acid anhydrides Examples thereof include resins obtained by hydrolyzing, half-esterifying, or half-amidating acid anhydride units by copolymerizing monomers alone or by copolymerization, and epoxy acrylates obtained by modifying epoxy resins with unsaturated monocarboxylic acids and acid anhydrides. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
Among the linear organic polymers, a linear organic polymer that is soluble or swellable in weak alkaline water is hereinafter also referred to as “alkali-soluble resin”.

  When a copolymer is used as the resin (for example, alkali-soluble resin) in the present invention, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters having an aliphatic hydroxyl group such as methacrylic acid esters.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among them, (meth) acrylic resins having an allyl group, a vinyl ester group and a carboxyl group in the side chain, and double in the side chain described in JP 2000-187322 A and JP 2002-62698 A An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Application Laid-Open No. 63-287944, Japanese Patent Application Laid-Open No. 63-287947, Japanese Patent Application Laid-Open No. Urethane binder polymers containing acid groups described in No. 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  The resin of the present invention is preferably a resin having a polymerizable group among the resins described above. The polymerizable group is preferably a group containing a double bond, and more preferably an acryloyl group or a methacryloyl group. The resin may be any of random polymer, block polymer, graft polymer and the like.

  The weight average molecular weight of the resin contained in the photosensitive resin composition in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1, It is 000 or more, More preferably, it is the range of 2,000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.

The resin in this invention may be used individually by 1 type, and may use 2 or more types together.
Although there is no limitation in particular as content (total content in the case of 2 or more) of resin in the total solid of the photosensitive resin composition of this invention, from the viewpoint of obtaining the effect of this invention more effectively. 5-50 mass% is preferable, 10-40 mass% is more preferable, 10-35 mass% is especially preferable.

<Polymerizable compound>
The photosensitive resin composition of the present invention contains a polymerizable compound.
As the polymerizable compound, for example, an addition polymerizable compound having at least one ethylenically unsaturated double bond can be used. Specifically, at least one terminal ethylenically unsaturated bond, preferably 2 is used. It is selected from compounds having at least one. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.

  Examples of monomers and their (co) polymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and (co) of these It is a polymer. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH ... (A)
(However, in general formula (A), R ⁴ and R ⁵ each represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, A photosensitive resin composition having an excellent photosensitive speed can be obtained.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of the photosensitive resin composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
Also, the polymerizable compound is compatible with other components (eg, photopolymerization initiator, colorant (pigment, dye), binder polymer, etc.) and dispersibility contained in the photosensitive resin composition. The selection and use method is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a support.

  The content of the polymerizable compound in the total solid content of the photosensitive resin composition of the present invention (the total content in the case of 2 or more types) is not particularly limited, but the viewpoint of obtaining the effect of the present invention more effectively. Is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, and particularly preferably 20 to 60% by mass.

<Photopolymerization initiator>
The photosensitive resin composition of the present invention contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can polymerize the above photopolymerizable compound, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, oxime compounds, and the like. Among these, an oxime compound is preferable from the viewpoint of further suppressing peeling of the light-shielding color filter (particularly, peeling when the light-shielding color filter is formed on a substrate having a structure).

The oxime compound (hereinafter also referred to as “oxime photopolymerization initiator”) is not particularly limited. For example, JP-A-2000-80068, WO-02 / 100903A1, JP-A-2001-233842, etc. The described oxime compounds can be used.
Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  Of these, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is particularly preferred. Examples of such oxime photopolymerization initiators include CGI-124 and CGI-242 (manufactured by Ciba Specialty Chemicals).

A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) ) Phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in JP-B 51-48516, and tinuvin 1130, 400. .

Moreover, you may use another well-known initiator other than the above-mentioned photoinitiator for the photosensitive resin composition of this invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Examples thereof include a teal-s-triazine compound.

The photosensitive resin composition of the present invention may contain only one kind of photopolymerization initiator or two or more kinds.
From the viewpoint of obtaining the effect of the present invention more effectively, the content of the photopolymerization initiator in the total solid content of the photosensitive resin composition of the present invention (total content in the case of two or more) is 3 to 3. 20 mass% is preferable, 4-19 mass% is more preferable, and 5-18 mass% is especially preferable.

