TWI437366B - Color photosensitive composition for solid-state imaging device, color filter for solid-state imaging device and fabricating method thereof - Google Patents

Description

Colored photosensitive composition for solid-state image sensor, color filter for solid-state image sensor, and method of manufacturing the same

The present invention relates to a color filter suitable for use in a solid-state imaging device (Charge Coupled Device (CCD), Complementary Metal Oxide Semiconductor (CMOS), etc.) A colored photosensitive composition for a color image, a color filter for a solid-state image sensor using the colored photosensitive composition, and a method for producing the same.

The method of producing a color filter used in a solid-state image sensor is the same as the method of fabricating a color filter used in a liquid crystal display device, and is generally known as a dyeing method, a printing method, a plating method, and a pigment dispersion method. .

When a color filter is produced by a pigment dispersion method, a photosensitive composition containing a pigment is applied onto a substrate by a spin coater or a roll coater, and dried to form a photosensitive composition. Coating film. The colored film is formed by patterning and developing the coating film. The above operation is repeated for each color, whereby a color filter can be formed. The photosensitive composition used for the pigment dispersion method is, for example, a negative-type (nega) photosensitive composition in which an alkali-soluble resin is used together with a photopolymerizable monomer (monomer) and a photopolymerization initiator (for example, reference) Japanese Patent Laid-Open No. 7-140654).

In recent years, it has been desired to further improve the definition and thickness of the color filter for a solid-state image sensor. For example, a technique for forming a film for maintaining spectroscopic characteristics reveals a coloring agent in a total solid content of a coloring photosensitive composition. A technique in which the content is increased and the pattern formation property is improved by a resin (for example, refer to Japanese Laid-Open Patent Publication No. 2006-276878). However, if the content of the colorant is increased, the content of the curable component is relatively reduced, so there is always a problem that the sensitivity is remarkably lowered.

On the other hand, various techniques for adding various polymerization inhibitors to impart stability over time to a negative photosensitive composition are disclosed (for example, refer to Japanese Patent Laid-Open No. Hei 8-292566, No. 2000-214580 Japanese Patent Laid-Open Publication No. 2003-177517. However, in recent years, when the content of the colorant is increased, the influence of the decrease in sensitivity caused by the polymerization inhibitor is increased, so that the problem of pattern peeling during development by a low exposure amount cannot be ignored.

The present invention has been made in view of the above problems, and an object thereof is to provide a method for suppressing peeling of a pixel pattern during development by using a low exposure amount even when the content of a colorant is high, and it is stable over time at room temperature or above. A colored photosensitive composition for a solid-state image sensor which is excellent in properties; and a color filter for a solid-state image sensor using the colored photosensitive composition and a method for producing the same.

<1> A coloring photosensitive composition for a solid-state image sensor, characterized in that it contains 50% by weight or more and 80% by weight or less of a coloring agent with respect to the total solid content, and 1.0 × 10 ^{-5 or more} A thermal polymerization inhibitor of a phenol compound which is wt% and less than or equal to 1.0 × 10 ^-3 wt%.

<2> The solid-state image sensor of the above <1> is composed of coloring photosensitive And the above coloring agent is a dye soluble in an organic solvent.

<3> The colored photosensitive composition for solid-state image sensor according to <1> or <2>, further comprising a resin containing an unsaturated double bond, which is selected from the following formula (1) to (3) at least one structural unit and acid group in the first structural unit group represented by any one of the formulas, and at least one structural unit selected from the second structural unit group represented by the following general formula (4), Further, the ratio (mol ratio) of the first structural unit to the second structural unit is 1.5 times or 1.5 times or more.

In the above formulae (1) to (3), A ¹ , A ² and A ³ each independently represent an oxygen atom, a sulfur atom or -N(R ²¹ )-, and R ²¹ represents a hydrogen atom or an alkyl group which may have a substituent. base. G ¹ , G ² and G ³ each independently represent a divalent organic group. X and Z each independently represent an oxygen atom, a sulfur atom or -N(R ²² )-, and R ²² represents an alkyl group which may have a substituent. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent or -N(R ²³ )-, and R ²³ represents a hydrogen atom or an alkyl group which may have a substituent. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a monovalent substituent. Further, in the above formula (4), R _A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R _B represents a divalent bonding group.

<4> The coloring photosensitive composition for a solid-state image sensor according to <3>, wherein the weight average molecular weight of the resin is 30,000 or more and 300,000 or less.

<5> Coloring for a solid-state image sensor according to any one of <1> to <4> A photosensitive composition further containing an oxime initiator.

The colored photosensitive composition for a solid-state image sensor of any one of the above-mentioned <1>, which is contained in the total solid content, and further contains 1.0 wt% - 40.0 wt%. Photopolymerization initiator.

(7) A method of producing a color filter for a solid-state image sensor, comprising: applying a coloring photosensitive composition for a solid-state image sensor according to any one of <1> to <6> to a support And forming a colored photosensitive composition layer; The coloring photosensitive composition layer is exposed and developed by a mask to form a pattern on the support.

<8> A color filter for a solid-state image sensor, which is formed by using the coloring photosensitive composition according to any one of <1> to <6>.

According to the present invention, it is possible to provide a solid-state image sensor which is capable of suppressing peeling of a pixel pattern during development even when the content of the colorant is high, and which is excellent in stability over time at room temperature or above. a colored photosensitive composition; and a color filter for a solid-state image sensor using the colored photosensitive composition and a method for producing the same.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

The inventors of the present invention conducted a research on a color-sensitive photosensitive composition suitable for producing a color filter for a solid-state image sensor, and as a result, found a color-sensitive photosensitive composition which is expressed in terms of the content of the total solid content and contains or is greater than or equal to 50wt% and 80wt% or less of the colorant is greater than equal to 1.0 × 10 ^-5 wt% and less than or equal to 1.0 × 10 ^-3 wt% of a thermal polymerization inhibitor, a phenol-based compound, thereby even a high content of the colorant, may The low exposure amount is used to suppress the peeling of the pixel pattern during development, and the stability with time is also good when stored at room temperature or above.

<Coloring photosensitive composition>

The colored photosensitive composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention") respectively contains a predetermined amount of at least one of (A) a colorant and a predetermined amount of (B) thermal polymerization selected from a phenolic compound. At least one of the inhibitors may be further composed of other components as needed.

Hereinafter, each component constituting the colored photosensitive composition of the present invention will be described in detail.

(A) colorant

The coloring photosensitive composition of the present invention contains 50% by weight or more and 80% by weight or less of the coloring agent, based on the total solid content. In the present invention, the "total solid content" means all components other than the solvent contained in the coloring photosensitive composition. As the above coloring agent, known pigments and dyes previously used for color filters can be used without particular limitation.

