KR101354008B1 - Photocurable composition, and color filter using the same - Google Patents

Abstract

Provided are a photocurable composition having sufficient color density, spectral characteristics, sensitivity, and curability, and excellent in rectangularity and developability of a pattern of a pixel when used in a color filter, and a color filter using the same.

The photocurable composition containing a coloring agent, a photopolymerizable compound, and a photoinitiator WHEREIN: The content of the said coloring agent is 40 mass% or more of total solid, and the said photopolymerizable compound has alkali-soluble group, The photocurable composition characterized by the above-mentioned.

Description

Photocurable composition and color filter using the same {PHOTOCURABLE COMPOSITION, AND COLOR FILTER USING THE SAME}

Fig. 1 is a first diagram showing the pixel pattern shape of the color filter of Example 1 (using a 5-functional monomer having a carboxyl group introduced).

Fig. 2 is a second diagram showing the pixel pattern shape of the color filter of Comparative Example 1 (using a six-functional monomer having no alkali-soluble group).

The present invention relates to a photocurable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device (LCD), a solid state image pickup device (CCD, CMOS, etc.), and a color filter using the photocurable composition.

As a method of manufacturing the color filter used for a liquid crystal display element or a solid-state image sensor, the dye method, the printing method, the electrodeposition method, and the pigment dispersion method are known.

Among them, the pigment dispersion method is a method of producing a color filter by photolithography using a colored radiation-sensitive composition in which the pigment is dispersed in various photosensitive compositions. Have In addition, since patterning is performed by the photolithography method, the positional accuracy is high, and thus it has been widely used as a preferable method for producing color filters for large screens and high-precision color display devices.

In the case of producing a color filter by the pigment dispersion method, the radiation-sensitive composition is coated on a glass substrate with a spin coater, a roll coater, or the like, dried to form a coating film, the coating film is subjected to pattern exposure, and developed to produce colored pixels. The color filter can be obtained by repeating this operation for each color.

As said pigment dispersion method, what described the negative photosensitive composition which used together the photopolymerizable monomer and the photoinitiator in alkali-soluble resin is Unexamined-Japanese-Patent No. 2-181704, Unexamined-Japanese-Patent No. 2-199403. , Japanese Patent Application Laid-Open No. 5-273411, Japanese Patent Application Laid-Open No. 7-140654, and Japanese Patent Application Laid-Open No. 10-332929.

In recent years, the color filter for a solid-state image sensor is required to be more precise. However, in the conventional pigment dispersion system, it is difficult to further improve the resolution, and there is a problem in the uniformity of colors between pixels, such as color staining caused by coarse particles of the pigment. For this purpose, it is not suitable for the use which requires a micropattern like a solid-state image sensor.

In order to solve the above problem, a technique of conventionally using a dye instead of a pigment is proposed in Japanese Patent Laid-Open No. Hei 6-75375. However, in general, the curable composition containing the dye has a problem of deterioration compared to the curable composition using the pigment with respect to various performances, such as light resistance, heat resistance, solubility, coating uniformity.

In particular, the color filter for a solid state image pickup device (image sensor) tends to have a thickness of 1.5 m or less in order to cope with improvement of light shielding and miniaturization of the device. However, when such thin film is formed, the content of the colorant contained in the film also inevitably decreases, which causes a problem in terms of color concentration. This tendency is particularly remarkable when dyes are used than when pigments are used as colorants.

In other words, when an organic pigment is used, molecules that become chromophores in the crystal phase are present in agglomerated state in the color filter, and when dyes are used, the molecules are present in a dispersed state, and further increase durability and heat resistance. For this reason, in addition to the chromophore molecules, the molecular chains for improving their properties are combined, so that the molecular chains made of the chromophores are further diluted to reduce the color concentration only in those portions.

As described above, in order to meet the demand for thinning the color filter in the solid state image pickup device, it is necessary to increase the content ratio of the colorant in the color filter. This requirement is particularly important when a dye is used than when a pigment is used as a colorant.

However, increasing the content of colorants inevitably reduces the proportion of other components contained in the composition. In this case, as a matter of course, when the ratio of other components is reduced, photocurability and alkali developability are lowered, and thus there is a limit to improvement of the content ratio of the colorant. In particular, when a dye is used as the colorant, a decrease in color concentration due to the thinning of the film is remarkable, and it is very difficult to achieve balance with practical characteristics other than the color concentration.

Further, Japanese Patent Laid-Open No. 10-62986 discloses a radiation-sensitive coloring composition containing a radiation sensitive component, a binder resin, a pigment, and a solvent, wherein the radiation sensitive component is an ethylene oxide chain or a propylene oxide chain as a polymerizable component. A radiation sensitive coloring composition containing at least one (meth) acrylate compound selected from the group of specific compounds included is proposed.

An object of the present invention is to provide a photocurable composition having sufficient color density, spectral characteristics, sensitivity, and curability, and excellent in rectangularity and developability of a pixel pattern when a color filter is used.

It is also an object of the present invention to provide a color filter having a sufficient color density and excellent in the rectangularity of the pixel pattern.

The present invention is accomplished by the following means.

<1> Photocurable composition containing a coloring agent, a photopolymerizable compound, and a photoinitiator WHEREIN: The content of the said coloring agent is 40 mass% or more of total solid, and the said photopolymerizable compound has an alkali-soluble group, The photocurable property characterized by the above-mentioned. Composition.

<2> The photocurable composition according to <1>, wherein a total content of the colorant, the photopolymerizable compound, and the photopolymerization initiator is 80% by mass or more based on the total solids in the photocurable composition.

<3> The photocurable composition according to <1>, wherein the number of polymerizable functional groups of the photopolymerizable compound is 3 or more.

<4> The photocurable composition according to <1>, wherein the colorant is mainly composed of a dye.

<5> The photocurable composition according to <1>, wherein 25% by mass or more of the colorant is an acid dye.

<6> The photocurable composition according to <1>, wherein the alkali-soluble group of the photopolymerizable compound is at least one of a carboxyl group, a phosphoric acid group and a sulfonic acid group.

The color filter which forms the coating film which consists of a photocurable composition as described in said <1> on a <7> board | substrate, and has formed the pixel by patterning by the photolithographic method using alkali image development.

<8> The color according to <7>, wherein the minimum transmittance is 10% or less in the range of 400 nm to 700 nm, and the difference between the maximum transmittance and the minimum transmittance is 65% or more in the wavelength range. filter.

<9> The color filter according to <7>, wherein the pixel has a thickness of 0.3 µm or more and 1.5 µm or less.

<10> The color filter according to <7>, wherein the maximum side of the pixel is 5.0 µm or less.

Hereinafter, the photocurable composition of the present invention and the color filter achieved using the same will be described.

<< photocurable composition >>

The photocurable composition of this invention contains a coloring agent, a photopolymerizable compound, and a photoinitiator, content of the said coloring agent is 40 mass% or more of total solid, and the said photopolymerizable compound has an alkali-soluble group, It is necessary, It is necessary. According to the present invention, an alkali-soluble resin and an organic solvent are contained.

The photocurable composition of the present invention is a photocurable composition containing a colorant, a photopolymerizable compound, and a photopolymerizable initiator, wherein the content of the colorant is 40% by mass or more of the total solids, and the photopolymerizable compound has an alkali-soluble group. In view of the fact that the alkali-soluble resin is not substantially used, the content of the photopolymerizable compound and the photopolymerization initiator, which are curable components, can be maintained even if the content of the colorant is increased to 40% by mass based on the total solid content.

In addition, the photocurable composition of the present invention ensures practical characteristics (color density, spectral characteristics, sensitivity, curability, etc.) as a coating film of a color filter, and adjusts the transmittance and pattern profile (pattern rectangularity) of pixels of the obtained color filter. It can be made favorable.

Moreover, in the photocurable composition of this invention, it is preferable that the total content of a coloring agent, a photopolymerizable compound, and a photoinitiator is 80 mass% or more with respect to a total solid. In other words, in the photocurable composition of the present invention, the total content of solid components other than the colorant, the photopolymerizable compound and the photopolymerization initiator is preferably less than 20% by mass.

If the total content of the colorant, the photopolymerizable compound, and the photopolymerization initiator is 80% by mass or more based on the total solids, the color concentration, the sensitivity, the curability, and the like can be more sufficiently improved.

Hereinafter, the various components contained in the photocurable composition of this invention are demonstrated.

<Colorant>

Although a coloring agent in particular in this invention is not restrict | limited, Conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types.

It is preferable that the colorant is mainly composed of a dye, and by using the dye as a main agent of the colorant, the uniformity of color characteristics can be increased and the nonuniformity of the color concentration distribution between pixels can be reduced.

Here, "substantially the dye is mainly" refers to the extent which does not impair the characteristic of a dye in terms of a color characteristic, Specifically, it means that the content rate of a dye is 60 mass% or more with respect to the total amount of a coloring agent.

