JP6091198B2 - Photosensitive resin composition, color filter, liquid crystal display device, and organic light emitting display device - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a color filter, a liquid crystal display device, and an organic light emitting display device.

Many thin image display devices represented by displays and the like, so-called flat panel displays, have been put on the market, characterized by being thinner than a cathode ray tube type display and taking up little space in the depth direction. The market price has become affordable year by year with the evolution of production technology, the demand has further expanded, and the production volume has been increasing year by year. In particular, color LCD TVs have almost reached the mainstream of TV. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, the amount of light is controlled by electrically driving the liquid crystal, and color expression is performed by the light passing through a color filter. Therefore, a color filter must be present in the color representation of a liquid crystal television and plays a major role in determining the performance of the display. In the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed as in the liquid crystal display device.

As a recent trend, there is a demand for power saving of an image display device, and in order to improve the utilization efficiency of a backlight, a high brightness of a color filter is particularly demanded. This is a big problem especially for mobile displays (cell phones, smartphones, tablet PCs).
Although the battery capacity has increased due to technological evolution, the amount of power stored in mobile remains the same, while the power consumption tends to increase as the screen size increases. An image display device including a color filter affects the design and performance of a mobile terminal in order to be directly linked to the usable time and charging frequency of the mobile terminal.

Here, the color filter is generally formed on a transparent substrate, a transparent layer formed on the transparent substrate, and composed of a colored layer of three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. And a light shielding portion formed.
As a method for forming such a colored layer, a pigment dispersion method using a pigment having excellent heat resistance and light resistance as a colorant has been widely used. However, with color filters using pigments, it has become difficult to achieve the current demand for higher brightness.

  As one means for achieving high brightness, a photosensitive resin composition for a color filter using a dye has been studied. Dyes generally have higher transmittance than pigments and can produce high-intensity color filters, but they have poor heat resistance and light resistance, and chromaticity tends to change during high-temperature heating in the color filter production process. there were. Moreover, the photosensitive resin composition using a dye has a problem that foreign matters are likely to precipitate during the drying process. When foreign matter is deposited on the coating film, the contrast is remarkably deteriorated and it is difficult to use it as a colored layer.

  In the blue pixel of the color filter, it is considered to use a triarylmethane dye excellent in luminance in place of the copper phthalocyanine pigment (PB15: 6) excellent in heat resistance and light resistance, which has been widely used conventionally. It has begun (for example, patent document 1). However, the triarylmethane dye was also poor in heat resistance and light resistance like the other dyes.

As a technique for improving the heat resistance and light resistance of a triarylmethane dye, it has been studied to make a triarylmethane dye into a lake and use it as a lake pigment.
For example, Patent Document 2 discloses a blue pigment for a color filter composed of an anion containing one or more elements selected from tungsten, silicon, and phosphorus as basic elements and oxygen as essential elements. It is described that by using the pigment, a liquid crystal display device capable of providing a liquid crystal display excellent in luminance over a long time even at high temperatures can be provided.

  Patent Documents 3 and 4 specify phosphorus or silicon, molybdenum, and tungsten as counter-anions of triarylmethane dye cations as lake color materials that have better heat resistance and light resistance than conventional lake pigments. Lake color materials using heteropolyoxometalate anions contained in the proportions of

  On the other hand, Patent Document 5 discloses a negative resist for a color filter, which contains a specific pigment dispersant, a pigment, a polyfunctional thiol compound, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. A composition is disclosed. According to Patent Document 5, it is described that the use of a combination of the specific pigment dispersant and the polyfunctional thiol compound suppresses the occurrence of water stain that occurs when the specific pigment dispersant is used. Has been.

JP 2009-186657 A JP 2011-186043 A International Publication No. 2012/039416 Pamphlet International Publication No. 2012/039417 Pamphlet JP 2010-237571 A

  The present inventors have studied to use the triarylmethane compounds described in Patent Documents 3 and 4 because they are excellent in heat resistance and light resistance and can be expected to increase color filter luminance. However, the photosensitive resin composition using the compound as a coloring material has been found to have a poor development adhesion when stored for a long period of time. In the present invention, the development adhesion refers to the adhesion between the developed pattern-like colored layer and the substrate during development. When the development adhesiveness is lowered, it becomes difficult to form fine pixels. For this reason, in a color filter for which further high definition is desired, development adhesion is an important problem.

  The present invention has been made in view of the above circumstances, a photosensitive resin composition excellent in developability and development adhesion even after storage for a long time, a color filter using the photosensitive composition, An object of the present invention is to provide a liquid crystal display device and an organic light emitting display device having the color filter.

The present inventors can use the photosensitive resin composition having a specific color material in combination with a polyfunctional thiol compound, even when the photosensitive resin composition is stored for a long period of time. The knowledge that the development adhesiveness with the coating film formed using the photosensitive resin composition and a board | substrate is hard to fall was acquired.
The present invention has been completed based on such knowledge.

The photosensitive resin composition according to the present invention contains a colorant represented by the following general formula (I), a dispersant, a polyfunctional thiol compound, a photosensitive binder component, and a solvent, and the polyfunctional The thiol compound is a polyfunctional secondary thiol compound .

(In the general formula (I), R ^I , R ^II , R ^III , R ^IV , R ^V and R ^VI each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, ^- is ^{_{(SiMoW 11 O 40) 4- /}} 4 and _{(P 2 Mo y W 18-} y O 62) 6- / 6 is represented by at least one, y = 1, 2 or 3 of an integer heteropoly Represents an oxometalate anion.)

  In the photosensitive resin composition according to the present invention, the polyfunctional thiol compound is a polyfunctional secondary thiol compound from the viewpoint of viscosity stability of the photosensitive resin composition and development adhesion to the substrate. preferable.

  In the photosensitive resin composition according to the present invention, the polyfunctional thiol compound is a polyfunctional thiol compound represented by the following general formula (II), the viscosity stability of the photosensitive resin composition, and the substrate From the viewpoint of development adhesion to

In (formula (II), ^{R 1} represents an alkyl group having 1 to 6 carbon atoms, ^{R 2} represents an alkylene group having 1 to 6 carbon atoms, Q is a polyhydric alcohol hydroxyl number 2-6 Represents a residue, and n is an integer of 2 to 6.)

  The color filter according to the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is the photosensitive resin composition according to the present invention. It is characterized by being a colored layer formed by curing.

The present invention provides a liquid crystal display device comprising the color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
The present invention also provides an organic light emitting display device comprising the color filter according to the present invention and an organic light emitter.

  According to the present invention, a photosensitive resin composition excellent in developability and development adhesion even after long-term storage, a color filter using the photosensitive composition, a liquid crystal display device having the color filter, In addition, an organic light emitting display device can be provided.

It is the schematic which shows an example of the color filter of this invention. It is the schematic which shows an example of the liquid crystal display device of this invention. It is the schematic which shows an example of the organic light emitting display apparatus of this invention.