~Pigment~

The pigment which can be contained in the colored photosensitive composition of the present invention may, for example, be various conventionally known inorganic pigments and organic pigments, and is preferably a pigment having a high light transmittance. The pigment having a high light transmittance is a pigment having a small absorbance of 600 nm to 700 nm in the case of a pigment used in a red filter; and a pigment used for a green filter, Means 525nm A pigment having a small absorbance of ~575 nm; and a pigment for use in a blue filter means a pigment having a small absorbance of 425 nm to 475 nm.

Examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, and titanium. a metal oxide such as magnesium, chromium, zinc or antimony or a composite oxide of the above metals.

Examples of the organic pigments include: CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199; CI Pigment Orange 36, 38, 43, 71; CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270; CI Pigment Violet 19, 23, 32,39; CI Pigment Blue 1,2,15,15:1,15:3,15:6,16,22,60,66; CI Pigment Green 7,36,37; CI Pigment Brown 25,28;CI Pigment black 1,7; carbon black and the like.

In the present invention, in particular, a pigment containing a basic N atom in the structural formula of the pigment can be preferably used. These pigments containing a basic N atom exhibit good dispersibility in the colored photosensitive composition of the present invention. The reason is not very clear, and it is inferred that the affinity between the polymerizable component and the pigment is high or low. Impact.

The pigment which can be preferably used in the present invention is exemplified by the following pigments. However, the invention is not limited to these pigments.

CI Pigment Yellow 11,24,108,109,110,138,139,150,151,154,167,180,185; CI Pigment Orange 36,71; CI Pigment Red 122,150,171,175,177,209,224,242,254,255,264;CI Pigment Violet 19,23,32;CI Pigment Blue 15:1,15:3,15:6,16,22,60,66 ; CI Pigment Black 1.

These organic pigments may be used singly or in combination of two or more kinds. By using two or more types in combination, the color purity of the pigment can be improved. For example, when the colored photosensitive composition of the present invention is used for forming a colored pattern of a color filter, it is preferred to use two or more kinds of pigments in combination. Thereby, the color purity of the colored pattern of the color filter can be further improved.

Specific examples of the combination of the pigment and the pigment are shown below.

For example, examples of the red pigment include an anthraquinone-based pigment, a perylene-based pigment, and a diketopyrrolopyrrole-based pigment, respectively; and at least one of the above red pigments and a disazo (disazo) is a combination of at least one of a yellow pigment, an isoindoline-based yellow pigment, a quinophthalone-based yellow pigment, and an anthraquinone-based red pigment.

For example, C.I. Pigment Red 177 is exemplified, and C.I. Pigment Red 155, C.I. Pigment Red 224, and diketoppyrrolepyrrole pigment, for example, C.I. Pigment Red 254 is exemplified.

In the present invention, in terms of color reproducibility, a combination of an anthraquinone pigment, an anthraquinone pigment, or a diketopyrrolopyrrole pigment and C.I. Pigment Yellow 139 is preferred.

The weight of the red pigment and the yellow pigment in the above combination is preferably from 100/50 to 100/5. By adjusting the above weight ratio to 100/5 or less, the light transmittance of 400 nm to 500 nm can be suppressed, so that it is easy to further improve the color purity. Further, by adjusting the above weight ratio to 100/50 or more, it is possible to prevent the dominant wavelength from being shifted to a short wavelength, and it is possible to further reduce the deviation from the target color of the National Television System Committee (NTSC). The above weight ratio is particularly preferably in the range of 100/30 to 100/10. Further, when two or more red pigments are combined, the respective content ratios can be adjusted to match the chromaticity.

Further, as the green pigment, a phthalocyanine halide pigment may be used alone, and the pigment may be mixed with a disazo yellow pigment, a quinophthalone yellow pigment, a azomethine yellow pigment or an isoindole. The porphyrin yellow pigment is used in combination. For example, a combination of such a combination of CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Yellow 185 is preferred. . green

The weight of the green pigment and the yellow pigment in the above combination is preferably from 100/150 to 100/5, particularly preferably from 100/120 to 100/30.

The blue pigment may be a phthalocyanine-based pigment alone, and the pigment may be used in combination with a dioxazine-based violet pigment. For example, a mixture of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23 is preferred.

The weight of the blue pigment and the violet pigment in the above combination is preferably from 100/30 to 100/1, more preferably from 100/10 to 100/1.

Further, when the colored photosensitive composition of the present invention is used for a pigment used in forming a black matrix of a color filter, carbon (carbon), titanium carbon, iron oxide, titanium oxide or the like may be used alone. The combination is preferably a combination of carbon and titanium carbon. Further, the weight of carbon and titanium carbon in the above combination is preferably in the range of 100/60 to 100/1.

When the colored photosensitive composition of the present invention is used in a color filter, the primary particle diameter of the colorant, that is, the pigment, is preferably 100 nm or less from the viewpoint of color unevenness or contrast, and is self-dispersing. From the viewpoint of stability, it is preferably 5 nm or more. The primary particle size of the pigment is preferably from 5 nm to 75 nm, further preferably from 5 nm to 55 nm, particularly preferably from 5 nm to 35 nm.

The primary particle diameter of the pigment can be measured by a known method such as an electron microscope.

Among them, the pigment is preferably a pigment selected from the group consisting of an anthraquinone, a methine azo, a benzylidene, a cyanine, a diketopyrroloxime, and a phthalocyanine.

~Dyestuff~

The coloring agent of the present invention is preferably a dye in terms of forming a finer pattern. Especially in the case where the fine pattern can be formed into a rectangular shape In other words, the colorant is preferably a dye which is soluble in an organic solvent, and more preferably the colorant is a dye which is soluble in an organic solvent. Further, in general, the dye has polymerization inhibition performance, so that the colorant is good in stability over time.

For the dye, a conventionally known dye can be used, for example, Japanese Patent Laid-Open No. Hei 64-90403, Japanese Patent Laid-Open No. Hei 64-91102, Japanese Patent Laid-Open No. Hei No. Hei 1-94301, and Japanese Patent Laid-Open No. Hei 6-11614 The pigment disclosed in Japanese Patent No. 2592207, the specification of the U.S. Patent No. 4,808,501, the specification of U.S. Patent No. 5,667,920, the specification of U.S. Patent No. 5,059,500, and the Japanese Patent Laid-Open No. Hei 6-35183. In terms of chemical structure, triphenylmethane, lanthanide, benzylidene, oxonol, cyanine, phenothiazine, pyrrole pyrazole can be used. A dye such as pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran or indigo. Particularly preferred are pyrazole azo, anilino azo, pyrazolotriazole azo, pyridone azo, anthrapyridone. dye.