Content of dye in the said coloring agent is 60 mass% or more, Preferably it is 65 mass% or more, More preferably, it is 70 mass%.

(dyes)

In this invention, as a dye as a coloring agent, it can use without restrict | limiting especially an organic solvent soluble dye, For example, well-known dye etc. are mentioned as a conventional color filter use. As said well-known dye, For example, Unexamined-Japanese-Patent No. 64-90403, Unexamined-Japanese-Patent No. 64-91102, Unexamined-Japanese-Patent No. 1-94301, Unexamined-Japanese-Patent No. 6-11614, Japan Patent Registration No. 2592207, US Patent No. 4,808,501, US Patent No. 5,667,920, US Patent No. 5,059,500, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183 The pigment | dye of Unexamined-Japanese-Patent No. 6-51115 and Unexamined-Japanese-Patent No. 6-194828 is mentioned. Further, from the viewpoint of the chemical structure, triphenylmethane, anthraquinone, benzilidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo The system etc. are mentioned. In the present invention, dyes of pyrazole azo, anilino azo, pyrazolotriazole azo, pyridone azo, anthraquinone and anthrapyridone are particularly preferred as the dye.

In the case of a resist system which performs water or alkali development, an acid dye and / or a derivative thereof can be preferably used as the dye in the present invention from the viewpoint of completely removing the binder and / or the dye by development. . In addition, in the present invention, as a dye, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, a useful dye, a food dye, and / or a derivative thereof may also be used.

It is preferable that 25 mass% or more of the photocurable composition of this invention is an acid dye with respect to all the coloring agents. Thereby, alkali developability can be maintained and it can be set as rectangularness and developability of a pattern.

Hereinafter, the acid dye will be described.

(Acid dye)

The acid dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, or phenolic hydroxyl group, but it is soluble in organic solvents and developing solutions, salt formability with basic compounds, absorbance, and cure with other components. It is selected in consideration of the entire performance required such as action, light resistance and heat resistance.

Hereinafter, the specific example of the said acid dye is mentioned. However, acid dyes in the present invention is not limited to these. For example, the following dyes and derivatives of these dyes are mentioned.

Acid Black 24;

Acid Blue 1, 7, 9, 15, 83, 86, 90, 103, 108, 113, 120, 249;

Acid Green 1, 3, 5, 9, 16, 50;

Acid Orange 7, 8, 10, 12, 50, 51, 52, 63;

Acid Red 4, 8, 14, 17, 18, 26, 27, 51, 66, 73, 80, 87, 88, 91, 92, 94, 103, 111, 114, 145, 150, 151;

Acid Violet 9, 17, 49;

Acid Yellow 1, 7, 9, 11, 17, 23, 34, 36, 38, 40, 65, 72, 76, 135, 228;

Direct Yellow 34;

Direct Orange 41, 61, 70;

Direct Violet 54;

Direct Blue 86, 108, 109, 199;

Mordant Yellow 8, 10, 20;

Mordant Red 9, 32;

Mordant Violet 2, 41;

Mordant Blue 1,3;

Mordant Green 4;

Food Yellow 3;

Solvent Yellow 14;

Solvent Orange 2, 7, 15;

Solvent Red 49;

Valifast Blue 2620

The following compounds can be used as an acid dye which can be used as a coloring agent in this invention.

Heterocyclic Azo Compounds

Heterocyclic azo compounds are compounds in which an azo group (-N = N-) is directly bonded to a heterocycle.

Here, the hetero ring has a hetero atom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring. Although any of a saturated ring and an unsaturated ring may be sufficient, it is preferable that it is an unsaturated ring. In addition, any of a monocyclic ring and a condensed ring may be sufficient, and may be unsubstituted or substituted by a substituent.

Specific examples of the heterocycle include furan, pyrrole, pyrazole, pyrazoline, imidazole, oxazole, thiazole, triazole, pyran, pyridine, pyrimidine, pyrazine, triazine, pyridone, isothiazole, thiadiazole , Benzothiazole, benzoxazole, benzoisothiazole and the like. In these, the heterocyclic ring (nitrogen hetero ring) which contains a nitrogen atom in a ring is preferable, and pyrazole, a pyridone, a pyridine, a pyrimidine is preferable among these.

Moreover, it is preferable to contain an acidic radical in arbitrary positions of a heterocyclic azo compound. As the acid group, any type of acid group can be used as long as it is a functional group capable of dissociating with an alkaline aqueous solution. Specific examples thereof include a sulfonic acid group, a carboxylic acid group, a phenolic hydroxyl group, a sulfonamido group, and a phosphoric acid group. These acid groups may be a divalent or higher metal salt, and examples of the metal in this case include magnesium, calcium, strontium, barium, zinc, aluminum, nickel, copper, cobalt and iron.

As the heterocyclic azo compound, 1) a compound in which a heterocyclic ring directly bonded to the number of bonds on one side of the azo group is a pyrazole ring, and a heterocyclic ring is directly bonded to the number of bonds on the other side of the azo group and has an acid group at any position in the structure. Is preferred, and also

2) The heterocyclic ring directly bonded to the bonding water on one side of the azo group is a pyrazole ring, the heterocyclic bond directly bonded to the bonding water on the other side of the azo group is a pyridine ring, and has a carboxylic acid and / or sulfonamide at any position in the structure. compound,

3) The heterocyclic ring directly bonded to the bonding water on one side of the azo group is a pyrazole ring, the heterocyclic ring directly bonded to the bonding water on the other side of the azo group is a pyrimidine ring, and a carboxylic acid ring and / or sulfonamide is substituted at any position in the structure. The compound which has is preferable.

Hereinafter, the specific example (example compound A1-1-A1-24, A2-1-A2-24, A3-1-A3-24) of a heterocyclic azo compound is shown. However, in this invention, it is not limited to this specific example.

Phthalocyanine-based compound

Phthalocyanine compounds are generally compounds represented by the following general formula (1).

Formula 1:

In Formula 1, M represents metals, and Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co and Fe, and AlCl, InCl, FeCl, TiCl _2, SnCl _2, SiCl _2, GeCl _2, such as a metal chloride, metal oxides such as TiO, VO, and a metal hydroxide such as Si (OH) _2. Z is preferably Zn, Pd, Cu, Ni, Co or VO, more preferably Zn, Cu, Co or VO, most preferably Cu.

Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent an atomic group necessary to form a six-membered ring containing a carbon atom. The 6-membered ring may be a saturated ring or an unsaturated ring, a hetero ring containing a nitrogen atom, or the like, may be unsubstituted or have a substituent, other 5- or 6-membered rings may be further condensed, and the ring which is condensed may be a substituent. You may have more. Specifically, a benzene ring, a cyclohexane ring, a cyclohexene ring, a pyridine ring, a naphthalene ring and the like are included.

R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ each independently represent a substituent described later. In the present invention, at least one of the substituents represented by the plurality of R ¹⁰¹ to R ¹⁰⁴ is preferably an organic group described later. As the organic group, an organic group (sulfur-containing device) containing a sulfur atom is preferable.

n1, n2, n3 and n4 respectively independently represent the integer of 0-4. It is preferable that the sum total of n1-n4 is 1 or more, More preferably, it is 2 or more.

In addition, the phthalocyanine compound preferably has an acid group at any position in the structure. The acid group may be any type as long as it is a functional group capable of dissociating with an alkaline aqueous solution. Specific examples thereof include a sulfonic acid group, a carboxylic acid group, a phenolic hydroxyl group, a sulfonamide group, and a phosphoric acid group.

In addition, these acid groups may consist of a bivalent or more metal salt, and magnesium, calcium, strontium, barium, zinc, aluminum, nickel, copper, cobalt, iron, etc. are mentioned as a metal in that case.

As the phthalocyanine compound, any one of the following cases is preferable.

1) M is Cu, a 6-membered ring formed by Z ¹ , Z ² , Z ³ and Z ⁴ is a benzene ring, at least one of a plurality of R ¹⁰¹ ~ R ¹⁰⁴ is a sulfur-containing organic compound,

2) M is Cu, the 6-membered ring formed by Z ¹ , Z ² , Z ³ and Z ⁴ is a benzene ring and / or a pyridine ring, and at least one of a plurality of R ¹⁰¹ to R ¹⁰⁴ is a halogen atom or a sulfur-containing device; Phosphorus compound. Also,

3) M is Cu, the 6-membered ring formed by Z ¹ , Z ² , Z ³ and Z ⁴ is a benzene ring, and at least one of the plurality of R ¹⁰¹ to R ¹⁰⁴ is —SR (R is an organic group described below) A compound containing an acid group at any position of the organic group R,

4) M is Cu, and the six-membered ring formed by Z ¹ , Z ² , Z ³ and Z ⁴ is a benzene ring and / or a pyridine ring, and at least one of a plurality of R ¹⁰¹ to R ¹⁰⁴ is a halogen atom or a sulfonamide group Compound is preferred.