Hereinafter, the photosensitive resin composition, the color filter, the liquid crystal display device, and the organic light emitting display device according to the present invention will be described in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. In the present invention, (meth) acryl means either acryl or methacryl, and (meth) acrylate means either acrylate or methacrylate.

[Photosensitive resin composition]
The photosensitive resin composition according to the present invention comprises a colorant represented by the following general formula (I), a dispersant, a polyfunctional thiol compound, a photosensitive binder component, and a solvent. To do.

(In the general formula (I), R ^I , R ^II , R ^III , R ^IV , R ^V and R ^VI each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, ^- is ^{_{(SiMoW 11 O 40) 4- /}} 4 and _{(P 2 Mo y W 18-} y O 62) 6- / 6 is represented by at least one, y = 1, 2 or 3 of an integer heteropoly Represents an oxometalate anion.)

  The photosensitive resin composition of the present invention has a brightness higher than that of a conventional phthalocyanine pigment and a conventional lake pigment by using a combination of the specific colorant, a dispersant, and a polyfunctional thiol compound. In addition to being superior in heat resistance and light resistance, it is also possible to suppress a decrease in development adhesiveness after storage over time, which was a peculiar problem that occurred when the colorant was used in a photosensitive resin composition. it can.

Although there is an unexplained part as an action that exerts the above effects by the specific combination, it is presumed as follows.
The colorant represented by the general formula (I) has higher brightness than phthalocyanine pigments and is superior in heat resistance and light resistance to conventional lake pigments. However, when the photosensitive resin composition prepared using the color material represented by the general formula (I) is used after storage as in Comparative Examples 1 to 3 to be described later, the development adhesion decreases, and the fine line There is a problem that the colored layer of the pattern is lost during development and cannot remain. The photosensitive resin compositions of Comparative Examples 1 to 3 were excellent in viscosity stability, and the above problem of deterioration in development adhesion was not solved simply by improving the dispersion stability. The reason for the decrease in development adhesion is unclear, but it is assumed that the adhesion between the colorant and the photosensitive binder component during storage will gradually decrease the adhesion to the substrate during development. Is done.
The present invention provides a photosensitive resin composition using a combination of a colorant represented by the general formula (I), a dispersant, a polyfunctional thiol compound, and a photosensitive binder component. It is estimated that the interaction between the coloring material and the photosensitive binder component is alleviated. As a result, even after the photosensitive resin composition is stored for a long period of time, the adhesion between the patterned colored layer formed using the photosensitive resin composition during development and the substrate does not deteriorate.

The photosensitive resin composition of the present invention contains a coloring material, a dispersant, a polyfunctional thiol compound, and a solvent, and other components may be added as necessary as long as the effects of the present invention are not impaired. It may be contained.
Hereinafter, each component of the photosensitive resin composition according to the present invention will be described in detail in order.

<Coloring material represented by general formula (I)>
In the present invention, a color material represented by the following general formula (I) is used.

(In the general formula (I), R ^I , R ^II , R ^III , R ^IV , R ^V and R ^VI each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, ^- is ^{_{(SiMoW 11 O 40) 4- /}} 4 and _{(P 2 Mo y W 18-} y O 62) 6- / 6 is represented by at least one, y = 1, 2 or 3 of an integer heteropoly Represents an oxometalate anion.)

  Since the color material represented by the general formula (I) is a color material obtained by rake-forming a dye, it is suitable for increasing the brightness as in the case of a conventional dye. Furthermore, since the specific heteropolyoxometalate anion is used, it is excellent in heat resistance and light resistance as compared with conventional color materials.

Examples of the alkyl group having 1 to 3 carbon atoms of R ^{I to} R ^{VI in} the general formula (I) include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group.

The structure of the cation moiety having a triarylmethane skeleton may be appropriately selected depending on the desired chromaticity and the like. Among these, from the viewpoint of easily achieving high brightness and high contrast, it is preferable to have the same structure as the cation portion of a conventionally known triarylmethane dye. As specific examples, for example, in the general formula (I), R ^{I to} R ^V are ethyl groups, R ^VI is a hydrogen atom, Basic Blue 7, R ^{I to} R ^IV are methyl groups, R ^V is a phenyl group, Basic Blue 26 in which R ^VI is a hydrogen atom, R ^{I to} R ^IV are methyl groups, R ^V is an ethyl group, Basic Blue 11 in which R ^VI is a hydrogen atom, R ^{I to} R ^V are methyl groups, and R ^VI is phenyl Examples thereof include a cation portion such as basic blue 8 and the like, and it is preferable to have a cation portion structure similar to that of basic blue 7 from the viewpoint of easily achieving high luminance and high contrast.

The general formula X in (I) ^{- _{is, (SiMoW 11 O 40) 4-}} / 4 and _{(P 2 Mo y W 18-} y O 62) 6- / 6 is represented by at least one, y = 1, It is a heteropolyoxometalate anion that is an integer of 2 or 3. X in the color material represented by the above general Formulas (I) ^{- _{The, (SiMoW 11 O 40) 4-}} / 4, _or, one _{(P 2 Mo y W 18-} y O 62) 6- / 6 it only may be ^{_{used, (SiMoW 11 O 40) 4-}} / 4 and _{(P 2 Mo y W 18-} y O 62) 6- / 6 of may be used as a mixture of two or more.

The heteropolyoxometalate anion represented by (SiMoW ₁₁ O ₄₀ ) ^4- / 4 is used as a corresponding heteropolyacid or a corresponding heteropolyoxometalate alkali metal salt, for example, Journal of American Chemical Society, 104 (1982). It can be obtained according to the method described in p3194. Specifically, a heteropolyacid can be obtained by mixing and stirring a nitric acid aqueous solution and an alkali metal molybdate aqueous solution, adding K ₈ (α-type SiW ₁₁ O ₃₉ ) thereto, and stirring for 2 to 6 hours. Furthermore, a heteropolyoxometalate alkali metal salt can be obtained by reacting the obtained heteropolyacid with an alkali metal chloride.

_Also, hetero polyoxometalate anion represented by _{(P 2 Mo y W 18-} y O 62) 6- / 6 the corresponding heteropoly acid, or the corresponding heteroaryl polyoxometallate alkali metal salts, for example, Inorganic Chemistry , vol 47, p3679. Specifically, the heteropolyacid is obtained by dissolving an alkali metal tungstate and an alkali metal molybdate in water, adding phosphoric acid thereto, and heating to reflux for 5 to 10 hours with stirring. Can be obtained. Furthermore, a heteropolyoxometalate alkali metal salt can be obtained by reacting the obtained heteropolyacid with an alkali metal salt compound. In addition, the number y of molybdenum in the said heteropolyoxometalate anion can be adjusted to the range of 1-3 by adjusting suitably the preparation amount of the said alkali metal tungstate and a molybdate alkali metal salt.