In addition, direct dyes, basic dyes, mordant dyes, acid dyes, azoic dyes, disperse dyes, oil-soluble dyes Oil soluble dyes, food dyes and/or derivatives of these dyes can also be used effectively.

<acid dye>

Here, the acid dye will be described. The acid dye which can be contained in the colored photosensitive composition of the present invention is not particularly limited as long as it has an acidic group such as a sulfo group, a carboxyl group or a phenolic hydroxyl group in the molecule, and can be considered as an organic solvent or a developer. The solubility in the medium, the salt formability of the basic compound, the absorbance, the interaction with other components in the composition of the present invention, the light resistance, and the heat resistance are selected.

Specific examples of the acid dye are listed below. However, the invention is not limited to these dyes.

For example, acid alizarin violet N; acid black 1,2,24,48; acid blue 1,7,9,15,18,23,25, 27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103,112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324:1,335,340; acid chrome violet K; acid fuchsin ( Acid fuchsin); acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;acid orange 6,7,8,10,12, 26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173; acid red 1,4,8,14,17,18,26,27,29,31, 34,35,37,42,44,50,51,52,57,66,73,80,87,88,91,92,94, 97,103,111,114,129,133,134,138,143,145,150,151,158,176,182,183,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349,382,383,394,401,412,417,418,422,426; Acid Violet (acid violet) 6B, 7,9,17,19; acid yellow (acid yellow) 1,3,7,9,11,17,23,25,29,34,36,38,40, 42,54,65,72,73,76,79,98,99,111,112,113,114,116,119,123,128,134,135,138,139,140,144,150,155,157,160,161,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,205,205,207,212,214,220,221,228,230,232,235,238,240,242,243, 251; direct yellow 2,33,34,35,38,39,43,47,50,54,58,68,69, 70,71,86,93,94,95,98,102,108,109,129,136,138,141; direct orange 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107; Direct red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250; direct violet 47,52,54,59,60,65,66,79,80, 81,82,84,89,90,93,95,96,103,104; direct blue (direct b Lue)57,77,80,81,84,85,86,90,93,94, 95,97,98,99,100,101,106,107,108,109,113,114,115,117,119,137,149,150,153,155,156,158,159,160,161,162,163,164,166,167,170,171,172,173,188,189,190,192,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252,256,257,259,260,268,274,275,293; Direct Green (direct green) 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82; mordant yellow (Mordant Yellow) 5,8,10,16,20,26,30,31,33,42,43,45,56,50,61,62,65; mordant orange 3,4,5,8, 12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,48; mordant red 1,2,3,4, 9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41,43,45,46,48,53, 56,63,71,74,85,86,88,90,94,95; mordant violet 2,4,5,7,14,22,24,30,31,32,37,40, 41,44,45,47,48,53,58;mord blue 2,3,7,8,9,12,13,15,16,19,20,21,22,23,24, 26,30,31,32,39,40,41,43,44,48,49,53,61,74,77,83,84; mordant green 1,3,4,5,10, 15,19,26,29,33,34,35,41,43,53; food yellow 3; and derivatives of these dyes.

Among the above acid dyes, preferred are: acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 74, 63; 4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249; Acid Violet 7; Acid Yellow 17,25,29,34,42,72,76,99,111,112,114,116,134,155,169,172,184,220,228,230,232,243; Acid Green 25; derivative.

As the derivative of the acid dye, an inorganic salt of an acid dye having a sulfo group or a carboxyl group, a salt of an acid dye and a nitrogen-containing compound, and/or an amide compound can be used, and if it is soluble in the composition of the present invention, Special restrictions. The derivative of the acid dye can be selected in consideration of the solubility in the organic solvent or the developer, the absorbance, the interaction with other components in the composition of the present invention, the light resistance, the heat resistance and the like.

The acid dye and the salt of the nitrogen-containing compound and the guanamine compound will be described.

The solubility of the acid dye can be improved (solubility imparted in an organic solvent) or the heat resistance and light resistance can be improved by forming a salt or a guanamine compound with an acid dye and a nitrogen-containing compound.

Further, for a nitrogen-containing compound that forms a salt with an acid dye, and with an acid The nitrogen-containing compound in which the dye forms a guanamine bond can comprehensively consider solubility of a salt or a guanamine compound in an organic solvent or a developer, salt formability, absorbance of a dye, color value, and composition of the present invention. The interaction of other components in the middle, the heat resistance of the colorant, the light resistance, and the like are selected. When selecting from the viewpoints of absorbance and color value, the above nitrogen-containing compound is preferably a compound having a molecular weight which is only likely to be small, and among them, a compound having a molecular weight of 300 or less is preferable, and a compound having a molecular weight of 280 or less is more preferable. Particularly preferred are compounds having a molecular weight of 250 or less.

The molar ratio (hereinafter referred to as n) of the nitrogen-containing compound/acid dye in the salt of the acid dye and the nitrogen-containing compound will be described. n is a value which determines the molar ratio of the acid dye molecule to the nitrogen-containing compound which becomes a counter ion, and can be freely selected according to the salt formation conditions of the acid dye and the nitrogen-containing compound. Specifically, depending on the number of acidic functional groups in the acid dye, a value between 0 and n≦5 is often used practically, and solubility in an organic solvent or developer, salt formability, absorbance, and The essential components such as the interaction, light resistance, and heat resistance of other components in the composition of the invention are selected. When selecting from the viewpoint of self-absorbance, the above n is preferably a value between 0 < n ≦ 4.5, and further preferably a value between 0 < n ≦ 4, particularly preferably 0 < n ≦ 3.5 The value between.

In the coloring agent for coloring the photosensitive composition of the present invention, a dye containing two or more hydrogen bond donors in the dye is particularly preferable from the viewpoint of suppressing development residue. Specific examples of the dyes include dyes and the like described in JP-A-2006-243040.

For the coloring agent of the colored photosensitive composition of the present invention, in the dye In particular, a dye containing at least one of phthalocyanine dyes which are soluble in an organic solvent is preferred from the viewpoint of light resistance and heat resistance. In the present invention, the phthalocyanine dye which is soluble in an organic solvent is not particularly limited and can be suitably used.

For example, the phthalocyanine dyes which are soluble in an organic solvent, such as those described in JP-A-H05-333207, JP-A-6-51115, and JP-A-6-194828 . Particularly preferred phthalocyanine dyes which are soluble in an organic solvent include the dye compounds represented by the following formula (I).

[Pigment compound represented by the formula (I)]

The dye compound represented by the formula (I) will be described. The dye compound represented by the following formula (I) is a phthalocyanine dye which is soluble in an organic solvent and has a good molar absorption coefficient ε and a good color value, and is a compound which satisfies both high light resistance and high heat resistance.