Hereinafter, the specific example (example compound A4-1-A4-19) of a phthalocyanine type compound is shown. However, in this invention, it is not limited to this specific example.

In the following specific examples (A5-1 to A5-38), ring A1, ring A2, ring A3 and ring A4 each independently represent a benzene ring or a pyridine ring. In the case of a pyridine ring, positional isomers in which the positions of N differ in the axial direction are present. In addition, isomers in which the substituents are substituted at different positions are also present.

Azomethine Compounds

As an azomethine type compound, the compound which has an azomethine group [RaC (Rb) = N-] in a molecule | numerator is shown. Ra and Rb represent arbitrary organic groups here.

It is preferable to contain a hetero ring as an azomethine type compound. Examples of the hetero ring include the same ones as the hetero ring in the heterocyclic azo compound described above. In these, the heterocyclic ring (nitrogen-containing heterocyclic ring) containing a nitrogen atom in a ring is preferable.

In addition, in this invention, it is preferable to have a structure which the hetero ring described above multiply condensed. Especially, the structure which condensed two hetero rings selected from pyrazole, pyrazoline, imidazole, triazole, and oxazole is preferable.

Moreover, it is preferable to have an acidic radical in the azomethine type compound in arbitrary positions in a structure. The acid group may be any kind as long as it is a functional group capable of dissociating with an alkaline aqueous solution. Specific examples thereof include a sulfonic acid group, a carboxylic acid group, a phenolic hydroxyl group, a sulfonamide group, and a phosphoric acid group. The acid group may be made of a divalent or higher metal salt, and examples of the metal in that case include magnesium, calcium, strontium, barium, zinc, aluminum, nickel, copper, cobalt and iron.

Preferred examples of the azomethine compound include compounds having a ring structure condensed with pyrazoline and triazole, an aromatic ring substituted at the nitrogen atom of the azomethine group, and an acid group at any position in the structure.

2) Structures in which pyrazoline and 1,2,4-triazole are condensed below [7H-pyrapyrazolo [1,5-b] [1,2,4] triazole or 7H-pyrazolo [from left] 5,1-c] [1,2,4] triazole], and the aromatic ring substituted by the nitrogen atom of the azomethine group is a quinoline skeleton, and a carboxylic acid and / or sulfonamide is formed at any position in the structure. The compound which has is preferable.

Hereinafter, the specific example (example compound A6-1-A6-28) of an azomethine type compound is shown. However, in this invention, it is not limited to these specific examples.

Description of the substituent

The "substituent" in this specification is demonstrated.

In the present specification, as a substituent, an inorganic or organic group is represented, and specifically, a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxylic acid group, a sulfonic acid group, a sulfinic acid group and an alkyl group (linear) , Branched, cyclic), alkenyl group (linear, branched, cyclic), alkynyl group, aryl group, heterocyclic group, formyl group or one kind of partial structure selected from the following (A) group, and alkyl group The group which arbitrarily combined 1 type of substructures chosen from alkenyl group, alkynyl group, an aryl group, and heterocyclic group is mentioned.

(A) group: ether group, amino group, thioether group, ketone group, ester group, amido group, urethane group [carbamoyl group -O-CO-N (R)-], urea group [-N (R)- CO-N (R)-], sulfinyl group [-SO-], sulfonyl group [-SO _2- ], sulfonic acid ester group [-SO ₂ -O-], sulfonamido group [-SO ₂ -N (R) -], Imido group [-CO-N (R) -CO-], sulfonyl amido group [-SO ₂ -N (R) -CO-], disulfonylimido group [-SO ₂ -N (R)- SO _2- ]

R bonded to the nitrogen atom in the group (A) represents any one of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

As for the "substituent", the alkyl group may be any of linear, branched and cyclic. In the case of a cyclic | annular, any of monocyclic and polycyclic may be sufficient. As an alkyl group, a C1-C30 alkyl group is preferable, Specifically, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group Etc. can be mentioned. Moreover, you may further have a substituent at arbitrary positions of these alkyl groups, and a substituent includes the said alkyl group itself, and the whole of said "substituent" is contained. In addition, in the case of a cyclic alkyl group, the partial structure selected from the group (A) mentioned above may be inserted in the arbitrary position of the carbon-carbon bond which comprises a ring.

In said "substituent", an alkenyl group may be either linear, branched or cyclic. In the case of a cyclic | annular, any of monocyclic and polycyclic may be sufficient. As an alkenyl group, a C1-C30 alkenyl group is preferable, Specifically, a vinyl group, an allyl group, 1-methylvinyl group, 3-buten-1-yl group, a cyclopentan-2-en-1-yl group, cyclo Hexane-2-en-1-yl group, a cyclohexane-1-en-1-yl group, etc. are mentioned. Moreover, these may further have a substituent at the arbitrary position of an alkenyl group, and the whole of said "substituent" is contained in a substituent. In the case of the cyclic alkenyl group, the partial structure selected from the above-mentioned (A) group may be inserted in arbitrary positions of the carbon-carbon bond which comprises a ring.

In said "substituent", the alkynyl group is an ethynyl group, but may be substituted with a hydrogen atom of the ethynyl group and may have a substituent. As a substituent, the whole of said "substituent" is contained here.

In said "substituent", as long as an aryl group is aromatic, any of a monocycle and a condensed ring may be sufficient, and a C6-C20 aryl group is preferable. Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, etc. are mentioned. In addition, these may further have a substituent at the arbitrary position of an aryl group, and the whole of said "substituent" is contained as a substituent.

In the "substituent", the heterocyclic group has a hetero atom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring, and may be a saturated ring, an unsaturated ring, a monocyclic ring, or a condensed ring. For example, tetrahydrofuranyl group, dihydrofuranyl group, dihydrofuranyl group, terahydropyranyl group, dihydropyranyl group, oxocanyl group, dioxanyl group, tetrahydrothiophenyl group, dithianil group, pyrrolidinyl group , Pyrrolinyl, tetrahydropyridinyl, piperadinyl, homopiperadinyl, piperidinyl, pyrrolyl, furyl, thiophenyl, benzopyrroyl, benzofuryl, benzothiophenyl, pyrazolyl, iso Xazolyl group, isothiazolyl group, isodazolyl group, benzoisoxazolyl group, benzoisothiazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, benzothiazolyl group , Pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrimidinyl, pyrazinyl, cinnaolinyl, phthalazinyl, quinazolinyl, quinoxarinyl, acridinyl, phenantridi Nyl group, phthalazinyl group, Carbazolyl group, uracil group, dithiouracil group, carborylyl group, prinyl group, thiadiazolyl group, etc. are mentioned. Moreover, you may further have a substituent at arbitrary positions of these heterocyclic groups, and the whole of said "substituent" is contained as a substituent.

In addition, the above-mentioned "substituent" means the thing containing at least a carbon atom among said "substituents".

In the above-mentioned phthalocyanine-based compound, as the organic group represented by R ¹⁰¹ to R ¹⁰⁴ , a sulfur-containing group is preferable, and may further have a substituent, and an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, and sulfone. Amide groups are preferred. In the azomethine compound, Ra and Rb are preferably organic groups represented by Ra and Rb to form a nitrogen-containing heterocyclic ring.

-Other dyes-

Next, the other dyes which can be contained in the composition of this invention are demonstrated. Although it does not restrict | limit especially as another dye which may contain further (containing organic solvent soluble dye), The dye conventionally known for the color filter can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. Hei 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent Registration 2592207, In the specification of U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-Open No. 6-51115 The pigment | dye of Unexamined-Japanese-Patent No. 6-194828, etc. can be used.

Examples of the chemical structure include azo dyes, triphenylmethane, anthraquinone, benzylidene, oxonol, phenothiazine, azomethine, xanthene, phthalocyanine and benzopyran other than those mentioned above. And pigments such as indigo type and anthrapyridone type.

In the case of forming a resist system which performs water or alkali development, at least one of the acid dyes and derivatives thereof may be preferably used since the dye is completely removed by development. In addition, it is also useful to use one or more selected from direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, useful dyes, food dyes and derivatives thereof.

Hereinafter, an acid dye and its derivative are demonstrated. The acid dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid or phenolic hydroxyl group, but it is soluble in an organic solvent or developer used in the preparation and development of the composition, the salt formability with basic compounds, and the absorbance. And the overall performance required for interaction with other components in the curable composition, light resistance, heat resistance, and the like.

Specific examples and preferred examples of the acid dyes include dyes described in Japanese Patent Application Laid-Open No. 2005-227722, but are not limited thereto.

As the derivative of the acid dye, inorganic salts of acid dyes having acid groups such as sulfonic acid and carboxylic acid, salts of acid dyes with nitrogen compounds, sulfonamides of acid dyes and the like can be used. The derivatives of the acid dyes are not particularly limited as long as they can be dissolved as a curable composition solution. However, all of the required performances such as solubility, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. Is selected in consideration of.