Also, an alkali metal molybdate salt is dissolved in water, hydrochloric acid is added thereto, and then an α2-type deficient Dawson-type phosphotungstic acid alkali metal salt such as K ₁₀ (α2-type P ₂ W ₁₇ O ₆₁ ) is added. By stirring at 10 to 30 ° C. for 30 minutes to 2 hours, it is possible to obtain only P ₂ Mo ₁ W ₁₇ O ₆₂ having no y distribution.

Examples of the heteropolyoxometalate alkali metal salt include K ₄ (SiMoW ₁₁ O ₄₀ ), K ₆ (P ₂ MoW ₁₇ O ₆₂ ), K ₆ (P ₂ Mo ₂ W ₁₆ O ₆₂ ), and K ₆ (P ₂ ). Mo ₃ W ₁₅ O ₆₂ ) and the like.

  The colorant represented by the above general formula (I) is obtained by salt-substitution of the heteropolyacid or heteropolyoxometalate alkali metal salt corresponding to the obtained heteropolyoxometalate anion and a dye having a desired structure. Can be obtained. From the viewpoint of high reaction yield of salt substitution, it is preferable to use a heteropolyoxometalate alkali metal salt rather than a heteropolyacid.

  The colorant represented by the general formula (I) may be a hydrate having water of crystallization or an anhydride. Moreover, you may use the color material represented by the said general formula (I) individually by 1 type or in combination of 2 or more types.

The average primary particle diameter of the color material represented by the above general formula (I) used in the present invention is not particularly limited as long as it can produce a desired color when used as a color layer of a color filter. That's fine. Especially, it is preferable to exist in the range of 10-200 nm, and it is more preferable that it is 10-100 nm. When the average primary particle diameter of the color material is in the above range, a display device including a color filter manufactured using the photosensitive resin composition of the present invention can be made with high contrast and high quality. . In addition, since it is superior in heat resistance and light resistance as compared with conventional color materials, there is less possibility of causing problems of heat resistance and light resistance due to miniaturization of the particle size of the color material. In the present invention, in particular, when used in combination with a dispersant described later, the dispersibility and dispersion stability are excellent, and the heat resistance is also improved, so the average particle diameter of the coloring material is in the above range. As shown in FIG. 1, the smaller the size compared with the conventional one, the more the characteristics of the photosensitive resin composition of the present invention can be exhibited.
In addition, the average particle diameter of the said color material can be calculated | required by the method of measuring the magnitude | size of a primary particle directly from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle were measured, and the average was taken as the particle diameter of the particle. Next, for each of 100 or more particles, the volume (weight) of each particle was obtained by approximating a rectangular parallelepiped having the obtained particle size, and the volume average particle size was obtained and used as the average particle size. Note that the same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

<Dispersant>
In the present invention, the dispersant can be appropriately selected from known dispersants. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.

  Examples of the polymer dispersant include polymer dispersants such as modified polyurethane, modified polyacrylate, modified polyester, and modified polyamide. Specifically, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (partial) ammonium Salts (partial) alkylamine salts; (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters having amino groups, (partial) acid-modified products of amino groups of the polymers; hydroxyl group-containing polyacrylic acid (Co) polymers of hydroxyl-containing unsaturated carboxylic acid esters such as esters and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; poly (lower alkylene imines) and free Examples thereof include amides obtained by reaction with carboxyl group-containing polyesters and salts thereof. Examples of such commercially available polymer dispersants include EFKA-4046, EFKA-4047, EFKA polymer 10, EFKA polymer 400, EFKA polymer 401, EFKA polymer 4300, EFKA polymer 4310, EFKA polymer 4320, and EFKA polymer 4330 (above , BASF Japan Co., Ltd.), Disperbyk111, Disperbyk161, Disperbyk165, Disperbyk167, Disperbyk182, Disperbyk2000, Disperbyk2001, BYK-LPN6919, BYK-LPN11619, BYK-LPN116SP Lube Manufactured tetrazole Ltd.), Ajisper manufactured (registered trademark) PB821, PB822 (Ajinomoto Fine-Techno Co.), and the like.

  The weight average molecular weight of the polymer dispersant is preferably in the range of 500 to 100,000 in terms of polystyrene, more preferably 1,000 to 30,000. If the weight average molecular weight is 500 or more, the dispersion stability is improved, and if it is 100,000 or less, more preferably 30,000 or less, the developability and resolution are improved.

  As the polymer dispersant, among them, a polymer dispersant having a nitrogen atom is preferable from the viewpoint of excellent dispersibility and dispersion stability of the colorant represented by the general formula (I). A polymer dispersant having a salt is more preferable.

When a polymer dispersant having an amine or ammonium salt is used, the amine value is preferably in the range of 200 mgKOH / g or less, more preferably in the range of 50 to 180 mgKOH / g, and in the range of 70 to 170 mgKOH, from the viewpoint of the stability of the dispersion. The range of / g is more preferable. When the amine value is in the above range, the adsorption amount of the amine portion of the dispersant is appropriate for the colorant represented by the general formula (I), and the dispersion stability is improved.
In the present invention, the amine value means the weight (mg) of potassium hydroxide (KOH) equivalent to the amount of hydrochloric acid necessary to neutralize 1 g of the solid content, and according to the method described in JIS K7237. Can be measured.
When a polymer dispersant having an amine or ammonium salt is used, the amine or ammonium salt is preferably present in the side chain or resin terminal.

  Examples of the polymer dispersant having an amine or ammonium salt include (partial) amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid; Polyurethanes; unsaturated polyamides; polyethyleneimine derivatives; polyallylamine derivatives and the like.

  As the dispersant used in the present invention, a block copolymer type or graft copolymer (comb type) type polymer dispersant in which a pigment adsorption site and a solvent affinity site are functionally separated in the molecule is a dispersible polymer. It is preferable from the point.

<Multifunctional thiol compound>
In the photosensitive resin composition of the present invention, the polyfunctional thiol compound is a compound having two or more thiol groups in one molecule.
In the photosensitive resin composition of the present invention, the colorant represented by the general formula (I) and the polyfunctional thiol compound are used in combination to prevent deterioration of the photosensitive resin composition over time, Even after long-term storage, it is excellent in developability and development adhesion.

The polyfunctional thiol compound can be appropriately selected from known compounds having two or more thiol groups in one molecule. In the photosensitive resin composition of this invention, a polyfunctional thiol compound may be used individually by 1 type, and may be used in combination of 2 or more type.
Specific examples of the polyfunctional thiol compound include, for example, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1, 2-cyclohexanedithiol, decanedithiol, ethylene glycol bisthioglycolate, ethylene glycol bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, 1,4-butanediol dithioglycolate, 1,4-butanediol Bis (3-mercaptopropionate), trimethylolpropane tristhioglycolate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakis (3-me Captopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptopropionate), and other polyhydric alcohols and thioglycolic acid, mercaptopropionic acid and other thiol groups Esters with carboxylic acids, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) ) -4,6-dimercapto-s-triazine and the like.