<Other ingredients>
(Sensitizer)
The photosensitive resin composition of the present invention may contain a sensitizer.
As the sensitizer, one that sensitizes the above-described photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
That is, for example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes, thioxanthones, cyanines, merocyanines, phthalocyanines, thiazines, acridines , Anthraquinones, squaliums (eg, squalium), acridine orange, coumarins, ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrins, spiro Compound, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thiobar Tool acid derivatives, acetophenone, benzophenone, thioxanthone, aromatic ketone compounds such as Michler's ketone, and heterocyclic compounds such as N- aryl oxazolidinone and the like.

  When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer in the photosensitive resin composition is calculated in terms of solid content from the viewpoint of light absorption efficiency to the deep part and starting decomposition efficiency. 0.1 to 20% by mass is preferable, and 0.5 to 15% by mass is more preferable.

(Co-sensitizer)
The photosensitive resin composition of the present invention may contain a co-sensitizer.
The co-sensitizer has functions such as further improving the sensitivity of the photopolymerization initiator and the sensitizer to actinic radiation or suppressing inhibition of polymerization of the photopolymerizable compound by oxygen.

  Examples of such a co-sensitizer include amines (for example, “Journal of Polymer Society” written by MR Sander et al., Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 44-20189. JP-A-51-82102, JP-A-52-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104 , Research Disclosure 33825 and the like, and specific examples include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like),

  Other examples of co-sensitizers include thiols and sulfides (for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. Naphthalene, etc.),

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  When the photosensitive resin composition of the present invention contains a co-sensitizer, the content of the co-sensitizer is selected from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range of 0.1 to 30% by mass is preferable, the range of 1 to 25% by mass is more preferable, and the range of 0.5 to 20% by mass is more preferable.

(Thermal polymerization inhibitor)
In the photosensitive resin composition of the present invention, a small amount of a thermal polymerization inhibitor can be added during production or storage of the composition in order to prevent unnecessary thermal polymerization of the photopolymerizable compound.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. .

(Adhesion improver)
In the photosensitive resin composition of this invention, in order to improve adhesiveness with hard surfaces, such as a support body, an adhesive improvement agent can be added. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

  Furthermore, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, plasticizers, and sensitizers may be added to the photosensitive resin composition of the present invention.

The photosensitive resin composition of the present invention includes a chain transfer agent, a non-ionic surfactant such as polyoxyethylene alkyl ether, an azo-based surfactant for improving coating uniformity, if necessary. Thermal polymerization initiators such as compounds and peroxide compounds, thermal polymerization components, ultraviolet absorbers such as alkoxybenzophenone, plasticizers such as dioctyl phthalate, developability improvers such as low molecular weight organic carboxylic acids, other fillers, and the above Various additives such as a polymer compound other than the alkali-soluble resin, an antioxidant, an aggregation inhibitor and the like, and a polyfunctional thiol and an epoxy compound can be contained for the purpose of increasing the strength and sensitivity of the film.
In addition, a thermosetting agent can be added for the purpose of increasing the degree of curing of the film by performing post-heating after exposure and development. As a thermosetting agent, it is possible to add thermopolymerization initiators, such as an azo compound and a peroxide, and thermosetting materials, such as a novolak resin, a resole resin, an epoxy compound, and a styrene compound.

Examples of the thiol compounds such as the chain transfer agent or polyfunctional thiol include N, N-dialkylaminobenzoic acid alkyl ester, 2-mercaptobenzothiazole, 2-mercapto-1-phenylbenzimidazole, 3-mercapto-4-methyl- 5-phenyl-1,2,4-triazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, 3 -Methyl mercaptopropionate, ethyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetra (mercaptoacetate), pentae Stall tetra (3-mercaptopropionate) and the like.
These thiol compounds can be used alone or in admixture of two or more.

≪Light-shielding color filter≫
The light-shielding color filter of the present invention is formed using the above-described photosensitive resin composition of the present invention.
For this reason, the light-shielding color filter of this invention is excellent in light-shielding ability, and generation | occurrence | production of a defect is suppressed. Furthermore, peeling is suppressed.

In the present invention, the “light-shielding color filter” means a light-shielding pattern obtained by exposing and developing a photosensitive resin composition containing at least a black color material, a photopolymerizable compound, a resin, a photopolymerization initiator, and a solvent. Say. The color of the “light-shielding color filter” in the present invention may be an achromatic color such as black or gray, or a black or gray color mixed with a chromatic color.
The “light-shielding color filter” is obtained by exposing and developing a photosensitive resin composition containing at least a black color material, a photopolymerizable compound, a resin, a photopolymerization initiator, and a solvent. Alternatively, it may be paraphrased as a light shielding filter.
For example, in a solid-state imaging device, the light-shielding color filter is used to shield light other than the light receiving portion on the light receiving element forming surface, to shield light on the surface opposite to the light receiving element forming surface, and color adjustment pixels (black, The pixel may be an achromatic pixel such as gray, or may be a pixel such as black or gray mixed with a chromatic color).