In the above formula (I), Rc ₁ represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, Sulfhydryl, hydroxy, aliphatic, aryloxy, acyloxy, amine methyloxy, heterocyclic oxy, aliphatic oxycarbonyloxy, N-alkyldecylamino, amine Mercaptoamine, sulfamoylamino, aliphatic oxycarbonylamino, aryloxycarbonylamino, aliphatic sulfonylamino, arylsulfonylamino, aliphatic sulfur A aryl group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, an amine sulfonyl group, a sulfo group, a quinone imine group, or a heterocyclic thio group. Zc ₁ represents a group of non-metal atoms necessary for forming a 6-membered ring together with a carbon atom, and the four Zc ₁ groups may be the same or different. M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide or a divalent metal chloride. Cm represents 0, 1 or 2, cn represents 0 or an integer from 1 to 5, and 4 cns may be the same or different. Wherein at least one of cn represents an integer from 1 to 5, and a plurality of Rc ₁ in the molecule may be the same or different. Cr1, cr2, cr3, and cr4 represent 0 or 1, and satisfy cr1+cr2+cr3+cr4≧1.

In the above formula (I), the aliphatic moiety of the "aliphatic group" is linear, branched or cyclic, and may be either saturated or unsaturated, for example, including an alkyl group, an alkenyl group, or a cycloalkane. The base or cycloalkenyl group may be unsubstituted or substituted with a substituent. Further, the "aryl group" may be either a monocyclic ring or a fused ring, and may be unsubstituted or substituted with a substituent. "Heterocyclyl" means a group in which a heterocyclic moiety has a hetero atom (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) in the ring, and may be either a saturated ring or an unsaturated ring, and may be a single ring or Any of the fused rings, which may be unsubstituted or substituted with a substituent.

Further, in the above formula (I), the "substituent" is a substitutable group For example, an aliphatic group, an aryl group, a heterocyclic group, a fluorenyl group, a fluorenylene group, an azo group, a decyloxy group, a decylamino group, an aliphatic oxy group, an aryloxy group, and a hetero aryl group may be mentioned. Epoxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, amine carbaryl group, aliphatic sulfonyl group, aryl sulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group , arylsulfonyloxy, heterocyclosulfonyloxy, sulfonyl, aliphatic sulfonamide, arylsulfonylamino, heterocyclosulfonylamino, amine, aliphatic amine Base, arylamine, heterocyclic amine, aliphatic oxycarbonylamino, aryloxycarbonylamino, heterocyclooxycarbonylamino, aliphatic sulfinyl, arylsulfin Base, aliphatic thio group, arylthio group, heterocyclic thio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, amine mercaptoamine group, amine sulfonyl group An amine group, a halogen atom, an aminesulfonylamine carbenyl group, an amine formammonium sulfonate group, a di-aliphatic oxyphosphinyl group, a diaryloxyphosphino group or the like.

As shown above, in the general formula (I), Rc ₁ represents a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an amine carbenyl group, an aliphatic oxycarbonyl group, or an aryloxycarbonyl group. , mercapto, hydroxy, aliphatic, aryloxy, decyloxy, amine methyl methoxy, heterocyclic oxy, aliphatic oxycarbonyloxy, N-alkyldecylamino, amine formazan Amino group, amine sulfonylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group An aliphatic sulfonyl group, an arylsulfonyl group, an amine sulfonyl group, a sulfo group, a quinone imine group or a heterocyclic thio group.

The halogen atom represented by the above Rc ₁ may, for example, be a fluorine atom, a chlorine atom or a bromine atom.

The aliphatic group represented by the above Rc ₁ may be unsubstituted or may have a substituent, may be saturated, may be unsaturated, and may be cyclic, preferably a fat having a total carbon number of 1 to 15. Family group. For example, a methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, an isopropenyl group, a 2-ethylhexyl group, etc. are mentioned.

The aryl group represented by the above Rc ₁ may be unsubstituted or may have a substituent, and is preferably an aryl group having a total carbon number of 6 to 16, more preferably an aryl group having a total carbon number of 6 to 12. For example, phenyl, 4-nitrophenyl, 2-nitrophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, 2,4-dimethylphenyl 2-methylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 2-methoxycarbonyl-4-nitrophenyl, and the like.

The heterocyclic group represented by the above Rc ₁ may be saturated or unsaturated, preferably a heterocyclic group having a total carbon number of 1 to 15, more preferably a heterocyclic group having a total carbon number of 3 to 10. . For example, 3-pyridyl, 2-pyridyl, 2-pyrimidinyl, 2-pyrazinyl, 1-piperidyl can be cited. Wait. Further, the above heterocyclic group may have a more substituent.

The amine carbenyl group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an amine carbenyl group having a total carbon number of 1 to 16, more preferably a total carbon number of 1 to 12. Aminomethyl thiol. For example, an amine methyl sulfonyl group, a dimethylamine methyl fluorenyl group, a dimethoxy ethylamine methyl fluorenyl group, etc. are mentioned.

The aliphatic oxycarbonyl group represented by the above Rc ₁ may be unsubstituted or may have a substituent, may be saturated, may be unsaturated, and may also be cyclic, and preferably has a total carbon number of 2 to 16. The aliphatic oxycarbonyl group is more preferably an aliphatic oxycarbonyl group having a total carbon number of 2 to 10. For example, a methoxycarbonyl group, a butoxycarbonyl group, etc. are mentioned.

The aryloxycarbonyl group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an aryloxycarbonyl group having a total carbon number of 7 to 17, more preferably a total carbon number of 7 to 15. Aryloxycarbonyl. For example, a phenoxycarbonyl group etc. are mentioned.

The mercapto group represented by the above Rc ₁ may be an aliphatic carbonyl group or an arylcarbonyl group, and may have a more substituent when it represents an aliphatic carbonyl group, and may have a more substituent when it represents an arylcarbonyl group, and may be saturated or not. Any of saturating, and may also be cyclic. The sulfhydryl group is preferably a fluorenyl group having a total carbon number of 2 to 15, more preferably a fluorenyl group having a total carbon number of 2 to 10. For example, an acetyl group, a pivaloyl group, a benzoyl group, etc. are mentioned. Further, the above mercapto group may have a more substituent.

The aliphatic oxy group represented by the above Rc ₁ may be unsubstituted or may have a substituent, may be saturated, may be unsaturated, or may be cyclic. The aliphatic oxy group is preferably an aliphatic oxy group having a total carbon number of from 1 to 12, more preferably an aliphatic oxy group having a total carbon number of from 1 to 10. For example, a methoxy group, an ethoxyethoxy group, a phenoxyethoxy group, a thiophenoxyethoxy group, etc. are mentioned.