  The polyfunctional thiol compound may be a polyfunctional thiol compound having a substituent at a carbon atom at the α-position and / or the β-position with respect to the thiol group. Specific examples thereof include 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, phthalic acid di (1-mercaptoethyl ester), and phthalic acid. Examples thereof include di (2-mercaptopropyl ester), diphthalic acid di (3-mercaptobutyl ester), and diphthalic acid di (3-mercaptoisobutyl ester).

  Further, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3 -Mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoprote) Pionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate) Octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate) , Ethylene glycol bis (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol Bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythris Tall hexakis (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexa Kiss (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (4-mercaptoisovalerate), diethylene glycol bis (4-merca) Ptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipenta Erythritol hexakis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercapto) Valerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerley) ), Dipentaerythritol hexakis (3-mercapto valerate), and the like.

  In the present invention, the polyfunctional thiol compound is preferably a polyfunctional secondary thiol compound having a secondary thiol group in which the carbon atom to which the thiol group is bonded is a secondary carbon atom. Since the secondary thiol is less reactive than the primary thiol, the reaction with each component in the photosensitive resin composition, such as a photosensitive binder component described later, is difficult to proceed. It is because it is excellent in storage stability.

  The polyfunctional thiol compound is preferably a polyfunctional thiol compound represented by the following general formula (II) from the viewpoint of stability, reactivity and odor when a photosensitive resin composition is used.

(In General Formula (II), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² represents an alkylene group having 1 to 6 carbon atoms, and Q represents a group having 2 to 6 hydroxyl groups. Represents a residue of a polyhydric alcohol, and n is an integer of 2 to 6.)

In formula (II), ^{R 1} is hydrogen atom, or an alkyl group having 1 to 6 carbon atoms. Among these, from the viewpoint of storage stability of the photosensitive resin composition, R ¹ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

  A C1-C6 alkyl group is a linear, branched, or cyclic alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl. Groups, tert-butyl groups, various pentyl groups, various hexyl groups, cyclopentyl groups, cyclohexyl groups, and the like. Moreover, as a C1-C6 alkylene group, it is a linear or branched alkylene group, and a methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, various hexylene groups, etc. are mentioned. be able to.

  Q is a residue of a polyhydric alcohol that forms an ester with a specific thiol group-containing carboxylic acid. Examples of the polyhydric alcohol used here include, but are not limited to, ethylene glycol, propylene glycol, butanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like. p represents the number of esters of a specific thiol group-containing carboxylic acid and a polyhydric alcohol, and is an integer of 2 to 6 corresponding to the number of hydroxyl groups in the residue of a polyhydric alcohol having 2 to 6 hydroxyl groups.

  In the polyfunctional thiol compound used in the present invention, the number of thiol groups in one molecule is preferably 3 or more, and more preferably 3 to 6 in order to preserve the storage stability of the photosensitive resin composition. It is preferable from the viewpoints of excellent developability and adhesion.

  Among the polyfunctional thiol compounds used in the present invention, butanediol bis (3-mercaptopropionate) (BDTP), trimethylolpropane tris (3-mercaptopropionate) (TMTP), pentaerythritol tetrakis (3 -Mercaptopropionate) (PETP), Tris (2-hydroxyethyl) isocyanurate tris (3-mercaptopropionate) (THEIC-BMPA), pentaerythritol tetra (3-mercaptobutyrate) (PTMP), trimethylol Propane tris (3-mercaptobutyrate) (TPMB), trimethylolethane tris (3-mercaptobutyrate) (TEMB), pentaerythritol tetrakis- (3-mercaptopropionate) (PEMP), etc. Luccaptoalkylate derivatives; ethylene glycol bisthioglycolate (EGTG), butanediol bisthioglycolate (BDTG), hexanediol bisthioglycolate (HDTG), trimethylolpropane tristhioglycolate (TMTG), pentaerythritol tetrakis Thioglycolic acid derivatives such as thioglycolate (PETG); 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5- Triazine-2,4,6 (1H, 3H, 5H) -trione is preferable from the viewpoint of storage stability, reactivity, and workability due to odor, but is not limited thereto.

<Photosensitive binder component>
The photosensitive resin composition of the present invention contains a photosensitive binder component. As the photosensitive binder component in the present invention, a negative photosensitive binder component is usually used.
As the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is suitably used. Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator will be specifically described.

(Alkali-soluble resin)
The alkali-soluble resin in the present invention has a carboxyl group, acts as a binder resin, and is suitably selected and used as long as it is soluble in a developer used for pattern formation, particularly preferably an alkali developer. be able to.
A preferable alkali-soluble resin in the present invention is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the colored resin composition for color filters.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the colored resin composition for a color filter, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

Examples of the acrylic copolymer having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec- Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxy Ethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, allyl (meth) acrylic 2,2′-oxybis (methylene) bis-2-propenoate, styrene, γ-methylstyrene, glycidyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, One or more selected from N-vinyl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, and the like, (meth) acrylic acid, 2- (meth) acryloyl Dimer of oxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, acrylic acid (for example, M-5600 manufactured by Toagosei Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid Examples of copolymers comprising at least one selected from these anhydrides It can be. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer, a polymer or the like into which an ethylenically unsaturated bond is introduced may be polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly preferable in that it becomes possible and the colored layer becomes more stable.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by weight, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by weight, there is a tendency that the formed pattern is easily detached from the substrate or the pattern surface is roughened during development with an alkali developer.

The acid value of the carboxyl group-containing copolymer is preferably 30 to 150 mgKOH / g. In the present invention, the acid value means the number of mg of potassium hydroxide required to neutralize the acid component contained in 1 g of the solid content of the polymer, and can be measured by the method defined in JIS-K0070. .
The weight average molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 4,000 to 25,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 50,000, pattern formation may be difficult during development with an alkaline developer. The weight average molecular weight here is determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
Although it does not specifically limit as an epoxy compound, A bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, an aliphatic epoxy compound, or Examples thereof include epoxy compounds such as bisphenolfluorene type epoxy compounds. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, (meth) acryloyloxyethyl hexahydrophthalic acid, (Meth) acrylic acid dimer, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like. These unsaturated group-containing monocarboxylic acids may be used alone or in combination of two or more.

Acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendo Dibasic acid anhydrides such as methylenetetrahydrophthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl Aromatic polycarboxylic acid anhydrides such as ether tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, endobicyclo- [2 , 2,1] -Hept-5-ene-2,3-dica Polycarboxylic anhydride derivatives such as carbon anhydride, and the like. These may be used alone or in combination of two or more.
Although the weight average molecular weight Mw of the epoxy (meth) acrylate compound having a carboxyl group thus obtained is not particularly limited, it is preferably 1000 to 40000, more preferably 2000 to 5000.

  The alkali-soluble resin used in the photosensitive resin composition of the present invention may be used singly or in combination of two or more, and the content thereof is included in the photosensitive resin composition. Usually, it is in the range of 10 to 1000 parts by weight, preferably in the range of 20 to 500 parts by weight, with respect to 100 parts by weight of the coloring material. If the content of the alkali-soluble resin is too small, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is too large, the ratio of the coloring material is relatively low, which is sufficient. The coloring density may not be obtained.