The film thickness of the light-shielding color filter is not particularly limited, but is preferably 0.1 μm to 10 μm, more preferably 0.3 μm to 5.0 μm, from the viewpoint of obtaining the effect of the present invention more effectively. 5 μm to 3.0 μm is particularly preferable.
The pattern size of the light-shielding color filter is not particularly limited, but is preferably 1000 μm or less, more preferably 500 μm or less, and particularly preferably 300 μm or less from the viewpoint of obtaining the effect of the present invention more effectively. The lower limit is not particularly limited but is preferably 1 μm.

In addition, the spectral characteristics of the light-shielding color filter of the present invention are not particularly limited, but from the viewpoint of improving the light shielding ability in the infrared region, which may be required for a solid-state imaging device, the light shielding ability between the visible region and the infrared region. From the viewpoint of balance and the viewpoint of obtaining the effect of the present invention more effectively, the ratio [OD ₁₂₀₀ / OD ₃₆₅ ] of the optical density (OD ₁₂₀₀ ) at a wavelength of ₁₂₀₀ nm to the optical density (OD ₃₆₅ ) at a wavelength of 365 nm is 0. It is preferably 5 or more and 3 or less.

  The optical density (OD) is obtained by measuring the transmittance of the obtained film using UV-3600 manufactured by Shimadzu Corporation, and converting the obtained transmittance (% T) by the following formula B to obtain the OD value. To do.

  OD value = −Log (% T / 100) Formula B

In the present invention, the optical density at the wavelength _{λ nm} is expressed as “OD _λ ”.
Furthermore, the following conditions are suitable as the optical density of the light-shielding color filter from the viewpoint of the balance between the light-shielding ability in the visible region and the infrared region, and from the viewpoint of obtaining the effects of the present invention more effectively.
That is, the _[OD 1200 _{/ OD 365]} is more preferably 0.5 to 2.5, particularly preferably 0.7 to 2.5.
The optical density (OD ₁₂₀₀ ) at a wavelength of 1200 nm of the light-shielding color filter is preferably 1.5 or more and 10 or less, and more preferably 2 or more and 10 or less.
The optical density (OD ₃₆₅ ) at a wavelength of 365 nm of the light-shielding color filter is preferably 1 or more and 7 or less, and more preferably 2 or more and 6 or less.
The light density of the light-shielding color filter in the wavelength region of 900 nm to 1300 nm is preferably 2 or more, 10 or less, more preferably 2 or more and 9 or less, and particularly preferably 2 or more and 8 or less.
The ratio [OD ₉₀₀ / OD ₃₆₅ ] of the light-shielding color filter is preferably 0.5 or more and 2.5 or less, and more preferably 1.1 or more and 2.5 or less.
The ratio [OD ₁₁₀₀ / OD ₃₆₅ ] of the light-shielding color filter is preferably 0.4 or more and 2.5 or less, and more preferably 0.6 or more and 2.5 or less.
The ratio [OD ₁₃₀₀ / OD ₃₆₅ ] of the light-shielding color filter is preferably 0.4 or more and 2.5 or less, and more preferably 0.5 or more and 2.5 or less.

  The light-shielding color filter of the present invention can be suitably used for a solid-state image sensor such as a CCD or CMOS, and is particularly suitable for a solid-state image sensor such as a CCD or CMOS exceeding 1 million pixels.

≪Method for manufacturing light-shielding color filter≫
The method for forming the light-shielding color filter of the present invention described above is not particularly limited. For example, a step of forming a photosensitive layer by applying a photosensitive resin composition on a support (hereinafter referred to as “ Abbreviated as “photosensitive layer forming step”), a step of exposing the photosensitive layer in a pattern (hereinafter abbreviated as “exposure step” as appropriate), and developing the photosensitive layer after exposure. And a step of forming a colored pattern (hereinafter abbreviated as “development step” as appropriate).
Hereinafter, each process in the manufacturing method of the light-shielding color filter of this invention is demonstrated.