The aryloxy group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an aryloxy group having a total carbon number of 6 to 18, more preferably an aryloxy group having a total carbon number of 6 to 14. base. For example, a phenoxy group, a 4-methylphenoxy group, etc. are mentioned.

The above fluorenyloxy group represented by Rc ₁ may be unsubstituted or may have a substituent, preferably a decyloxy group having a total carbon number of 2 to 14, more preferably a total of 2 to 10 carbon atoms. base. For example, an ethyl methoxy group, a methoxy ethoxy group, a benzyl hydryl oxy group, etc. are mentioned.

The amine methyl methoxy group represented by the above Rc ₁ may be unsubstituted or may have a substituent, and is preferably an amine methyl oxy group having a total carbon number of 1 to 16, more preferably a total carbon number of 1 ～. Aminomethyl methoxy group of 12. For example, a dimethylamine methyl methoxy group, a diisopropyl amine methyl methoxy group, etc. are mentioned.

The heterocyclic oxy group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably a heterocyclic oxy group having a total carbon number of from 1 to 15, more preferably a total carbon number of from 3 to 10. Heterocyclic oxy group. For example, 3-furyloxy, 3-pyridyloxy, N-methyl-2-piperidyloxy, etc. are mentioned.

The aliphatic oxycarbonyloxy group represented by the above Rc ₁ may be unsubstituted or may have a substituent, may be saturated, may be unsaturated, or may be cyclic. The aliphatic oxycarbonyloxy group is preferably an aliphatic oxycarbonyloxy group having a total carbon number of 2 to 16, more preferably an aliphatic oxycarbonyloxy group having a total carbon number of 2 to 10. For example, a methoxycarbonyloxy group, a (third) butoxycarbonyloxy group, etc. are mentioned.

The N-alkyldecylamino group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an N-alkyldecylamino group having a total carbon number of 3 to 15, more preferably The N-alkyldecylamino group having a total carbon number of 3 to 12 is used. For example, N-methylacetamidoamine group, N-ethoxyethyl benzhydrylamino group, N-methylmethoxyethyl fluorenyl group, etc. are mentioned.

The amine mercaptoamine group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an amine carbenylamino group having a total carbon number of 1 to 16, more preferably the total carbon number is Aminomercaptoamine group of 1-12. For example, N,N-dimethylamine-mercaptoamino group, N-methyl-N-methoxyethylamine-formylamino group, etc. are mentioned.

The aminesulfonylamino group represented by the above Rc ₁ may be unsubstituted or may have a substituent, and is preferably an aminesulfonylamino group having a total carbon number of 0 to 16, more preferably the total carbon number is Aminosulfonylamino group of 0~12. For example, N,N-dimethylaminesulfonylamino group, N,N-diethylaminesulfonylamino group, etc. are mentioned.

The aliphatic oxycarbonylamino group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an aliphatic oxycarbonylamino group having a total carbon number of 2 to 15, more preferably a total carbon. The number is 2 to 10 aliphatic oxycarbonylamino groups. For example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, etc. are mentioned.

The aryloxycarbonylamino group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an aryloxycarbonylamino group having a total carbon number of 7 to 17, more preferably the total carbon number is 7~15 aryloxycarbonylamino group. For example, a phenoxycarbonylamino group, a 4-methoxyphenoxycarbonylamino group, etc. are mentioned.

The aliphatic sulfonylamino group represented by the above Rc ₁ may be unsubstituted or may have a substituent, may be saturated, may be unsaturated, or may be cyclic. The aliphatic sulfonylamino group is preferably an aliphatic sulfonylamino group having a total carbon number of 1 to 12, more preferably an aliphatic sulfonylamino group having a total carbon number of 1 to 8. For example, a methanesulfonylamino group, a butasulfonylamino group, etc. are mentioned.

The arylsulfonylamino group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an arylsulfonylamino group having a total carbon number of 6 to 15, more preferably a total carbon. The number is 6 to 12 arylsulfonylamino groups. For example, a benzenesulfonylamino group, a 4-toluenesulfonylamino group, etc. are mentioned.

The aliphatic thio group represented by the above Rc ₁ may be unsubstituted or may have a substituent, may be saturated, may be unsaturated, or may be cyclic. The aliphatic sulfur group is preferably an aliphatic sulfur group having a total carbon number of 1 to 16, more preferably an aliphatic sulfur group having a total carbon number of 1 to 10. For example, a methylthio group, an ethylthio group, an ethoxyethylthio group, etc. are mentioned.

The arylthio group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an arylthio group having a total carbon number of 6 to 22, more preferably an aromatic sulfur having a total carbon number of 6 to 14. base. For example, a phenylthio group, a 2-t-butylphenylthio group, etc. are mentioned.

The aliphatic sulfonyl group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an aliphatic sulfonyl group having a total carbon number of 1 to 15, more preferably a total carbon number of 1~ 8 aliphatic sulfonyl groups. For example, a methylsulfonyl group, a butyl sulfonyl group, a methoxy sulfonyl group, etc. are mentioned.

The arylsulfonyl group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an arylsulfonyl group having a total carbon number of 6 to 16, more preferably a total carbon number of 6~ 12 arylsulfonyl. For example, a benzenesulfonyl group, a 4-t-butylbenzenesulfonyl group, a 4-toluenesulfonyl group, a 2-toluenesulfonyl group, etc. are mentioned.

The amine sulfonyl group represented by the above Rc ₁ may be unsubstituted or may have a substituent, preferably an amine sulfonyl group having a total carbon number of 0 to 16, more preferably a total carbon number of 0 to 12. Aminesulfonyl. For example, an amine sulfonyl group, a dimethyl sulfonyl group, etc. are mentioned.

The quinone imine group represented by the above Rc ₁ may be further ring-enriched, preferably a quinone imine group having a total carbon number of 3 to 22, more preferably a quinone imine group having a total carbon number of 3 to 15. For example, succinimide, phthalimide group, etc. are mentioned.

The heterocyclic thio group represented by the above Rc ₁ may be unsubstituted or may have a substituent, and is a 5- to 7-membered ring, preferably a heterocyclic thio group having a total carbon number of 1 to 20, more preferably A heterocyclic thio group having 1 to 12 carbon atoms. For example, a 3-furylthio group, a 3-pyridylthio group, etc. are mentioned.

In the above formula (I), Zc ₁ represents a group of non-metal atoms necessary for forming a 6-membered ring together with a carbon atom, and the four Zc ₁ groups may be the same or different. The 6-membered ring formed may be either an aryl ring or a heterocyclic ring, or may be ring-enhanced, and the ring-enhanced ring may have a more substituent. Examples of the 6-membered ring include a benzene ring, a pyridine ring, a cyclohexene ring, a naphthalene ring, and the like, and the 6-membered ring is preferably a benzene ring.