The salt of the said acid dye and a nitrogen compound is demonstrated.

The method of forming a salt of an acidic dye and a nitrogen-containing compound is sometimes effective in improving the solubility of the acidic dye (solubility in organic solvents) or in improving heat resistance and light resistance.

The nitrogen compound which forms a salt with an acid dye, and the nitrogen compound which forms an amide bond with an acid dye are demonstrated.

Nitrogen-containing compounds are selected in consideration of the solubility of salts or amide compounds in organic solvents or developers, salt formation, absorbance and transmittance of dyes, interaction with other components in the curable composition, and heat and light resistance as colorants. do. When selecting only from the viewpoint of absorbance and transmittance, it is preferable that the molecular weight of the nitrogen compound is as low as possible, and among these, the molecular weight is preferably 300 or less, more preferably 280 or less, and more preferably 250 or less. Particularly preferred.

In the salt of the acid dye and the nitrogen compound, the molar ratio of the nitrogen compound / acid dye (hereinafter referred to as “n”) will be described.

N is a value for determining a molar ratio between an acid dye molecule and an amine compound which is a large ion, and can be freely selected according to salt forming conditions of the acid dye-amine compound. Specifically, numerical values between 0 <n≤5 of the number of functional groups of the acid in acid dyes are practically used, and the solubility, salt formation, absorbance of the organic solvent or developer, interaction with other components in the curable composition, It selects in consideration of all the required performances, such as light resistance and heat resistance. When selecting from the viewpoint of absorbance only, n preferably takes a value between 0 <n≤4.5, more preferably takes a value between 0 <n≤4, and a value between 0 <n≤3.5 It is particularly desirable to take

Since the acid dyes indicated above are acid dyes by introducing an acid group in preparation thereof, the acid dyes can be converted into a non acid dye by changing the substituent.

The acid dye may act preferably in the case of alkali development. On the other hand, since it may be overdeveloped, it may be preferable to use a non acid dye.

These dyes use monochromatic dyes when composing the complementary colors yellow, magenta and cyan, respectively. However, when composing the primary colors red, green and blue, two or more dyes are used in combination. In the present invention, it is preferable to combine two or more dyes to form a primary color system.

(Pigment)

As a pigment which can be used as a coloring agent in this invention, various inorganic pigments or organic pigments conventionally known can be used. In addition, even if it is an inorganic pigment or an organic pigment, considering that it is desirable to have a high transmittance, it is preferable to use as fine as possible, and considering the handleability, the average particle diameter of the pigment is preferably 0.01 μm to 0.1 μm, and 0.01 μm -0.05 micrometer is more preferable.

In addition, the inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, and composite oxides of the above metals.

As said organic pigment, the following pigments are mentioned, for example.

Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C.I. Pigment orange 36, 38, 43, 71;

C.I. Pigment red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C.I. pigment violet 19, 23, 32, 39;

Pigment blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment green 7, 36, 37;

C.I. Pigment brown 25, 28;

C.I. Pigment black 1,7;

Examples of pigments that can be preferably used in the present invention include the following pigments. However, the present invention is not limited to these.

Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C.I. pigment orange 36,71,

Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C.I. peakment violet 19, 23, 32,

Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

Pigment green 7, 36, 37;

C.I.Pigment Black 1

In the present invention, the photocurable colored resin composition preferably contains green, red or blue organic pigments as the organic pigments.

Each of these organic pigments may be used alone or in various combinations to increase color purity.

Specific examples, such as the said combination, are shown below.

Examples of the red pigment include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or mixed pigments of red pigments thereof, at least one of these pigments and JIS yellow pigments and isoindolin yellow pigments. And mixed pigments with a quinophthalone yellow pigment can be used.

Examples of the anthraquinone pigments include CI peakment red 177, perirene pigments include CI pigment red 155 and CI peakment red 224, and diketopyrrolopyrrole pigments include CI. Picment Red 254 is mentioned, and mixing with CI peakment yellow 139 is preferable at the point of color reproducibility.

In addition, the mass ratio of the red pigment and the yellow pigment is preferably 100: 5 to 100: 75. If it is out of this range, it is difficult to suppress transmittance | permeability and color purity may not be raised. Moreover, as a preferable mass ratio, it is 100: 10-100: 50.

As the green pigment, a halogenated phthalocyanine pigment may be used alone or in combination with a JIS azo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment.

For example, such examples include C.I. Peakment green 36 alone or in C.I. peakment green 7, 36,37 and C.I. Preference is given to mixing peakment yellow 83, C. I. peakment yellow 138, C. I. peakment yellow 139, C. I. pigmet yellow 150, C. I. pigment yellow 180 or C. I. pigment yellow 185.

The mass ratio of green pigment and yellow pigment is preferably 100: 5 to 100: 150.

As the blue pigment, a phthalocyanine-based pigment may be used alone, or a mixture of this and a dioxazine-based purple pigment may be used.

For example, mixing of C.I. Pigment Blue 15: 6 with C.I.Pigment Violet 23 is preferred.

The mass ratio between the blue pigment and the purple pigment is preferably 100: 0 to 100: 30.

Moreover, in the photocurable composition of this invention, content of the said coloring agent is 40 mass% or more in total solid. If the content of the colorant is less than 40 mass%, sufficient color concentration cannot be obtained when the film thickness of the pixel is 1.5 µm or less, and for example, color separation of the image sensor (solid-state image sensor) using the same It will lower.

As content of the said coloring agent, it is 40 mass% or more with respect to whole solid content, Preferably it is 45 mass% or more, More preferably, it is 50 mass% or more. Moreover, although the upper limit of content of the said coloring agent is not specifically limited, In order to prevent the fall of curability and a sensitivity, it is preferable that it is 80 mass% or less from the point which ensures content of a photopolymerizable compound and a photoinitiator to some extent, and is 70 mass% or less More preferred.

(Photopolymerizable compound)

Next, the photopolymerizable compound will be described.

In the present invention, the photopolymerizable compound needs to have an alkali-soluble group in the molecule. Here, the alkali-soluble group in the molecule is not particularly limited even if the alkali-soluble group is bonded to the main chain of a conventionally known photopolymerizable compound or the compound in which the alkali-soluble group is bonded to the side chain.

The photocurable composition of the present invention eliminates the need to use an alkali-soluble resin generally used by using a photopolymerizable compound having an alkali-soluble group in a molecule, and as a result, the total content of the colorant, the photopolymerizable compound and the photopolymerizable initiator is reduced. It can increase and also film hardenability can be ensured by light irradiation.

Moreover, also in the thinning of the color filter of this invention, by using the said photocurable composition of this invention, it has sufficient color purity, maintains alkali developability, and is excellent in the rectangularity of the pattern profile of a pixel. .

It does not specifically limit as said alkali-soluble group, It is acidic groups, such as a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Of these, carboxyl groups are preferred.

The side chain to which the alkali-soluble group is bonded is not particularly limited, and examples thereof include ethylene oxide chain, vinyl alcohol, vinylpyrrolidone, hydroxy group, and styrene group.

The position of the side chain to which the alkali-soluble group is bonded is not particularly limited at the end portion of the side chain or at the center portion of the side chain.

As said well-known polymeric compound, a radically polymerizable monomer etc. are mentioned, for example. The photopolymerizable compound used in the present invention preferably has at least one ethylenic double bond (polymerizable functional group) capable of addition polymerization, and the number of the polymerizable functional groups is two or more, preferably 3 It is 20 or more pieces, More preferably, they are 3 pieces or more and 15 or less, Most preferably, they are 3 or more and 10 or less. If the number of functional groups is too large, the reactivity decreases, which is undesirable.

Moreover, the compound which has a boiling point of 100 degreeC or more under normal pressure is also preferable, and, as for the said photopolymerizable compound, it is more preferable to combine with the said polymerizable functional group.

Examples of the radically polymerizable monomer include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy ethyl (meth) acrylate, and polyethylene glycol di; (Meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth ) Acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate,

After adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane tri (acryloyloxy propyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane and then (meth) acrylic The urethane acrylates described in Japanese Patent Application Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193; Japanese Patent Publication No. 48-64183 , Polyester acrylates described in Japanese Patent Application Laid-Open Nos. 49-43191 and Japanese Patent Laid-Open No. 52-30490; multifunctional compounds such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid. And acrylates thereof, and mixtures thereof. Moreover, the thing introduced as a photocurable monomer and an oligomer can be mentioned in Japanese adhesive association Vol.20, No. 7, page 300-308.

Specific examples are given below as the photopolymerizable compound in the present invention. However, in this invention, a photopolymerizable compound is not limited to these.

It is preferable that content of the said photopolymerizable compound in the photocurable composition of this invention is determined so that the total content of a coloring agent and a photoinitiator may be 80 mass% or more as mentioned above, From a viewpoint of color concentration etc., the whole 85 mass% or more is more preferable with respect to solid content, and 90 mass% or more is especially preferable.