<Photosensitive layer forming step>
In the photosensitive layer forming step, the photosensitive resin composition of the present invention is applied on a support to form a photosensitive layer.

Examples of the support that can be used in this step include a photoelectric conversion element substrate used for a solid-state imaging element, such as a silicon substrate (silicon wafer), a complementary metal oxide semiconductor (CMOS), and the like.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

In the light-shielding color filter and the manufacturing method thereof according to the present invention, when a substrate having a structure (that is, a substrate on which a pattern structure is formed) is used as a support, the effect of suppressing peeling according to the present invention is more effective. Played.
Examples of the pattern structure include various pattern structures such as a thin film transistor, a photoelectric conversion element, and a passivation film. Further, as the pattern structure, a colored pattern (for example, a red pattern, a green pattern, a blue pattern, a transparent pattern, etc.) already provided on the substrate prior to the light-shielding color filter to be formed in the present invention. It may be.

  As a coating method of the photosensitive resin composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied. .

  When producing a light-shielding color filter, the coating film thickness (after drying) of the photosensitive resin composition is preferably 0.35 μm to 3.0 μm, preferably 0.50 μm to 2 from the viewpoint of resolution and developability. More preferably, it is 5 μm.

  The photosensitive resin composition coated on the support is usually dried at 70 ° C. to 130 ° C. for about 2 minutes to 4 minutes to form a photosensitive layer.

<Exposure process>
In the exposure step, the photosensitive layer formed in the photosensitive layer forming step is exposed and cured in a pattern, for example, through a mask (in the case of exposure through a mask, a light-irradiated coating film Only the part is cured).
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 3000 mJ, more preferably 10 mJ to 2000 mJ, and most preferably 10 mJ to 1000 mJ.

<Development process>
Subsequent to the exposure step, the exposed photosensitive layer is developed by, for example, an alkali development process to form a pattern (development step).
In the development step, the non-light-irradiated portion in the exposure step is eluted in the alkaline aqueous solution. Thereby, only a light irradiation part remains.
As the developer, an organic alkali developer is desirable in that it does not damage the underlying circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 240 seconds.

  Examples of the alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. An alkaline aqueous solution obtained by diluting an organic alkaline compound such as] -7-undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In the method for producing a light-shielding color filter of the present invention, after the photosensitive layer forming step, the exposure step, and the development step described above, the formed pattern is cured by heating and / or exposure as necessary. A curing step may be included.

≪Solid-state imaging device≫
The solid-state imaging device according to the present invention includes the above-described light-shielding color filter according to the present invention.
Since the solid-state imaging device of the present invention is provided with the light-shielding color filter of the present invention having excellent light shielding ability and few defects, noise is reduced and color reproducibility is excellent.
The configuration of the solid-state imaging device of the present invention is a configuration provided with the light-shielding color filter of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. It has a light receiving element composed of a plurality of photodiodes and polysilicon constituting a light receiving area of an image sensor (CCD image sensor, CMOS image sensor, etc.), and has a light receiving element forming surface side of the support (for example, other than the light receiving part) A configuration in which the light-shielding color filter of the present invention is provided on the side opposite to the formation surface.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

<Synthesis of specific resins 1-7>
(Synthesis of specific resin 1)
Into a 500 mL three-necked flask, 600.0 g of ε-caprolactone was introduced and 22.8 g of 2-ethyl-1-hexanol was introduced and dissolved while stirring while blowing nitrogen. Monobutyltin oxide 0.1g was added and it heated at 100 degreeC. After 8 hours, it was cooled to 80 ° C. after confirming disappearance of the raw material by gas chromatography. After adding 0.1 g of 2,6-di-t-butyl-4-methylphenol, 27.2 g of 2-methacryloyloxyethyl isocyanate was added. After 5 hours, after confirming disappearance of the raw material by ¹ H-NMR, the raw material was cooled to room temperature to obtain 200 g of a solid precursor M1 [the following structure]. Being M1 was confirmed by ¹ H-NMR, IR, and mass spectrometry.

  Precursor M1 80.0 g, methacrylic acid 20.0 g, dodecyl mercaptan 2.3 g and propylene glycol monomethyl ether acetate 233.3 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). And heated to 75 ° C. while flowing nitrogen into the flask. To this was added 0.2 g of 2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. After 2 hours, 0.2 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% solution of the specific resin 1 described below was obtained.