(Polyfunctional monomer)
The polyfunctional monomer used in the colored resin composition for a color filter of the present invention is not particularly limited as long as it can be polymerized by a photoinitiator described later. Usually, two ethylenically unsaturated double bonds are present. A compound having the above is used, and it is particularly preferably a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups.

  Examples of such polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, propylene glycol di (meth) acrylate, and glycerol di (meth). Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, triglycerol di (Meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, methoxylated cyclohexyl Di (meth) acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di Bifunctional (meth) acrylates such as (meth) acrylate, phthalic acid di (meth) acrylate, phosphoric acid di (meth) acrylate, and zinc di (meth) acrylate may be mentioned.

  Examples of the trifunctional or higher polyfunctional (meth) acrylate include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, succinic anhydride-modified pentaerythritol tetra (meth) acrylate, tri (meth) acrylate phosphate, tris (acryloxyethyl) isocyanurate, tris ( Methacryloxyethyl) isocyanurate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol Tora (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, succinic anhydride-modified dipentaerythritol penta (meth) acrylate, urethane tri (Meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (meth) acrylate and the like.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, when the photosensitive resin composition of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three (trifunctional) or more polymerizable double bonds. Some are preferable, and poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Succinic acid modification of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate Acid-modified product, dipentaerythritol hex (Meth) acrylate are preferable.
Although there is no restriction | limiting in particular in content of the said polyfunctional monomer used in the photosensitive resin composition of this invention, Usually, about 5-500 weight part with respect to 100 weight part of said alkali-soluble resin, Preferably it is 20-300. The range is parts by weight. If the content of the polyfunctional monomer is less than the above range, the photocuring may not sufficiently proceed and the exposed part may be eluted, and if the content of the polyfunctional monomer is more than the above range, the alkali developability may be deteriorated. There is.

(Photoinitiator)
There is no restriction | limiting in particular as a photoinitiator used in the photosensitive resin composition of this invention, It can select suitably from various photoinitiators known conventionally. For example, aromatic ketones such as benzophenone, Michler ketone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. Benzoin ethers, benzoin such as methylbenzoin, ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-tria Reel imidazole dimer 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl- 5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) ) Halomethyloxadiazole compounds such as 1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl Ru-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloro Halomethyl-S-triazine compounds such as methyl-S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl Sulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, Isopropylthioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 4-benzoyl-methyldiphenyl sulfide, 2-benzyl 2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- ( 4-morpholinyl) phenyl] -1-butanone, α-di Butoxy -α- phenyl acetophenone, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type. Among them, in terms of luminance and heat resistance, it contains at least one selected from 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2,4-diethylthioxanthone. Is preferred.

  Content of the photoinitiator used in the photosensitive resin composition of this invention is about 0.01-100 weight part normally with respect to 100 weight part of said polyfunctional monomers, Preferably it is 5-60 weight part. If this content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the hardness of the colored layer may not be sufficient. On the other hand, if the content is more than the above range, the photosensitive resin composition In some cases, the content of the coloring material or the like in the solid content is relatively low, and a sufficient coloring density may not be obtained.

<Solvent>
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the photosensitive resin composition and can dissolve or disperse them. Specifically, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve acetate, ethyl Ethylene glycol alkyl ether acetates such as cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; propylene glycol methyl ether Propylene glycol alkyl ether acetates such as cetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone And ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, Estes such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate Kind; and the like. These solvents may be used alone or in combination of two or more.
Among the above, ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate and diethylene glycol ethyl methyl ether Is preferred.

<Optional components>
The photosensitive resin composition of the present invention may contain other color materials and various additives as necessary within the range where the object of the present invention is not impaired.

(Other color materials)
You may mix | blend another color material as needed for the purpose of control of a color tone. As the other colorant, for example, conventionally known organic pigments and dyes can be selected according to the purpose, and one or more kinds can be used.
Specific examples of other coloring materials include C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38; C.I. I. Pigment blue 1, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Acid Red 52, C.I. I. Acid Red 289 and the like.

  When other color materials are used, the blending amount is not particularly limited as long as the effect of the present invention is not impaired. As the blending amount of the other color material, for example, the weight ratio of the color material represented by the general formula (I) and the other color material is preferably 99: 1 to 30:70, and 99: 1 More preferably, it is -50: 50, and it is especially preferable that it is 90: 10-60: 40. This is because, within this range, the color tone can be controlled without impairing the high transmittance characteristic of the color material represented by the general formula (I).

(Additive)
The photosensitive resin composition of this invention may contain an additive as needed. Examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
Specific examples of the surfactant include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol Examples include distearate, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine-modified polyurethanes. In addition, a fluorosurfactant can also be used.
Furthermore, examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.

<Combination ratio of each component in the photosensitive resin composition>
The total content of the color material represented by the general formula (I) and other color materials blended as necessary is 5 to 65% by weight based on the total solid content of the photosensitive resin composition. Preferably it is blended in a proportion of 8 to 55% by weight. If it is more than the said lower limit, the colored layer at the time of apply | coating the photosensitive resin composition to predetermined | prescribed film thickness (usually 1.0-5.0 micrometers) has sufficient color density. Moreover, if it is below the said upper limit, while being excellent in the dispersibility and dispersion stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained.
In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also contained.
Further, the content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, the content of the dispersant is 1 with respect to 100 parts by weight of the solid content of the photosensitive resin composition. Up to 50 parts by weight can be used. Furthermore, it is preferable to mix | blend in the ratio of 2-30 weight part with respect to 100 weight part of solid content of the photosensitive resin composition, and it is preferable to mix | blend especially in the ratio of 2-15 weight part. If it is more than the said lower limit, it is excellent in the dispersibility and dispersion stability of a coloring material, and is excellent in storage stability. Moreover, if it is below the said upper limit, developability will become favorable.
The content of the polyfunctional thiol compound is preferably 0.01 to 10 parts by weight and more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the solid content of the photosensitive resin composition. If content of a polyfunctional thiol compound is more than the said lower limit, even if it is after long-term storage, the developability and adhesiveness fall of the photosensitive resin composition are suppressed. Moreover, if it is below the said upper limit, reaction with a polyfunctional thiol compound and another component will not produce easily, and it is excellent in the storage stability of the photosensitive resin composition.
The total amount of the photosensitive binder component is preferably 24 to 94% by weight, preferably 40 to 87% by weight, based on the total solid content of the photosensitive resin composition. If it is more than the said lower limit, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. Moreover, if it is below the said upper limit, it is excellent in developability and generation | occurrence | production of the fine wrinkles by heat shrink is also suppressed.
Moreover, what is necessary is just to set content of a solvent suitably in the range which can form a colored layer accurately. Usually, it is preferably in the range of 65 to 95% by weight, more preferably in the range of 75 to 88% by weight, based on the total amount of the photosensitive resin composition containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