<Photopolymerization initiator>

As said photoinitiator, For example, halomethyloxadiazole of Unexamined-Japanese-Patent No. 57-6096; Halomethyl of Unexamined-Japanese-Patent No. 59-1281, Unexamined-Japanese-Patent No. 53-133428, etc. are mentioned, for example. active halogen compounds such as -s-triazine; aromatic carbonyl compounds such as ketal, acetal or benzoin alkyl ethers described in US Patent USP-4318791, European Patent Publication EP-88050A, etc .; benzophenones described in US Patent USP-4199420 Aromatic ketone compounds such as; (thio) xanthones or acridine compounds described in Fr-2456741; compounds such as coumarin or ropindimers described in JP-A-10-62986; JP-A-8-015521 Sulfonium organoboron complexes such as those described in Japanese Patent Application Laid-Open.

In the present invention, as the photopolymerization initiator, acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, acridine series, coumarin series, and ropin dimer series It is preferable to use photoinitiators, such as a biimidazole type.

As said acetophenone type photoinitiator, 2, 2- diethoxy acetophenone, p-dimethylamino acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethyl, for example Aminoacetophenone, 4'-isopropyl-2-hydroxy-2-methyl- propiophenone, etc. are mentioned preferably.

As said ketal type photoinitiator, benzyl dimethyl ketal, benzyl- (beta)-methoxy- ethyl acetal, etc. are mentioned preferably, for example.

As said benzophenone type photoinitiator, a benzophenone, 4, 4'- (bis dimethyl amino) benzophenone, 4, 4'- (bisdiethyl amino) benzophenone, 4, 4'- dichloro benzophenone, for example , 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tril-2-dimethyl amino-1- (4 -Morpholinophenyl) -butanone 1,2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropaneone-1, etc. are mentioned preferably.

As said benzoin type or benzoyl type photoinitiator, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoate, etc. are mentioned preferably, for example.

As said xanthone type photoinitiator, diethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, chloro thioxanthone, etc. are mentioned preferably, for example.

As said triazine type photoinitiator, 2, 4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2, 4-bis (trichloromethyl) -6-p- Methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4- Bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxysty Reyl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6 -Di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxy Carbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine etc. are mentioned preferably.

As said halomethyloxadiazole type photoinitiator, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole and 2-trichloromethyl-5- (cyanostyryl) -1, for example , 3, 4-oxo diazole, 2-trichloro methyl-5- (naphtho-1-yl) -1, 3, 4-oxo diazole, 2-trichloro methyl-5- (4-styryl) Styryl-1, 3, 4-oxodiazole etc. are mentioned preferably.

As said acridine type photoinitiator, 9-phenyl acridine, 1, 7 bis (9-acridinyl) heptane, etc. are mentioned preferably, for example.

As said coumarin-type photoinitiator, it is 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenyl coumarin, 3-chloro-5-diethylamino- (( s-triazin-2-yl) amino) -3-phenyl coumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenyl coumarin, etc. are mentioned preferably. have.

As said lopindimer type | system | group photoinitiator, 2- (o-chlorophenyl) -4, 5-diphenyl imidazolyl dimer, 2- (o-methoxyphenyl) -4, 5-diphenyl, for example Imidazolyl dimer, 2- (2, 4-dimethoxy phenyl) -4, 5-diphenyl imidazolyl dimer, etc. are mentioned preferably.

As said biimidazole type photoinitiator, 2-mercapto benz imidazole, 2, 2'- benzo thiazolyl disulfide, etc. are mentioned preferably, for example.

In addition, as said photoinitiator, 1-phenyl- 1, 2-propanedione- 2- (o-ethoxycarbonyl) oxime, O-benzoyl-4'- (benz mercapto) benzoyl-hexyl- ketoxime, 2, 4, 6-trimethylphenyl carbonyl diphenyl phosphonyl oxide, hexafluoro phosphoro trialkyl phenyl phosphonium salt, etc. are mentioned.

In this invention, it is not limited to the above photoinitiator, Another well-known thing can also be used. For example, bisinalpolyketolaldonyl compounds disclosed in US Pat. Nos. 2,367,660 and α- disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Carbonyl Compound, Acyloin Ether, as disclosed in US Pat. No. 2, 448, 828, Aromatic Hydrocarbon Substituted with α-Hydrocarbon, as disclosed in US Pat. No. 2, 722, 512, USA Polynuclear quinone compounds disclosed in the specification of Patent Nos. 3, 046, 127 and 2, 951, 758, and triallylimidazole dimer / p-amino phenyl disclosed in US Pat. No. 3, 549, 367 And a benzothiazole compound / trihalomethyl-s-triazine compound disclosed in a combination of ketones and JP-A-51-48516.

Moreover, these photoinitiators can also be used together.

The usage-amount of the said photoinitiator is 0.1-10.0 mass% of the total solid of a photocurable colored resin composition, Preferably it is 0.5-5.0 mass%. When the usage-amount of a photoinitiator is less than 0.1 mass%, it may be difficult for superposition | polymerization to advance, and when it exceeds 10.0 mass%, film strength may become weak.

(Other additives)

About the photocurable composition of this invention, an additive can be contained other than the above-mentioned coloring agent, a photopolymerizable compound, and a photoinitiator. However, it is preferable that total content other than the said coloring agent, a photopolymerizable compound, and a photoinitiator is less than 20 mass% with respect to the total solid of a composition, It is more preferable that it is less than 15 mass%, It is especially preferable that it is less than 10 mass%.

Below, in the photocurable composition of this invention, an additive other than the said coloring agent which can be used, a photopolymerizable compound, and a photoinitiator is demonstrated.

Alkali-soluble binder

First, an alkali-soluble binder is demonstrated.

The photocurable composition of this invention can add an alkali-soluble binder in the range which does not impair the effect of this invention.

The alkali-soluble binder is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

As said alkali-soluble binder, it is a linear organic polymer aggregate, and what melt | dissolves in the organic solvent and can develop with a weak alkali aqueous solution is preferable. As such linear organic polymer aggregates, polymers having a carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid described in each of Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048 The copolymer, the partial ester maleic acid copolymer, etc. are mentioned, The acidic cellulose derivative which has a carboxylic acid in the side chain similarly is useful.

In addition to the above, examples of the alkali-soluble binder include an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxy styrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), poly Vinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful.

In addition, the linear organic polymer aggregate may be a copolymer of a monomer having hydrophilicity. Examples include alkoxyalkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, glycerol (meth) acrylates, (meth) acrylamides, N-methylol acrylamides, secondary or tertiary alkyl acrylamides. , Dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl ( Meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, or phenoxy hydroxy propyl (meth) acrylate, etc. are mentioned.

Bridge

In this invention, the film | membrane hardened | cured even more highly using a crosslinking agent can be obtained complementarily. Hereinafter, a crosslinking agent is demonstrated.

The crosslinking agent usable in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin, (b) a methylol group, an alkoxy methyl group, and an acyloxymethyl group. Phenol substituted with at least one substituent selected from melamine compound, guanamine compound, glycoluril compound or urea compound, (c) methylol group, alkoxy methyl group, and acyloxy methyl group, substituted with at least one substituent selected from A compound, a naphthol compound, or a hydroxyanthracene compound is mentioned. Especially, polyfunctional epoxy resin is preferable.

As said (a) epoxy resin, as long as it has an epoxy group and has crosslinkability, any may be sufficient, For example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, Glycidyl group-containing low-molecular weight compounds such as hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, phthalic acid diglycidyl ester, N, N-diglycidyl aniline, and the like Glycidyl group-containing low-molecular weight compounds of the three values represented by olpropane triglycidyl ether, trimethylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, and the like, pentaerythritol tetraglycidyl ether, tetramethylol bisphenol Glycidyl group-containing low-molecular weight compounds of four values represented by A tetraglycidyl ether and the like, dipentaerythritol pentaglycidyl ether and dipentaerythr Polyhydric glycidyl group-containing low molecular weight compounds, such as hexaglycidyl ether, polyglycidyl (meth) acrylate, 1, 2-epoxy-4- (2 of 2, 2-bis (hydroxymethyl) -1-butanol A glycidyl group containing high molecular compound etc. represented by -oxyranyl) cyclohexane addition product etc. are mentioned.

As the number substituted by the methylol group, the alkoxy methyl group, and the acyloxy methyl group contained in the said crosslinking agent (b), it is 2-6 in the case of a melamine compound, 2-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound, Preferably it is 5-6 for a melamine compound, and 3-4 for a glycoluril compound, a guanamine compound, and a urea compound.

Hereinafter, the melamine compound, guanamine compound, glycoluril compound, and urea compound of the above (b) are collectively referred to as the compound (containing methylol group, alkoxy methyl group or acyloxy methyl group) associated with (b).