(Synthesis of specific resins 2-7)
Specific resins 2 to 7 described below were synthesized by the same synthesis method as that for specific resin 1. Table 1 below shows the composition ratio, the number of graft chain atoms excluding hydrogen atoms, and the weight average molecular weight.

[Example 1]
<Preparation of titanium black dispersion>
The mixture having the following composition was subjected to a dispersion treatment using an ultra apex mill manufactured by Kotobuki Industries Co., Ltd. as a dispersing device (bead mill).
Hereinafter, the first type of solvent used in preparing the titanium black dispersion is referred to as “dispersion solvent 1”, and the second type of solvent is referred to as “dispersion solvent 2”.
~composition~
-Gemco Co., Ltd. Titanium Black 13M-T ... 270 parts-Solsperse 5000 (manufactured by Nippon Lubrizol Corporation; first stage dispersant)
... 80 parts ・ Propylene glycol monomethyl ether acetate (PGMEA; Dispersion solvent 1)
... 600 parts, methyl amyl ketone (dispersion solvent 2) ... 50 parts

At this time, the dispersing apparatus was operated under the following conditions.
・ Bead diameter: φ0.05mm
・ Bead filling rate: 75% by volume
・ Peripheral speed: 7m / sec
・ Pump supply amount: 10kg / hour
・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15L
・ Amount of liquid mixture to be dispersed: 5kg

After the start of dispersion, the volume average particle size was measured at 30 minute intervals (one pass time).
The volume average particle diameter decreased with the dispersion time (number of passes), but the amount of change gradually decreased.
When the volume average particle diameter change when the dispersion time is extended by 30 minutes becomes 10 nm or less (that is, when the volume average particle diameter change becomes 10 nm / pass or less; Then, the following composition was added to the dispersion.

~composition~
・ Solsperse 5000 (manufactured by Nippon Lubrizol Co., Ltd .; second stage dispersant) 90 parts ・ Propylene glycol monomethyl ether acetate (solvent 1 at dispersion) 166 parts ・ Methyl amyl ketone (solvent 2 at dispersion) 14 parts

After the addition of the above composition, the dispersion treatment was further continued, and when the volume average particle size change was 10 nm or less per 30 minutes (this is the “second-stage dispersion treatment”). Completed.
Thus, a titanium black dispersion (hereinafter also referred to as “final titanium black dispersion”) was obtained.

<Preparation of photosensitive resin composition>
The following composition was mixed and the photosensitive resin composition was obtained.
Hereinafter, the first type of solvent used at the time of preparing the photosensitive resin composition is referred to as “solvent 1 at the time of preparing the composition”, and the second type of solvent is referred to as “solvent 2 at the time of preparing the composition”.
-Composition of photosensitive resin composition-
The final titanium black dispersion prepared above: 38 parts Dipentaerythritol hexaacrylate (T-1 below) 7 parts Oxime photopolymerization initiator (K-1 below) 6 parts Resin (J below) -1; Weight average molecular weight (Mw) and copolymerization ratio (molar ratio) are as follows: 9 parts propylene glycol monomethyl ether acetate (solvent 1 at the time of composition preparation)
... 31 parts methyl amyl ketone (solvent 2 during preparation of composition) ... 4 parts

<Production of light-shielding color filter>
(Preparation of substrate with pattern structure)
A commercially available 6-inch silicon wafer was coated with SR7200 manufactured by Hitachi Chemical Co., Ltd. to form a coating film, and the resulting coating film was subjected to pattern exposure, development, and heat treatment at 200 ° C. for 30 minutes to form a pattern. A structure was formed.
Thus, a substrate with a pattern structure in which pattern structures having a height of 15 μm and a pattern size of 300 μm × 300 μm were regularly arranged was obtained.

(Production of light-shielding color filter)
The photosensitive resin composition obtained above is applied to the pattern structure forming surface side of the substrate with the pattern structure by spin coating, and then heated at 120 ° C. for 2 minutes on a hot plate to form a photosensitive layer. Obtained.
Next, the obtained photosensitive layer is exposed using an i-line stepper so as to coincide with the pattern structure produced above (that is, to have the same pattern size as the pattern structure produced above). Went. Here, the exposure of the photosensitive layer was performed separately for an exposure spot with an exposure dose of 50 mJ / cm ^{2 and} an exposure spot with an exposure dose of 200 mJ / cm ² .
The light-shielding film after the exposure was subjected to paddle development for 60 seconds at 23 ° C. using a 0.3% aqueous solution of tetramethylammonium hydroxide. Thereafter, rinsing was performed with a spin shower, followed by washing with pure water to obtain a light-shielding color filter having a film thickness of 2.2 μm.
The light-shielding color filter was formed on the pattern structure. That is, the light-shielding color filter has the same pattern size as the pattern structure and is formed at the same position as the pattern structure so as to overlap the pattern structure.