<Method for producing photosensitive resin composition>
The manufacturing method of the photosensitive resin composition includes the color material represented by the general formula (I), the dispersant, the polyfunctional thiol compound, the photosensitive binder component, and various additive components used as desired. Any method can be used as long as it can be uniformly dissolved or dispersed in a solvent, and is not particularly limited, and can be prepared by mixing using a known mixing means.
As a method for preparing the resin composition, for example, (1) a color material dispersion liquid is prepared by adding a color material and a dispersant represented by the general formula (I) in a solvent and dispersing the dispersion using a disperser. On the other hand, a photosensitive binder resin composition prepared by adding an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator in another solvent is prepared, and the colorant dispersion and the photosensitive resin are prepared. A method of mixing a functional binder resin composition, a polyfunctional thiol compound, and various additive components used as required, (2) a colorant represented by the general formula (I) in a solvent, a dispersant, A method of simultaneously adding and mixing a functional thiol compound, a photosensitive binder component, and various additive components used as desired, and (3) a dispersant, a polyfunctional thiol compound, and a photosensitive binder component in a solvent And used as desired It is added and various additive components, were mixed, and the like method of mixing by adding a coloring material thereto represented by the general formula (I).
Among these methods, the method (1) is preferable because it can effectively prevent aggregation of the color material and can be uniformly dispersed.

  In the preparation of the color material dispersion in the above method (1), as a disperser for performing the color material dispersion treatment, a roll mill such as a two-roll or three-roll, a ball mill such as a ball mill or a vibration ball mill, or a paint shaker And bead mills such as a continuous disk type bead mill and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2 mm, more preferably 0.05 to 1 mm. Specifically, pre-dispersion is performed with 1 to 2 mm zirconia beads having a relatively large bead diameter, and further main dispersion is performed with 0.03 to 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a membrane filter of about 5.0 to 0.2 μm after dispersion. Thereby, a color material dispersion excellent in dispersibility of the color material is obtained.

[Color filter]
The color filter according to the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is the photosensitive resin composition according to the present invention. It has a colored layer formed by curing.

  Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

(Colored layer)
At least one of the colored layers used in the color filter of the present invention is a colored layer formed by curing the photosensitive resin composition according to the present invention.
The colored layer is usually formed in an opening of a light shielding part on a transparent substrate, which will be described later, and is usually composed of three or more colored patterns.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the photosensitive resin composition, but is usually preferably in the range of 1 to 5 μm.

The colored layer can be formed by the following method, for example.
First, the photosensitive resin composition of the present invention described above is applied onto a transparent substrate described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a call coating method, a spin coating method, A wet paint film is formed.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized. It is set as the coating film of the photosensitive resin composition. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately determined depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive resin composition to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the photosensitive resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a laminate of two Cr films, and a CrO _x film (x is an arbitrary number) with a reduced reflectance. , CrN _y film (y is an arbitrary number) and three layers of Cr film may be laminated.
When the light-shielding part is a material in which a black colorant is dispersed or dissolved in a binder resin, the method for forming the light-shielding part is not particularly limited as long as the light-shielding part can be patterned. For example, a photolithography method, a printing method, an ink jet method and the like using the colored resin composition for the light shielding part can be exemplified.

  In the above case, when a printing method or an inkjet method is used as a method for forming the light shielding part, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxy Examples thereof include ethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin and the like.

  In the above case, when a photolithography method is used as a method for forming the light shielding portion, the binder resin may be, for example, an acrylate-based, methacrylate-based, polyvinyl cinnamate-based, or cyclized rubber-based reactive material. A photosensitive resin having a vinyl group is used. In this case, a photopolymerization initiator may be added to the colored resin composition for a light shielding part containing a black colorant and a photosensitive resin, and further, a sensitizer, a coating property improver, and a development as necessary. You may add an improving agent, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, etc.

  On the other hand, when the light shielding part is a metal thin film, the method for forming the light shielding part is not particularly limited as long as the light shielding part can be patterned, and for example, photolithography, vapor deposition using a mask. Method, printing method and the like.

  The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and about 0.5 to 2 μm in the case where a black colorant is dispersed or dissolved in a binder resin. Is set.

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.
The color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the transparent substrate, the light shielding portion, and the colored layer. .

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. In addition, the liquid crystal layer can be formed by overlapping the color filter and the counter substrate under reduced pressure and bonding them with a sealant. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

[Organic light emitting display]
An organic light emitting display device according to the present invention includes the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

(Synthesis Example 1: Synthesis of blue color material A)
(1) Preparation of K ₄ (SiMoW ₁₁ O ₄₀ ) 16.4 ml of 1 mol / l Na ₂ MoO ₄ aqueous solution was added to 9.8 ml of 13 mol / l HNO ₃ aqueous solution and stirred. To this solution, 16.4 g of K ₈ (α-type SiW ₁₁ O ₃₉ ) · 13H ₂ O prepared by the method described in Inorganic Synthesis vol 27 p85 was added little by little. After stirring at room temperature for 4 hours, the mixture was washed with a saturated aqueous KCl solution. The obtained solid was dried at room temperature to obtain 12.2 g of K ₄ (SiMoW ₁₁ O ₄₀ ).

(2) Synthesis of blue color material A C.I. I. 6.46 g of Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into 390 ml of purified water and dissolved by stirring at 40 ° C. Separately from this, 12.2 g of K ₄ (SiMoW ₁₁ O ₄₀ ) prepared in the above (1) was dissolved in 50 ml of purified water. A K ₄ (SiMoW ₁₁ O ₄₀ ) solution was added to the BB7 solution, and the mixture was stirred at 40 ° C. for 1 hour. Next, the internal temperature was raised to 80 ° C., and the mixture was further stirred for 1 hour to be raked. After cooling, the mixture was filtered and washed with 300 ml of purified water three times. The obtained solid was dried at 90 ° C. to obtain 13.4 g of a blue color material A which was a black-blue solid and had an average primary particle size of 50 nm.

(Synthesis Example 2: Synthesis of Blue Color Material B)
_{(1) K 6 (P 2} MoW 17 O 62) prepared NaWO 4 · _2H 2 _O of (Wako Pure Chemical Industries, _{Ltd.) 44.0g, Na 2 MoO 4 ·} 2H 2 O ( Kanto Chemical Co., Ltd.) 1 .90 g was dissolved in 230 g of purified water. To this solution, 64.9 g of 85% phosphoric acid was added with stirring using a dropping funnel. The resulting solution was heated to reflux for 8 hours. The reaction solution was cooled to room temperature, 1 drop of bromine water was added, and 45 g of potassium chloride was added with stirring. After further stirring for 1 hour, the precipitate was filtered off. The obtained solid was dried at 90 ° C. to obtain 29.4 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ).