The methylol group-containing compound related to (b) can be obtained by heating the alkoxy methyl group-containing compound related to (b) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methane sulfonic acid in alcohol. The acyloxy methyl group containing compound which concerns on said (b) can be obtained by mixing and stirring the methylol group containing compound which concerns on (b) with an acyl chloride in presence of a basic catalyst.

Hereinafter, the specific example of the compound which concerns on (b) which has the said substituent is mentioned.

Examples of the melamine compound include compounds in which 1 to 5 of the methylol groups of hexamethylol melamine, hexamethoxy methyl melamine, and hexamethylol melamine are methoxy methylated, or mixtures thereof, hexamethoxy ethyl melamine, and hexa acyloxy methyl. The compound in which 1-5 of the methylol groups of melamine and the hexamethylol melamine acyloxylated, or its mixture, etc. are mentioned.

Examples of the guanamine compound include compounds in which methoxy methylated 1 to 3 methylol groups of tetramethylol guanamine, tetramethoxy methyl guanamine, and tetra methylol guanamine are mixed, and tetramethoxy ethyl guanamine And tetraacyloxy methyl guanamine, a compound obtained by acyloxy methylation of one to three methylol groups of tetramethylol guanamine, or a mixture thereof.

As said glycoluril compound, the compound in which methoxymethylated 1-3 of the methylol groups of tetramethylol glycoluril, tetramethoxymethyl glycoluril, and tetramethylol glycoluril, or its mixture, tetramethylol glycol is mentioned, for example. The compound which carried out 1-3 acyloxy methylation of the methylol group of usyl, or its mixture, etc. are mentioned.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxy methylation of 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, tetramethoxyethyl urea and the like. .

The compounds related to these (b) may be used alone or in combination.

The phenol compound, the naphthol compound, or the hydroxyanthracene compound substituted with at least one group selected from the crosslinking agent of (c), ie, methylol group, alkoxy methyl group, and acyloxy methyl group, is the same as that of the crosslinking agent (b). In other words, the thermal crosslinking suppresses mixing with the upper coating photoresist and at the same time increases the film strength. Hereinafter, these compounds are collectively referred to as compounds (containing methylol group, alkoxy methyl group or acyloxy methyl group) associated with (c).

As the number of methylol groups, acyloxy methyl groups or alkoxy methyl groups contained in the crosslinking agent (c), at least two are required per molecule, and from the viewpoints of thermal crosslinkability and storage stability, two-position and four-position of the phenol compound to be a skeleton The compound in which all are substituted is preferable. Moreover, as for the naphthol compound and the hydroxyanthracene compound which become skeleton, the compound in which both the ortho position and para position of an OH group are substituted is preferable. The 3-position or 5-position of the said phenol compound may be unsubstituted or may have a substituent.

Also in the said naphthol compound, it may be unsubstituted or may have a substituent except the ortho position of an OH group.

The methylol group-containing compound according to the above (c) uses a compound in which the 2-position or 4-position of the phenolic OH group is a hydrogen atom as a raw material, which is basic such as sodium hydroxide, potassium hydroxide, ammonia, tetraalkyl ammonium hydroxide and the like. Obtained by reacting with formalin in the presence of a catalyst.

The alkoxy methyl group containing compound which concerns on said (c) can be obtained by heating the methylol group containing compound which concerns on (c) in presence of acid catalysts, such as hydrochloric acid, a sulfuric acid, nitric acid, methane sulfonic acid, in alcohol.

The acyloxy methyl group-containing compound related to (c) can be obtained by reacting the methylol group-containing compound related to (c) with an acyl chloride in the presence of a basic catalyst.

As a skeletal compound in a crosslinking agent (c), a phenolic compound, a naphthol, a hydroxyanthracene compound, etc. which are unsubstituted in the ortho position or para position of a phenolic OH group are mentioned, for example, each of phenol and cresol Bisphenols, such as an isomer, 2, 3- xylenol, 2, 5- xylenol, 3, 4- xylenol, 3, 5- xylenol, bisphenol A, 4, 4 'bishydroxy biphenyl , TrisP-PA (manufactured by Honshu Kagaku Kogyo KK), naphthol, dihydroxy naphthalene, 2, 7-dihydroxyanthracene, and the like are used.

As a specific example of the said crosslinking agent (c), For example, the compound which methoxy methylated 1-2 methylol groups of trimethylol phenol, a tri (methoxy methyl) phenol, and a trimethylol phenol, trimethylol-3- as a phenol compound Dimethylolcresol, such as a compound which methoxymethylated 1-2 methylol groups of cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, and 2,6-dimethylol-4-cresol, tetra Methylol bisphenol A, tetramethoxy methyl bisphenol A, the compound which methoxymethylated 1-3 methylol groups of tetramethylol bisphenol A, tetra methylol 4, 4'-bishydroxybiphenyl, tetramethoxy methyl 4 , A compound in which 1 to 5 methylol groups of 4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, and hexamethylol of TrisP-PA are methoxy methylated; Hydroxy methyl naphthalene diol and the like.

Examples of the hydroxyanthracene compound include 1, 6-dihydroxy methyl-2, 7-dihydroxyanthracene, and the like. Examples of the acyloxy methyl group-containing compound include the compounds of the methylol group-containing compound. The compound etc. which carried out partial or all the acyloxy methylation of the methylol group are mentioned.

Preferred among these compounds are hexamethylol bodies of trimethylol phenol, bishydroxy methyl-p-cresol, tetra methylol bisphenol A, TrisP-PA (manufactured by Honshu Chemical Industries, Ltd.) or such methylol groups are alkoxy methyl groups. And phenol compounds substituted with both methylol groups and alkoxy methyl groups.

The compounds related to these (c) may be used alone or in combination.

As total content in the photocurable composition of the said crosslinking agent, although it changes with a raw material, 0.1-7 mass% is preferable with respect to solid content (mass) of the said photocurable composition from a viewpoint of improving sclerosis | hardenability, and 0.1-6 mass % Is more preferable, and 0.15-5 mass% is the most preferable.

- Thermal polymerization inhibitor -

In addition to the above, it is preferable to add a thermal-polymerization inhibitor to the photocurable composition of this invention further. For example, hydroquinone, p-methoxy phenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4, 4′-thiobis (3-methyl-6-t -Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butyl phenol), 2 mercaptobenzoimidazole and the like are useful.

As content of a thermal-polymerization inhibitor, 0.1-15 mass% is preferable with respect to solid content (mass) of the said photocurable composition from a viewpoint of the stability of a photocurable composition.

Organic solvents

Although the organic solvent which can be used for this invention satisfy | fills solubility of each component and the applicability | paintability of a photocurable composition is not specifically limited fundamentally, It is preferable to select especially in consideration of the solubility, coating property, and safety of a coloring agent. Moreover, when preparing the photocurable composition of this invention, it is preferable to contain at least 2 type of organic solvent.

As said organic solvent, ester, For example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl Esters, methyl lactate, ethyl lactate, oxy methyl acetate, ethyl oxy acetate, oxy butyl acetate, methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethyl ethoxy acetate and the like;

3-oxy propionic acid alkyl esters, such as 3-oxy methyl propionate and 3-oxy ethyl ethyl, for example, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy Ethyl propionate, and the like; 2-oxy propionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate, 2-oxy propionic acid propyl, for example, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxy propionic acid propyl, 2-ethoxy methyl propionate, 2-ethoxy propionate ethyl, 2-oxy-2-methyl propionate, 2-oxy-2-methyl ethyl propionate, 2-methoxy 2-methyl methyl propionate , 2-ethoxy-2-methyl ethyl propionate; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl aceto acetate, ethyl aceto acetate, methyl 2-oxo butyrate, ethyl 2-oxo butyrate, etc. ;

Ethers such as diethylene glycol dimethyl ether, tetra hydrofuran, ethylene glycol monomethyl ether, ethylene glycol mono ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol mono butyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like; aromatic hydrocarbons such as toluene, xylene and the like are preferable.

As mentioned above, such an organic solvent may mix 2 or more types from a viewpoint of the solubility of the containing component of the photocurable composition of this invention, the improvement on an application surface, etc. Especially, the said 3-ethoxy methyl propionate and 3-ethoxy Ethyl propionate, ethyl cellosolve acetate, lactic acid ethyl, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy propionate methyl, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether , And a mixed solution composed of two or more selected from propylene glycol methyl ether acetate is preferably used.

It is preferable to make the usage-amount of the organic solvent in this invention into the quantity which becomes 5-80 mass% of total solid content concentration of the photocurable composition of this invention from a viewpoint of applicability | painting, 5-60 mass% is more preferable, , 10-50 mass% is especially preferable.

Various Additives

In the photocurable composition of the present invention, various additives, for example, fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and the like can be blended.