In the above formula (I), M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide or a divalent metal chloride. Examples of the M include VO, TiO, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ , Si(OH) ₂ , H _{2 ,} etc., and the aspect where M is VO, Zn, Mn, Cu, Ni or Co is suitable.

In the above formula (I), cm represents 0, 1 or 2 (preferably 0), and cn represents 0 or an integer of 1 to 5 (preferably 0 or 1). The four cn in the molecule may be the same or different, and one of the cn represents an integer of 1 to 5. When a plurality of cns are present in the molecule, the plurality of Rc ₁ may be the same or different.

Further, cr1, cr2, cr3, and cr4 represent 0 or 1, satisfying cr1+cr2+cr3+cr4≧1. Of these, it is preferred that cr1+cr2+cr3+cr4 is a state of 3 or 4.

Among the dye compounds represented by the above formula (I), a dye represented by the following formula (I-1) is preferred.

In the above formula (I-1), Rc ₂ represents a substituent, and the substituent may be a group which may be substituted, and examples thereof include the groups listed in the "Substituent". Preferred are aliphatic groups, aryl groups, heterocyclic groups, N-alkyldecylamino groups, aliphatic oxy groups, aryloxy groups, heterocyclic oxy groups, aliphatic oxycarbonyl groups, aryloxycarbonyl groups, Heterocyclic oxycarbonyl, amine mercapto, aliphatic sulfonyl, sulfonyl, aliphatic sulfonylamino, arylsulfonylamino, aliphatic amine, arylamine, aliphatic oxy More preferably, a carbonylamino group, an aryloxycarbonylamino group, an aliphatic thio group, an arylthio group, a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, an amine mercaptoamine group, an aminesulfonylamino group, a halogen atom, or more preferably It is an aliphatic group, an N-alkyl mercaptoamine group, an aliphatic oxy group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, an aliphatic thio group, an arylthio group, a sulfo group, a carboxyl group, and a halogen atom.

In the above formula (I-1), cp represents an integer of 0 to 4, preferably 0 or 1. Among them, cp+cr1, cp+cr2, cp+cr3, and cp+cr4 all represent integers of 0~4. When a plurality of Rc ₂ are present in the molecule, the plurality of Rc ₂ may be the same or different.

Further, Rc ₁ , M, cm, cn and cr1, cr2, cr3 and cr4 in the formula (I-1) have the same meanings as in the above formula (I), and preferred embodiments are also the same.

Among the dye compounds represented by the above formula (I-1), a dye represented by the following formula (I-2) is more preferred.

In the above formula (I-2), Rc ₁ , Rc ₂ , M, cm, cn and cr1, cr2, cr3 and cr4 have the same meanings as in the above formulae (I) and (I-1), respectively. The same is true. Further, cq in the formula (I-2) represents 0 or 1. Further, the phthalocyanine skeleton has a structure in which four benzene rings are condensed on the outer side of the tetraazaporphyrin skeleton, and each benzene ring has four sites (carbon atoms) into which a substituent can be introduced, and the above formula ( I-2) is a hydrogen atom bonded to two (beta) positions of the benzene ring away from the tetraazaporphyrin skeleton.

In the above formula (I-2), from the viewpoint of more effectively exhibiting the effects of the present invention, it is preferred that the above Rc ₁ is a halogen atom, an aliphatic group, a cyano group, an amine carbaryl group, or an aliphatic group. Oxycarbonyl, aryloxycarbonyl, hydroxy, aliphatic oxy, amine methyl methoxy, heterocyclic oxy, aliphatic oxycarbonyloxy, amine carbylamino, amine sulfonylamino, fat Alkoxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, amine sulfonyl group, hydrazine In the case of an imido group or a sulfo group, it is more preferred that the above Rc ₁ is an aliphatic group, an amine carbenyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an aliphatic oxy group, an aliphatic oxycarbonyl group. Oxyl, amine mercaptoamine, amine sulfonylamino, aliphatic oxycarbonylamino, aliphatic sulfonylamino, arylsulfonylamino, aliphatic sulfonyl, aryl sulfonate In the form of a mercapto group, an amine sulfonyl group, a quinone imine group or a sulfo group, it is preferred that the above Rc ₁ is an amine carbenyl group, an aliphatic oxycarbonyl group, an aliphatic oxy group, or an aliphatic oxycarbonyl group. The aspect of an oxy group, an aminomethylamino group, an aliphatic oxycarbonylamino group, an arylsulfonyl group, a quinone imine group or an aliphatic sulfonyl group.

Similarly, in terms of more effectively exerting the effects of the present invention, it is preferred that the above Rc ₂ is an aliphatic group, an N-alkyldecylamino group, an aliphatic oxy group, an aliphatic oxycarbonyl group, or a fat. The aspect of the sulfonyl group, the aliphatic thio group, the arylthio group, the sulfo group, the carboxyl group or the halogen atom is more preferably such that Rc ₂ is an aliphatic group or a halogen atom. Similarly, in the aspect in which the effects of the present invention can be exerted more effectively, it is preferred that the above cq is 0. Similarly, in the aspect in which the effect of the present invention can be more effectively exerted, it is preferred that the above M is a state of VO, Mn, Co, Ni, Cu, Zn or Mg, and more preferably, this M is VO, Co. In the case of Cu or Zn, it is preferable that this M is a Cu state. Also, it is preferred that the cm is 0. Further, it is preferable that cn is 1 or 2, and more preferably cn is 1.

From the viewpoint of further exerting the effects of the present invention, in the above formula (I-2), it is preferred that the above Rc ₁ is a halogen atom, an aliphatic group, a cyano group, an amine formazan group, or a fat. Alkoxycarbonyl, aryloxycarbonyl, hydroxy, aliphatic oxy, amine methyl methoxy, heterocyclic oxy, aliphatic oxycarbonyloxy, amine carbylamino, amine sulfonylamino, An aliphatic oxycarbonylamino group, an aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, an amine sulfonyl group, The above-mentioned M is VO, Co, Cu or Zn, the above cq is 0, the above cm is 0, and the above cn is 1; more preferably, the above Rc ₁ is fat. Group, amine methyl sulfonyl, aliphatic oxycarbonyl, aryloxycarbonyl, aliphatic oxy, aliphatic oxycarbonyloxy, amine carbylamino, amine sulfonylamino, aliphatic oxygen a carbonylamino group, an aliphatic sulfonylamino group, an arylsulfonylamino group, an aliphatic sulfonyl group, an arylsulfonyl group, an amine sulfonyl group, a quinone imine group or a sulfo group, and the above M is a VO Co Cu or Zn, the above-described cq is 0, 0 cm above, and the above aspects 1 to cn.