<Evaluation>
The following evaluation was performed about the photosensitive resin composition and light-shielding color filter obtained above.
The evaluation results are shown in Table 2 below.

(Evaluation of coating defects)
The photosensitive resin composition obtained above is applied to a commercially available 6-inch silicon wafer by spin coating, and then heated at 120 ° C. for 2 minutes on a hot plate to obtain a photosensitive layer (light-shielding film). It was.
In the obtained photosensitive layer (light-shielding film), the area within an area of 100 cm ² was confirmed with an optical microscope (1000 magnifications), and the number of coating defects (foreign matters, bubbles, etc.) within the range was counted.
Based on the number of defects obtained, coating defects were evaluated according to the following evaluation criteria.

~Evaluation criteria~
A: The number of defects is less than 1 per 100 cm ² B: The number of defects is 1 or more and less than 3 per 100 cm ² C ... The number of defects is 3 or more and less than 5 per 100 cm ² D ... The number of defects is 5 or more per 100 cm ²

(Evaluation of shading color filter peeling)
About the obtained light-shielding color filter, the presence or absence of peeling was observed by optical microscope observation (magnification 1000 times), and peeling of the light-shielding color filter was evaluated according to the following evaluation criteria.

~Evaluation criteria~
A: There is no peeling at a portion formed at an exposure amount of 50 mJ / cm ² .
B: Although there is peeling at a portion formed at an exposure amount of 50 mJ / cm ² , there is no peeling at a portion formed at an exposure amount of 200 mJ / cm ² .
C: Peeling occurs in both the portion formed with an exposure amount of 50 mJ / cm ² and the portion formed with an exposure amount of 200 mJ / cm ² .

(Stability over time)
First, the photosensitive resin composition was diluted 500 times with propylene glycol monomethyl ether acetate, and the absorbance of the diluted solution was measured to obtain absorbance (i).
Next, the photosensitive resin composition was allowed to stand at room temperature for 1 month.
After standing for 1 month, the photosensitive resin composition from the liquid surface to 2 cm was sampled. The sampled photosensitive resin composition was diluted 500 times with propylene glycol monomethyl ether acetate, and the absorbance of the diluted solution was measured to obtain absorbance (ii).
From the absorbance (i) and the absorbance (ii), the rate of change in absorbance before and after standing for 1 month was determined, and the temporal stability (storage stability) was evaluated according to the following evaluation criteria.

~Evaluation criteria~
A: The rate of change in absorbance was less than 3%.
B: The rate of change in absorbance was 3% or more and less than 10%.
C: The rate of change in absorbance was 10% or more.

[Examples 2, 3, 6 to 19]
Table 2 shows the types of solvent 1 during dispersion, solvent 2 during dispersion, type of dispersant, type of solvent 1 during composition preparation, type of solvent 2 during composition preparation, and type of photopolymerization initiator. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the changes were made as shown.
Using the obtained photosensitive resin composition, a light-shielding color filter was produced on a wafer with a pattern structure in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2 below.

Example 4
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the solvent 2 was not used at the time of preparing the composition and the amount of the solvent 1 was changed to 35 parts at the time of preparing the composition.
Using the obtained photosensitive resin composition, a light-shielding color filter was produced on a wafer with a pattern structure in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2 below.

Example 5
In the first stage dispersion treatment, the dispersion solvent 2 was not used, and the amount of the dispersion solvent 1 was changed to 650 parts. In the second dispersion process, the dispersion solvent 2 was not used and the dispersion was performed. A photosensitive resin composition was produced in the same manner as in Example 1 except that the amount of solvent 1 was changed to 180 parts.
Using the obtained photosensitive resin composition, a light-shielding color filter was produced on a wafer with a pattern structure in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2 below.