Specific examples of the various additives include fillers such as glass and alumina; high molecular compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic and anionic Surfactants, such as type; vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxy ethoxy) silane, N- (2-amino ethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxy cyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth Adhesion promoters such as oxysilane Antioxidants such as 2, 2-thiobis (4-methyl-6-t-butyl phenol) and 2, 6-di-t-butyl phenol; 2- (3-t-butyl-5-methyl-2-hydride Ultraviolet absorbers such as oxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and anti-aggregation agents such as sodium polyacrylate.

Moreover, when promoting alkali solubility of a non-image part and further improving developability of the photocurable composition of this invention, organic carboxylic acid, low molecular weight organic carboxylic acid of molecular weight 1000 or less is preferably used for the said composition. Can be added.

Specifically, For example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid and caprylic acid; oxalic acid, malonic acid, succinic acid Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimeric acid, sublinic acid, azeline acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid and citraconic acid Aliphatic tricarboxylic acids such as carboxylic acid, tricarbaric acid, aconitic acid and canhoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemeric acid, and mesitylene acid; phthalic acid, isophthalic acid Aromatic polycarboxylic acids such as terephthalic acid, trimellitic acid, trimesic acid, meropanic acid and pyromellitic acid; phenyl acetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atroic acid, cinnamic acid, Methyl Cinnamic Acid, Cinnamic And other carboxylic acids such as acid benzyl, cinnamilidene acetic acid, coumalic acid and unbelic acid.

<< color filter >>

Next, the color filter of this invention is explained in full detail through the manufacturing method.

In the manufacturing method of the color filter of this invention, the photocurable composition of this invention of technology is used.

The color filter of this invention forms the coating film which consists of said photocurable composition on a board | substrate, and has the pixel formed by patterning the said coating film by the port lithography method using alkali image development.

By setting it as such a structure, the color filter of this invention can be made excellent in the color uniformity between pixels, and also excellent in the rectangularity of the pattern profile of a pixel.

In the color filter of this invention, it is preferable that the minimum transmittance | permeability is 10% or less in the range of wavelength 400 nm-700 nm, and the difference of the maximum transmittance and the said minimum transmittance is 65% or more in the said wavelength range.

Especially, from the viewpoint of color separation and transmittance of the color filter, the minimum transmittance is preferably 8% or less, particularly preferably 6% or less.

Moreover, the difference between the maximum transmittance and the minimum transmittance in the wavelength range is more preferably 70% or more, particularly preferably 75% or more.

In such a combination, a more preferable combination is more preferable.

In the color filter of this invention, it is preferable that the thickness of the pixel formed on a board | substrate is 1.5 micrometers or less from a viewpoint of thinning of a color filter, It is more preferable that it is 1.3 micrometers or less, It is especially preferable that it is 1.2 micrometers or less.

Although the lower limit of the thickness of the said pixel is not specifically limited, It is preferable that it is 0.3 micrometer or more and 0.5 micrometer or more from a viewpoint of the function as a color filter, productivity, and smoothness.

Moreover, it is preferable that it is 5.0 micrometers or less, and, as for the length of the largest side (maximum side in the case of observing a pixel from the top) of said pixel from a viewpoint of making a pixel high density and realizing a high resolution, it is more preferable that it is 4 micrometers or less. And it is especially preferable that it is 3.5 micrometers or less.

Although the lower limit of the maximum side of the said pixel is not specifically limited, It is preferable that it is 0.4 micrometer or more from the nature of the function of the filter which permeate | transmits visible light.

Moreover, specifically, the manufacturing method of the color filter of this invention apply | coats the photocurable composition of this invention on the board | substrate by application | coating methods, such as rotation coating, casting | flow_spread coating, roll coating, etc., and an application layer (photocurable composition). Layer), the layer is exposed through a predetermined mask pattern, and alkali developed by a developing solution such as an alkaline aqueous solution to form a negative colored pattern (pixel) (image forming step).

Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

Moreover, in manufacture of the color filter of this invention, the color filter which becomes a desired color can be manufactured by repeating the said image forming process (and the hardening process as needed) by a desired number of colors. As light or radiation used at this time, particularly ultraviolet rays such as g-rays, h-rays, and i-rays are preferably used.

Examples of the substrate include soda glass, pyrex (registered trademark) glass, quartz glass and a transparent conductive film attached thereto, or a photoelectric conversion element substrate used for an imager, for example, silicon. A substrate, a complementary metal oxide film semiconductor (CMOS), and the like. Such a board | substrate may be provided with the black stripe which isolate | separates each pixel.

Further, on the substrate, a lower coating layer may be provided, if necessary, in order to improve adhesion to the upper layer, to prevent diffusion of substances, or to planarize the substrate surface.

As the developer, any one can be used as long as it is made of a composition in which the unirradiated portion (uncured portion) of the photocurable composition of the present invention is dissolved while the irradiated portion (cured portion) is not dissolved.

Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used. As said organic solvent, the above-mentioned organic solvent used when preparing the photocurable composition of this invention is mentioned.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethyl amine, dimethyl ethanol amine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, Alkaline compounds such as pyrrole, piperidine and 1,8-diazabicyclo- [5.4.0] -7-undecene are dissolved in a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Alkaline aqueous solution is preferable. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it generally washes with water after image development.

The color filter of this invention can be used for solid-state image sensors, such as a liquid crystal display element and CCD, and it is especially preferable for a CCD element, CMOS, etc. of high resolution exceeding 1 million pixels. The color filter of this invention can be used as a color filter arrange | positioned, for example between the light-receiving part of each pixel which comprises CCD, and the micro lens for condensing.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the meaning is exceeded. In addition, "part" is a "mass part" unless there is particular notice.

[Example 1]

1) Preparation of Transparent Layer

Coating liquid CT-2000L (manufactured by Fujifilm Electronics Co., Ltd.) for transparent layers was applied on a 6-inch-diameter silicon substrate on which a photodiode was formed by spin coating, and then heated in an oven at 220 ° C for 1 hr. It dried and the transparent layer of 2 micrometers of film thicknesses was obtained.

2) Preparation of Photocurable Composition

Solvent: Cyclohexanone # 800 parts

Photopolymerizable Compound A 70Part

Photoinitiator: o-acyl oxime compound (CGI-124: Chiba Specialty Chemicals Co., Ltd.) # 30 parts

Acid dye A: Balifast # Blue # 2620 (made by Orient Chemical Co., Ltd.) "25 parts" dye B: 75 parts of following dye (B) was mixed and dissolved, and the photocurable composition was prepared.

The dye B was synthesized according to the following scheme.

Scheme

(Synthesis of Compound B)

25.5 g (0.162 mole) of Compound A was dissolved in 100 ml of methanol and 23 ml of triethylamine, and 9 ml of 30% hydrogen peroxide was added dropwise while maintaining 5 ml of 30% hydrogen peroxide at 5 ° C under cooling stirring. The reaction solution was further stirred at 25 ° C for 30 minutes, cooled to 5 ° C again, 15 ml of concentrated hydrochloric acid was added dropwise under stirring, 200 ml of water was further added, and the mixture was stirred at 25 ° C for 1 hour. Precipitated crystals were filtered off, washed sufficiently with water, and the obtained crystals were dried to obtain 24.7 g of a white crystal (Compound B). The yield was 99.5%.

(Synthesis of Compounds C, D, E)

100 ml of toluene and 0.25 m of dimethylacetoamide were added to 17.5 parts by mass (0.114 mol) of the compound B, and 25 ml of thionyl chloride was added dropwise for 10 minutes under reflux. After further refluxing for 1 hour, the mixture was concentrated under reduced pressure to obtain a viscous liquid. On the other hand, 10 ml of dimethylacetoamide and 100 ml of acetonitrile were added to 38.0 parts by mass (0.235 mol) of diethoxyethylamine, and the viscous liquid was added dropwise while maintaining the mixture at 15 ° C for 15 minutes while stirring. After further stirring for 30 minutes, the mixture was poured into 100 ml of water and 100 ml of ethyl acetate, the ethyl acetate layer was separated, and washed twice with 100 ml of water. The ethyl acetate layer was dried over magnesium sulfate, ethyl acetate was distilled off under reduced pressure to obtain a pale yellow viscous liquid (Compound C).

To this pale yellow viscous liquid (Compound C), 50 ml of water, 200 ml of ethanol and 12 parts by mass (0.200 mol) of zinc powder were added, and a solution of 10 ml of sulfuric acid diluted in 40 ml of water was added dropwise for 20 minutes under reflux. The mixture was further heated and stirred for 30 minutes, then cooled, and the insolubles were filtered out. 50 ml of saturated saline and 100 ml of ethyl acetate were added to the obtained solution, the solution was separated, and the ethyl acetate layer was washed twice with 100 ml of water. The ethyl acetate layer was dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a pale yellow viscous liquid (Compound D).