Particularly preferably, from the viewpoint of the effects of the present invention, it is preferred that the above Rc ₁ is an aminomethyl sulfonyl group, an aliphatic oxycarbonyl group, an aliphatic oxy group, an amine carbarylamino group, an aliphatic oxycarbonylamine. a group, an aliphatic sulfonyl group, an arylsulfonyl group or a quinone imine group, wherein the above M is Cu, the above cq is 0, the above cm is 0, and the above cn is 1.

Specific examples of the dyes (dyes) represented by the above formulas (I), (I-1), and (I-2) (exemplary compounds C-1 to C-35, C-41 to C-59) are listed below. . However, the present invention is not limited to this.

The coloring agent content in the total solid content of the colored photosensitive composition of the present invention is 50% by weight or more and 80% by weight or less, and from the viewpoint of improving the absorbance and film hardenability by using a coloring agent, it is preferably 52. Wt%~75 wt%, especially preferably 55 wt%~70 wt%.

(B) Thermal polymerization inhibitor

Next, the thermal polymerization inhibitor will be described. The coloring photosensitive composition of the present invention is required to contain a thermal polymerization inhibitor of a phenolic compound of 1.0 × 10 ^-5 wt% or more and 1.0 × 10 ^-3 wt% or less, based on the total solid content.

Examples of the phenolic compound to be added as a thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, and di-t-butyl-p-cresol. Pyrogallol, catechol, tert-butyl catechol, 4,4'-thiobis(3-methyl-6-tert-butylphenol) (4, 4'-thio bis(3-methyl-6-t-butyl phenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (2,2'-methylene bis (4-methyl-6-t-butyl phenol)), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylene double (6- Third butyl m-cresol).

Among them, the thermal polymerization inhibitor represented by the following formula (7) is preferred in terms of both sensitivity and stability over time.

In the formula (7), R ₁ represents a hydroxyl group or an alkoxy group, and R ₂ represents a hydrogen atom or an alkyl group.

R _{1 is} preferably a hydroxyl group, a methoxy group, an ethoxy group or a propyl group, more preferably a hydroxyl group or a methoxy group, and most preferably a methoxy group.

R _{2 is} preferably a hydrogen atom, a methyl group or a third butyl group, more preferably a hydrogen atom, a third butyl group, and most preferably a hydrogen atom.

Specific examples of particularly preferable examples represented by the formula (7) include hydroquinone, p-methoxyphenol, and 2,6-di-t-butyl-4-methoxyphenol.

The amount of the above-mentioned thermal polymerization inhibitor to be added must be 1.0 × 10 ^-5 wt% or more and 1.0 × 10 ^-3 wt% or less in the total solid content of the colored photosensitive composition of the present invention. When the amount added is less than 1.0 × 10 ^-5 wt%, the stability over time is not sufficient. On the other hand, if the addition amount is more than 1.0 × 10 ^-3 wt%, the use of a low exposure amount will result in a significant pattern peeling phenomenon. The thermal polymerization inhibitor of the phenolic compound is preferably added in an amount of 3.0 × 10 ^-5 wt% or more and 5.0 × 10 ^-4 wt% or less, and the most preferable addition amount is 5.0 × 10 ^-5 wt% or more. Less than or equal to 3.0 × 10 ^-4 wt%.

(C) resin

The colored photosensitive composition of the present invention preferably contains a predetermined amount of a resin. The resin (hereinafter also referred to as a binder) which can be contained in the composition of the present invention is not particularly limited, and is preferably selected from the viewpoints of heat resistance, developability, and availability.

The binder is preferably a linear organic high molecular polymer, a binder which is soluble in an organic solvent and which can be developed using a weak aqueous alkali solution. Such a linear organic high molecular polymer is a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese The methacrylic acid copolymer described in the specification of each of Japanese Patent Publication No. Sho 59-53848, Japanese Patent Laid-Open Publication No. SHO 59-53848, Acrylic copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. Acidic cellulose derivatives having a carboxylic acid in the side chain are also useful. In addition, an acid anhydride is added to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polysiloxane resin, or a poly((meth)acrylate 2-hydroxy group). Poly(2-hydroxyethyl(meth)acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful.

Further, a monomer having hydrophilicity may be copolymerized, and examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and glycerol (meth)acrylate. (meth)acrylate), (meth) acrylamide, N-methylol acrylamide, secondary and tertiary alkyl acrylamide, dialkylamine (meth) acrylate Alkyl ester, morpholine (meth)acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinyl imidazole, vinyl Triazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branched or linear butyl (meth)acrylate, (meth)acrylic acid Phenoxypropyl propyl ester and the like.

In addition, as a hydrophilic monomer, it contains a tetrahydrofurfuryl, a phosphoric acid, a phosphate, an ammonium salt, an ethyleneoxy chain, a propyleneoxy chain, A monomer such as a sulfonic acid or a salt thereof, a morpholinylethyl group or the like is also useful.

The resin of the present invention is preferably a resin containing an unsaturated group. The light sensitivity can be improved by the resin containing an unsaturated group.

Examples of the resin containing an unsaturated group include the following resins as representative resins: a carboxyl group-containing resin and a glycidyl group-containing unsaturated compound or alkene such as glycidyl (meth)acrylate or allyl glycidyl ether. a resin obtained by reacting an unsaturated alcohol such as propanol, 2-hydroxy acrylate or 2-hydroxy methacrylate; reacting a carboxyl group-containing resin having a hydroxyl group with an unsaturated compound containing a free isocyanate group or an unsaturated acid anhydride Resin; a resin obtained by reacting an addition reaction of an epoxy resin with an unsaturated carboxylic acid with a polybasic acid anhydride; and an addition reaction of a conjugated diene copolymer with an unsaturated dicarboxylic anhydride; a resin obtained by reacting a polymerizable monomer of a hydroxyl group; a dehydration reaction is generated by an alkaline treatment to synthesize a resin having a specific functional group imparting an unsaturated group, and then the resin is subjected to an alkali treatment to form an unsaturated group. Resin of the group.

Among them, a resin obtained by reacting a carboxyl group-containing resin with a glycidyl group-containing unsaturated compound such as glycidyl (meth)acrylate or allyl glycidyl ether; and a hydroxyl group-containing (methyl group) a resin obtained by reacting a resin obtained by polymerizing an acrylate-based compound with a (meth) acrylate having a free isocyanate group such as 2-isocyanatoethyl (meth)acrylate; and conforming to the following formula (1) Resin to (3); The resin is subjected to a reaction to synthesize a resin having a specific functional group imparting an unsaturated group, and then the resin is subjected to an alkali treatment to form a resin having an unsaturated group.