[Comparative Example 1]
In the first stage dispersion treatment, the dispersion solvent 2 was not used, and the amount of the dispersion solvent 1 was changed to 650 parts. In the second stage dispersion treatment, the dispersion solvent 2 was not used and the dispersion solvent was used. The amount of 1 was changed to 180 parts, and in the preparation of the photosensitive resin composition, the solvent 2 was not used at the time of preparing the composition, and the amount of the solvent 1 at the time of preparing the composition was changed to 35 parts. A photosensitive resin composition was prepared in the same manner as in Example 1.
Using the obtained photosensitive resin composition, a light-shielding color filter was produced on a wafer with a pattern structure in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2 below.

[Comparative Example 2]
In the first stage dispersion process, the amount of the first stage dispersant was changed to 170 parts, the amount of solvent 1 during dispersion was changed to 766 parts, the amount of solvent 2 during dispersion was changed to 64 parts, and the dispersion of the second stage A photosensitive resin composition was prepared in the same manner as in Example 1 except that the treatment was not performed.
Using the obtained photosensitive resin composition, a light-shielding color filter was produced on a wafer with a pattern structure in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2 below.

[Comparative Example 3]
In the first stage dispersion treatment, the amount of the first stage dispersant was changed to 170 parts, the amount of solvent 1 during dispersion was changed to 830 parts, and the solvent 2 during dispersion was not used. Photosensitization was carried out in the same manner as in Example 1 except that no solvent 2 was used in the preparation of the photosensitive resin composition and the amount of the solvent 1 was changed to 35 parts during the preparation of the composition. A functional resin composition was prepared.

In Table 2 below, specific resin 1 to specific resin 7 are the resins synthesized above.
In Table 2 below, “Compound (VI)” is the following triazine photopolymerization initiator (Compound (VI)).
In Table 2 below, “IRG369” is the following aminoalkylphenone photopolymerization initiator (Irgacure 369).
In Table 2 below, “K-2” is an oxime photopolymerization initiator represented by K-2 described above.

~ Explanation of Table 2 ~
“PGMEA” represents propylene glycol monomethyl ether acetate, and “PGME” represents propylene glycol monomethyl ether.

  As shown in Table 2, in Examples 1 to 19 in which photosensitive resin compositions containing a specific solvent component were prepared by multistage dispersion treatment, the occurrence of coating defects was suppressed. In Examples 1 to 19, peeling of the light-shielding color filter when the light-shielding color filter was produced on a substrate having a structure was suppressed. Further, in Examples 1 to 19, the temporal stability of the photosensitive resin composition was also excellent.

  In the above embodiment, an example in which a substrate with a pattern structure (wafer) is used as a support has been described, but by using a solid-state imaging device substrate on which a light receiving element such as a photodiode is formed as a support, A solid-state imaging device with little noise and excellent color reproducibility can be manufactured.

Claims (9)

Titanium black, a dispersant, a resin, a polymerizable compound, a photopolymerization initiator, at least one selected from a propylene glycol alkyl ether solvent and a propylene glycol alkyl ether acetate solvent, an aromatic solvent, and In the process of producing a photosensitive resin composition containing at least one selected from ketone solvents,
For the mixed liquid containing titanium black and a dispersant, a dispersion treatment is performed until the change in volume average particle diameter of the titanium black is 10 nm / pass or less,
The manufacturing method of the photosensitive resin composition which adds a dispersing agent to the dispersion liquid obtained by the said dispersion process, and performs a dispersion process until the change of the volume average particle diameter of the said titanium black is 10 nm / pass or less .   The method for producing a photosensitive resin composition according to claim 1, wherein the mixed solution contains at least one selected from a propylene glycol alkyl ether solvent and a propylene glycol alkyl ether acetate solvent.   The method for producing a photosensitive resin composition according to claim 1 or 2, wherein at least one selected from the aromatic solvent and the ketone solvent is at least one selected from an aliphatic ketone solvent. .   The method for producing a photosensitive resin composition according to any one of claims 1 to 3, wherein the photopolymerization initiator is an oxime photopolymerization initiator.   The photosensitive resin composition manufactured by the manufacturing method of the photosensitive resin composition of any one of Claims 1-4.   The photosensitive resin composition of Claim 5 used for formation of the light-shielding color filter for solid-state image sensors. A step of applying a photosensitive resin composition according to claim 5 or 6 to form a photosensitive layer on a support;
Exposing the photosensitive layer in a pattern;
Developing the photosensitive layer after exposure to form a colored pattern;
The manufacturing method of the light-shielding color filter which has this.   A light-shielding color filter produced by the method for producing a light-shielding color filter according to claim 7.   A solid-state imaging device comprising the light-shielding color filter according to claim 8.