70 ml of dimethylacetamide and 15 parts by mass (0.108 mol) of potassium carbonate were added to the viscous liquid (compound D) under stirring in a nitrogen atmosphere, and 19.7 parts by mass of 3-nitrobutaronitrile (0.113 moles) under stirring at 20 ° C. Was added slowly at 25 ° C or lower. After further stirring for 30 minutes, the mixture was poured under stirring with 300 ml of water, and the obtained crystal was filtered and thoroughly washed. The obtained crystals were recrystallized from 70 ml of methanol, the precipitated crystals were washed with 30 ml of cold methanol, dried and 35.0 parts by mass (0.082 mol) of white crystals (Compound E) were obtained. The yield of compound E was 72.6%.

Synthesis of Dye B

150 ml of butanol, 6.7 parts by mass of ammonium carbonate (0.070 moles) and 4.7 parts by mass of copper chloride (0.035 moles) were added to 34.4 parts by mass (0.081 moles) of compound E, and the mixture was heated and stirred for 7 hours. Then, butanol was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography to obtain 25 parts by mass (0.020 mol) of the powder of the dye B. The yield was 72.7%.

Absorption of the obtained dye B in ethyl acetate was (lambda) max 70, 6.8 nm, (epsilon) 55.600.

3) Preparation, exposure and development of photocurable coating film

The coating liquid of the said 2) photocurable composition is apply | coated to the transparent layer obtained by 1) by the spin coat method, it heats (prebakes) by 100 degreeC * 120 second by a hotplate, and makes a film thickness into 1 micrometer A chemical conversion coating film was obtained.

Then, i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Corporation) was used, and the coating film was irradiated at an exposure dose of 3000 mJ / cm ² through an island pattern mask having a maximum side 2 μm at a wavelength of 365 nm. did.

After exposure, the board | substrate which formed the photocurable coating film on the horizontal rotating table of the spin shower developing machine (made by DW-30 type chemistry company) was mounted, and it developed developer CD-2000 (made by Fujifilm Electronics Materials Co., Ltd.). ), Paddle development was carried out at 23 ° C. for 60 seconds.

Thereafter, the water is fixed to the horizontal rotating table by a vacuum zipper method, while the substrate is rotated at 50 rpm by a rotating device, pure water is supplied from the jet nozzle to the shower stall above the center of rotation, washed, and then sprayed. It dried and the color filter was obtained.

4) Pattern profile of color filter and evaluation method of residue

About each said color filter, one pattern is observed directly from the top using SEM (made by Hitachi Ltd., S-9260A), and it is "(circle)" that a rectangle is bad about a pattern profile, "△" It evaluated that it was blurred and whose contour was not sure as "x". The shape of the pixel pattern is shown in FIG. In FIG. 1, (1) shows a pixel, and (2) shows a transparent layer surface. Moreover, about the residue, "(circle)" that there was no residue in the unexposed part, "△" that the residue remained a little, and evaluated that the residue remained as "x" were evaluated. The evaluation results are shown in Table 2.

5) Evaluation method of absorption maximum transmittance and absorption minimum transmittance of the coating film for color filters

The photocurable composition was apply | coated on the glass substrate by the spin-coating method, it heat-processed (prebaked) by 100 degreeC x 120 second with a hot plate, and the film thickness became 1.0 micrometer, and the coating film for color filters was obtained.

The transmittance | permeability of wavelength 400nm-700nm was measured for the said coating film for color filters using the spectrophotometer (The product of Otsuka Electronic Co. Ltd., MCPD-2000).

The difference was calculated as the minimum transmittance as the absorption minimum transmittance and the maximum transmittance as the absorption maximum transmittance among the above transmittances. If the evaluation criteria are less than 65%, there is a problem in practical use, if it is 65% or more and less than 75%, there is no problem in practical use, and if it is 75% or more, it is excellent. The evaluation results are shown in Table 2.

[Examples 2-7]

In Example 1, the photocurable composition was prepared like Example 1 except having changed each composition contained in the photocurable composition into the composition shown in following Table 1, and producing a color filter And it evaluated similarly to Example 1.

In addition, the resist layer in the evaluation method of Example 1 formed and evaluated the coating film for color filters using the said photocurable composition.

[Comparative Examples 1-4]

In Example 1, the comparative photocurable composition was prepared like Example 1 except having changed each composition contained in the photocurable composition into the composition shown in following Table 1, and comparing A color filter was produced and evaluated in the same manner as in Example 1. The shape of the pixel pattern in the comparative example 1 is shown in FIG. In FIG. 2, (1) shows a pixel and (2) shows a transparent layer surface.

Moreover, the coating film for color filters in the evaluation method of Example 1 formed the coating film for color filters using the said photocurable composition, and evaluated it similarly to Example 1.

In Table 1, each compound is as follows.

Photopolymerizable compound C: dipentaerythritol hexaacrylate (product of Nippon Kayaku Co.Ltd.)

Acid dye A ： Valifast Blue 2620 (product of Orient Chemical Industries Ltd.)

Dye B: The dye B

Resin A: Benzyl methacrylate / methacrylic acid copolymer (70/30 copolymerization ratio average molecular weight 30,000)

In the said Table 1, photopolymerizable compound A, photopolymerizable compound B, and photopolymerizable compound D are as showing below.

In addition, the pigment dispersion used in Example 7 shown in Table 1 was prepared as follows.

<Preparation of pigment dispersion>

The following composition was stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was dispersed for 4 hours using a beads disperser (trade name: DISPERMAT, manufactured by GETZMANN Co., Ltd.) using 0.1 mm zirconia beads to obtain a dispersion.

Composition of pigment dispersion

Pigment Blue 15: 6 Part 15

Dispersion resin: 9 parts of propylene glycol monomethyl ether acetate solutions (solid content: 50 mass%) of the benzyl methacrylate / methacrylic acid copolymer (= 75/25 [mass ratio], weight average molecular weight Mw: 16000)

3 parts of a propylene glycol monomethyl ether acetate (30%) solution of a dispersant (brand name: Disperbyk-161, product of BYK-Chemie Japan K.K)

Propylene Glycol Monomethyl Ether Acetate 73 Parts

In the embodiment of the present invention, as shown in Table 2, a pixel having a good pattern profile was obtained, there was no developing residue, and a high color density (difference between absorption maximum transmittance and absorption minimum transmission) was obtained.

1 and 2, the outline of the pixel is sharp in the first embodiment of the present invention of FIG. 1, and is sharper than the angle of the pixel viewed from above. In the comparative example 1 of FIG. 2, the outline of the pixel is blurred. It turned out that the skirt became the shape which spread | disconnected at the interface with the transparent layer surface of a base, and it turned out that it was rounder than each angle of this pixel.

According to the present invention, it is possible to provide a photocurable composition having sufficient color density, spectral characteristics, sensitivity and curability, and excellent in the rectangularity and developability of the pattern of the pixel when used in a color filter.

Further, according to the present invention, it is possible to provide a color filter having a sufficient color density and excellent in the rectangularity of the pattern of the pixel.

Claims (16)

In the photocurable composition containing a coloring agent, a radically polymerizable monomer, and a photoinitiator, Content of the said coloring agent is 40 mass% or more of all solid content, The coloring agent has an acid dye of 25% by mass or more based on the total amount of the coloring agent, The radically polymerizable monomer has an alkali soluble group. The photocurable composition according to claim 1, wherein the total content of the colorant, the radically polymerizable monomer, and the photopolymerization initiator is 80% by mass or more based on the total solids in the photocurable composition. The photocurable composition according to claim 1, wherein the number of polymerizable functional groups of the radically polymerizable monomer is three or more. delete delete The photocurable composition according to claim 1, wherein the alkali-soluble group of the radically polymerizable monomer is at least one of a carboxyl group, a phosphoric acid group and a sulfonic acid group. A color filter comprising a pixel formed by forming a coating film made of the photocurable composition according to claim 1 on a substrate, and patterning by a photolithography method using alkali development. The color filter according to claim 7, wherein the minimum transmittance is 10% or less in the range of 400 nm to 700 nm, and the difference between the maximum transmittance and the minimum transmittance is 65% or more in the wavelength range. 8. The color filter according to claim 7, wherein the pixel has a thickness of 0.3 µm or more and 1.5 µm or less. 8. The color filter of claim 7, wherein a maximum side of the pixel is 5.0 mu m or less. The photocurable composition according to claim 1, wherein the acid dye has a sulfonic acid group, a carboxylic acid group or a phenolic hydroxyl group. The photocurable composition of Claim 1 whose content of the dye containing the said acid dye is 60 mass% or more with respect to the total amount of the said coloring agent. The photocurable composition according to claim 1, wherein the radically polymerizable monomer is the following photopolymerizable compound A or photopolymerizable compound B.

The photocurable composition according to claim 1, wherein the photopolymerization initiator is an o-acyl oxime compound. The photocurable composition according to claim 1, wherein the number of polymerizable functional groups of the radically polymerizable monomer is 3 or more and 10 or less. The photocurable composition of Claim 1 whose content of the said radically polymerizable monomer is 90 mass% or more with respect to the total solid in the said photocurable composition.

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