(2) Synthesis of blue color material B 5.30 g of BB7 was put into 350 ml of purified water and dissolved by stirring at 40 ° C. Separately, 10.0 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) prepared in the above (1) was dissolved in 40 ml of purified water. A K ₆ (P ₂ MoW ₁₇ O ₆₂ ) solution was added to the BB7 solution, and the solution was stirred at 40 ° C. for 1 hour. Next, the internal temperature was raised to 80 ° C., and the mixture was further stirred for 1 hour to be raked. After cooling, the mixture was filtered and washed with 300 ml of purified water three times. The obtained solid was dried at 90 ° C. to obtain 10.4 g of a triarylmethane lake blue color material B having a black-blue solid and an average primary particle size of 40 nm.

(Production Example 1: Preparation of colorant dispersion A)
As a dispersant, 6.5 parts by weight of LPN21116 (non-volatile content 40% manufactured by Big Chemie), 13 parts by weight of blue color material A of Synthesis Example 1, PGMEA solution of methacrylic acid / methyl methacrylate / benzyl methacrylate copolymer (molar ratio) : 10/30/50, weight average molecular weight: 9000, acid value: 70 mg KOH / g, solid content 40 wt%) 17.9 parts by weight, PGMEA (propylene glycol monomethyl ether acetate) 62.6 parts by weight, particle size 2. Put 100 parts by weight of 0mm zirconia beads in a mayonnaise bin, shake for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a preliminary crush, then change to 200 parts of zirconia beads with a particle size of 0.1 mm and paint as the main crush Dispersion was performed with a shaker for 6 hours to obtain a colorant dispersion A.

(Production Example 2: Preparation of colorant dispersion B)
A color material dispersion B was obtained in the same manner as in Production Example 1 except that the blue color material A was changed to the blue color material B in Production Example 1.

(Reference Production Example 1: Preparation of pigment dispersion)
In Production Example 1, 8.1 parts by weight of LPN21116, PGMEA solution of methacrylic acid / methyl methacrylate / benzyl methacrylate copolymer (molar ratio: 10/30/50, weight average molecular weight: 9000, acid value: 70 mgKOH / g, solid content 40% by weight) 16.3 parts by weight, PGMEA 62.6 parts by weight, instead of blue colorant A, 13 parts by weight of commercially available pigment blue 15: 6 pigment (PB15: 6) Prepared a pigment dispersion in the same manner as in Production Example 1.

(Production Example 3: Preparation of alkali-soluble resin A)
A methacrylic acid / methyl methacrylate / benzyl methacrylate copolymer (weight ratio: 18/30/40) was prepared by a known synthesis method, and then 12% by weight of glycidyl methacrylate was reacted with methacrylic acid in the presence of oxygen. A PGMEA solution of alkali-soluble resin A (solid content: 40% by weight) was obtained. The weight average molecular weight of the alkali-soluble resin A determined as a standard polystyrene conversion value by gel permeation chromatography (GPC) was 9,000, and the acid value determined by the above-mentioned method was 75 mgKOH / g.

(Production Example 4: Preparation of photosensitive binder resin composition A)
Dipentaerythritol hexaacrylate (DPHA) (Aronix M403 (manufactured by Toagosei Co., Ltd.)) 19 as a polyfunctional monomer with respect to 36.1 parts by weight of the alkali-soluble resin A solution (solid content 40% by weight) obtained in Production Example 3 4 parts by weight, Irgacure 907 (manufactured by BASF) as an initiator, 3.6 parts by weight, Kayacure DETX-S (manufactured by Nippon Kayaku), 1.2 parts by weight, PGMEA 39.8 parts by weight, and photosensitive binder Resin composition A was obtained.

(Production Example 5: Preparation of photosensitive binder resin composition B)
Dipentaerythritol hexaacrylate (DPHA) Aronix M403 (manufactured by Toagosei Co., Ltd.) 15.8 as a polyfunctional monomer with respect to 44.1 parts by weight of the alkali-soluble resin A solution (solid content 40% by weight) obtained in Production Example 3 In addition, 3.6 parts by weight of Irgacure 907 (manufactured by BASF) and 1.2 parts by weight of Kayacure DETX-S (manufactured by Nippon Kayaku) are added as an initiator, and 35.3 parts by weight of PGMEA is added to form a photosensitive binder resin composition. Product B was obtained.

(Example 1: Preparation of photosensitive resin composition)
30.9 parts by weight of the colorant dispersion A obtained in Production Example 1, 28.9 parts by weight of the photosensitive binder resin composition A obtained in Production Example 4, pentaerythritol tetra (3-mercaptobutyrate) (PTMP; Showa Denko Co., Ltd., “Karenz MT (trademark) PE1”)) 0.4 parts by weight, silane coupling agent KBM-503 (manufactured by Shin-Etsu Silicone) 0.4 parts by weight, surfactant MegaFac R08MH (manufactured by DIC) 0 .04 parts by weight and 39.2 parts by weight of PGMEA were mixed to obtain a photosensitive resin composition of Example 1.

(Example 2: Preparation of photosensitive resin composition)
In Example 1, instead of pentaerythritol tetra (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate) (TPMB; manufactured by Showa Denko KK) was used in the same manner as in Example 1. Thus, a photosensitive resin composition of Example 2 was obtained.

(Example 3: Preparation of photosensitive resin composition)
In Example 1, instead of pentaerythritol tetra (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate) (TEMB; manufactured by Showa Denko KK) was used in the same manner as in Example 1. Thus, a photosensitive resin composition of Example 3 was obtained.

( Reference Example 4 : Preparation of photosensitive resin composition)
In Example 1, instead of pentaerythritol tetra (3-mercaptobutyrate), pentaerythritol tetrakis- (3-mercaptopropionate) (PEMP; manufactured by Sakai Chemical Co., Ltd.) was used. Thus, a photosensitive resin composition of Reference Example 4 was obtained.

(Example 5: Preparation of photosensitive resin composition)
In Example 1, instead of the photosensitive binder resin composition A, the photosensitive resin of Example 5 was used in the same manner as in Example 1 except that the photosensitive binder resin composition B obtained in Production Example 5 was used. A composition was obtained.

(Example 6: Preparation of photosensitive resin composition)
30.9 parts by weight of the colorant dispersion B obtained in Production Example 2, 28.9 parts by weight of the photosensitive binder resin composition A obtained in Production Example 4, pentaerythritol tetra (3-mercaptobutyrate) (PTMP ; Showa Denko Co., Ltd., "Karenz MT (trademark) PE1") 0.4 parts by weight, silane coupling agent KBM-503 (Shin-Etsu Silicone) 0.4 parts by weight, surfactant MegaFac R08MH (manufactured by DIC) 0 .04 parts by weight and 39.2 parts by weight of PGMEA were mixed to obtain a photosensitive resin composition of Example 6.

(Example 7: Preparation of photosensitive resin composition)
In Example 6, instead of pentaerythritol tetra (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate) (TPMB; manufactured by Showa Denko KK) was used in the same manner as in Example 6. Thus, a photosensitive resin composition of Example 7 was obtained.

(Example 8: Preparation of photosensitive resin composition)
In Example 6, instead of pentaerythritol tetra (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate) (TEMB; manufactured by Showa Denko KK) was used in the same manner as in Example 6. Thus, a photosensitive resin composition of Example 8 was obtained.

(Comparative Example 1: Preparation of photosensitive resin composition)
30.9 parts by weight of colorant dispersion A obtained in Production Example 1, 29.8 parts by weight of photosensitive binder resin composition A, 0.4 parts by weight of silane coupling agent KBM-503 (manufactured by Shin-Etsu Silicone), interface Activator Megafac R08MH (manufactured by DIC) 0.04 parts by weight and PGMEA 38.6 parts by weight were mixed to obtain a photosensitive resin composition of Comparative Example 1 containing no polyfunctional thiol compound.

(Comparative Example 2: Preparation of photosensitive resin composition)
In the comparative example 1, the photosensitive resin composition of the comparative example 2 was obtained like the comparative example 1 except having used the photosensitive binder resin composition B instead of the photosensitive binder resin composition A.

(Comparative Example 3: Preparation of photosensitive resin composition)
30.9 parts by weight of colorant dispersion B obtained in Production Example 2, 29.8 parts by weight of photosensitive binder resin composition A, 0.4 parts by weight of silane coupling agent KBM-503 (manufactured by Shin-Etsu Silicone), interface Activator Megafac R08MH (manufactured by DIC) 0.04 parts by weight and PGMEA 38.6 parts by weight were mixed to obtain a photosensitive resin composition of Comparative Example 3 containing no polyfunctional thiol compound.

(Reference Example 1: Preparation of photosensitive resin composition)
30.9 parts by weight of the pigment dispersion obtained in Reference Production Example 1, 29.8 parts by weight of the photosensitive binder resin composition B obtained in Production Example 3, and silane coupling agent KBM-503 (manufactured by Shin-Etsu Silicone) 0 The photosensitive resin composition of Reference Example 1 was obtained by mixing 4 parts by weight, 0.04 part by weight of a surfactant Megafac R08MH (manufactured by DIC) and 38.6 parts by weight of PGMEA.

<Alkali developability evaluation>
Each of the photosensitive resin compositions of Examples 1 to 3, 5 to 8, Comparative Examples 1 to 3, and Reference Examples 1 and 4 is a glass substrate having a thickness of 0.7 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.). On top, it was applied using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 40 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer was formed was shower-developed using an aqueous 0.05 wt% potassium hydroxide solution as an alkaline developer, and the colored layer was completely dissolved and the colored layer was formed. The time until the glass surface appeared was measured as the development time. The results are shown in Table 1.

<Development adhesion evaluation>
Each of the photosensitive resin compositions of Examples 1 to 3, 5 to 8, Comparative Examples 1 to 3, and Reference Examples 1 and 4 is a glass substrate having a thickness of 0.7 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.). On top, it was applied using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 40 mJ / cm ² using a super high pressure mercury lamp through a photomask pattern in which a thin line having a width of 1 μm to 100 μm was formed. Thereafter, the glass plate on which the colored layer is formed is shower-developed using an aqueous 0.05 wt% potassium hydroxide solution as an alkaline developer, and the exposed portion of the colored layer is observed with an optical microscope and remains. The minimum pattern was confirmed. The smaller the remaining minimum pattern width, the better the development adhesion, and it is preferable that a pattern with a width of 10 μm or less remains. The results are shown in Table 1.

<Storage stability evaluation>
The photosensitive resin compositions of Examples 1 to 3, 5 to 8, Comparative Examples 1 to 3, and Reference Examples 1 and 4 were each stored at 25 ° C. After the storage for 7 days and 30 days, the stored photosensitive resin compositions were subjected to the alkali developability evaluation and the development adhesion evaluation, respectively.
Moreover, the viscosity stability test of the photosensitive resin composition was performed as follows.
The viscosity of the photosensitive resin composition was measured immediately after preparation and after storage for 30 days at 25 ° C. When the viscosity after storage for 30 days is 1.1 times or less, the viscosity is 1.1 times or less and 1.2 times or less is Δ or 1.2 times or more than the viscosity immediately after adjustment. did. ○ and Δ are practical ranges. The viscosity was measured with a B-type viscometer (manufactured by Toki Sangyo) at 60 rpm / 25 ° C. The results are shown in Table 1.

[Summary of results]
The photosensitive resin compositions of Comparative Examples 1 to 3 that contain the colorant represented by the general formula (I) but do not contain a polyfunctional thiol compound have the same developability as that of the examples as long as they are just prepared. Although it had development adhesiveness, it became clear that the thin line pattern was easily peeled off as the storage period became longer, and the development adhesiveness was lowered. As in Reference Example 1, such a problem is a problem that cannot be seen with a conventionally widely used pigment.
The photosensitive resin compositions of Examples 1 to 3 , 5 to 8 and Reference Example 4 using a combination of the colorant represented by the general formula (I), the dispersant, and the polyfunctional thiol compound are 7 It was revealed that developability and development adhesion did not decrease even after storage for 30 days and after storage for 30 days.
From the comparison between Examples 1 to 3 using a polyfunctional secondary thiol compound and Reference Example 4 using a polyfunctional primary thiol compound, by using the polyfunctional secondary thiol compound, developability and development adhesion It became clear that the property was more difficult to decrease. Further, Examples 1 to 3 using a polyfunctional secondary thiol compound are superior in viscosity stability of the photosensitive resin composition to Reference Example 4 using a polyfunctional primary thiol compound. I understood.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

Claims (5)

It contains a colorant represented by the following general formula (I), a dispersant, a polyfunctional thiol compound, a photosensitive binder component, and a solvent, and the polyfunctional thiol compound is a polyfunctional secondary thiol compound. A photosensitive resin composition.
(In the general formula (I), R ^I , R ^II , R ^III , R ^IV , R ^V and R ^VI each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, ^- is ^{_{(SiMoW 11 O 40) 4- /}} 4 and _{(P 2 Mo y W 18-} y O 62) 6- / 6 is represented by at least one, y = 1, 2 or 3 of an integer heteropoly Represents an oxometalate anion.) The polyfunctional thiol compound is polyfunctional thiol compound represented by the following formula (II), the photosensitive resin composition of claim 1.
In (formula (II), ^{R 1} represents an alkyl group having 1 to 6 carbon atoms, ^{R 2} represents an alkylene group having 1 to 6 carbon atoms, Q is a polyhydric alcohol hydroxyl number 2-6 Represents a residue, and n is an integer of 2 to 6.) A color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is formed by curing the photosensitive resin composition according to claim 1 or 2. A color filter, which is a colored layer. A liquid crystal display device comprising: the color filter according to claim 3 ; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate. An organic light emitting display device comprising the color filter according to claim 3 and an organic light emitter.