The resin in the composition of the present invention is particularly preferably one having at least one selected from the structural unit (first structural unit) represented by any one of the following general formulae (1) to (3) as the unsaturated double A polymer compound in the bond portion.

In the above formulae (1) to (3), A ¹ , A ² and A ³ each independently represent an oxygen atom, a sulfur atom or -N(R ²¹ )-, and R ²¹ represents a hydrogen atom or an alkyl group which may have a substituent. base. G ¹ , G ² and G ³ each independently represent a divalent organic group. X and Z each independently represent an oxygen atom, a sulfur atom or -N(R ²² )-, and R ²² represents a hydrogen atom or an alkyl group which may have a substituent. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent or -N(R ²³ )-, and R ²³ represents a hydrogen atom or an alkyl group which may have a substituent. R ¹ to R ²⁰ each independently represent a monovalent substituent.

In the above formula (1), R ¹ to R ³ each independently represent a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among them, R ¹ and R ^{2 are} preferably a hydrogen atom, and R ^{3 is} preferably a hydrogen atom or a methyl group.

R ⁴ to R ⁶ each independently represent a monovalent substituent, and R ⁴ may, for example, be a hydrogen atom or an alkyl group which may have a more substituent. Among them, preferred are a hydrogen atom, a methyl group, and an ethyl group. Further, R ⁵ and R ⁶ each independently include a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a more substituent, An alkoxy group which may have a substituent, an aryloxy group which may have a more substituent, an alkylsulfonyl group which may have a more substituent, an arylsulfonyl group which may have a more substituent, etc., among which is preferably A hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a more substituent, and an aryl group which may have a more substituent.

Here, examples of the substituent which may be contained include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a methyl group, an ethyl group, a phenyl group and the like.

A ¹ represents an oxygen atom, a sulfur atom or -N(R ²¹ )-, and X represents an oxygen atom, a sulfur atom or -N(R ²² )-. Here, R ²¹ and R ²² may, for example, be a hydrogen atom or an alkyl group which may have a substituent.

G ¹ represents a divalent organic group, and preferably an alkylene group which may have a substituent. More preferably, an alkylene group having a substituent of 1 to 20 carbon atoms, a cycloalkylene group having a carbon number of 3 to 20 which may have a substituent, and a substituent having a carbon number of 6 to 20 may be mentioned. An aromatic group or the like, which may have a linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and a carbon number The aromatic group which may have a substituent of 6 to 12 is preferable in terms of properties such as strength and developability.

Here, the substituent of G ¹ may preferably be a substituent other than a hydroxyl group and a substituent other than a hydroxyl group having a hetero atom bonded to a hydrogen atom (for example, an amine group, a thiol group, a carboxyl group, etc.). base.

The structural unit represented by the above formula (1) is preferably a case where A ¹ is an oxygen atom, a sulfur atom or -N(R ²¹ )-, and X is an oxygen atom, a sulfur atom or -N(R ²² )- , G ¹ is an alkylene group which may have a substituent, R ¹ and R ² are each a hydrogen atom, R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or an alkyl group, and R ⁵ and R ⁶ are each independently hydrogen. An atom, an alkoxycarbonyl group, an alkyl group or an aryl group, and R ²¹ and R ²² are each an alkyl group.

In the above formula (2), R ⁷ to R ⁹ each independently represent a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among them, R ⁷ and R ^{8 are} preferably hydrogen. The atom, R ^{9 is} preferably a hydrogen atom or a methyl group.

R ¹⁰ to R ¹² each independently represent a monovalent substituent, and specific examples of the substituent include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, and a cyano group. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a more substituent, an aryloxy group which may have a more substituent, and an alkylsulfonyl group which may have a more substituent Further, an arylsulfonyl group which may have a substituent, and the like, among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a more substituent, and an aryl group which may have a more substituent are preferable.

Here, the substituent which may be possessed may be similarly exemplified as the substituents exemplified in the general formula (1).

A ² represents an oxygen atom, a sulfur atom or -N(R ²¹ )-. Here, R ²¹ may, for example, be a hydrogen atom or an alkyl group which may have a substituent.

G ² represents a divalent organic group, and preferably an alkylene group which may have a substituent. Preferably, an alkylene group having a substituent of 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms which may have a substituent, and a substituent having a carbon number of 6 to 20 may be mentioned. An aromatic group or the like, which may have a linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and a carbon number The aromatic group which may have a substituent of 6 to 12 is preferable in terms of properties such as strength and developability.

Here, the substituent of G ² may preferably be a substituent other than a hydroxyl group and a substituent other than a hydroxyl group having a hetero atom to which a hydrogen atom is bonded (for example, an amine group, a thiol group, a carboxyl group, or the like).

When G ² has a substituent having a hetero atom bonded to a hydrogen atom other than a hydroxyl group, the onium salt compound may be used as a starting agent to be described later, and the storage stability may be lowered.

Y represents an oxygen atom, a sulfur atom, -N(R ²³ )- or a phenylene group which may have a substituent. Here, examples of R ²³ include a hydrogen atom, an alkyl group which may have a substituent, and the like.

The structural unit represented by the above formula (2) is preferably a case where R ¹⁰ is a hydrogen atom or an alkyl group, and R ¹¹ and R ¹² are each independently a hydrogen atom, an alkoxycarbonyl group, an alkyl group or an aryl group, and R ⁷ , R ⁸ is a hydrogen atom, R ⁹ is a hydrogen atom or a methyl group, A ² is an oxygen atom, a sulfur atom or -N(R ²¹ )-, and G ² is a straight group having a carbon number of 1 to 10 which may have a substituent. a chain or branched alkylene group, a cycloalkylene group having 3 to 10 carbon atoms which may have a substituent or an aromatic group having a carbon number of 6 to 12 which may have a substituent, and Y is an oxygen atom or a sulfur atom. , -N(R ²³ )- or a phenylene group which may have a substituent, and R ²¹ and R ²³ are each independently a hydrogen atom or an alkyl group which may have a substituent.

In the above formula (3), R ¹³ to R ¹⁵ each independently represent a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among them, R ¹³ and R ¹⁴ are preferably each. The hydrogen atom, R ^{15 is} preferably a hydrogen atom or a methyl group.

R ¹⁶ to R ²⁰ each independently represent a monovalent substituent, and examples of R ¹⁶ to R ²⁰ include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, and the like. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a more substituent, an alkylsulfonyl group which may have a more substituent, The arylsulfonyl group or the like which may have a more substituent is preferably a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a more substituent. The substituent which can be introduced can be exemplified by the substituents exemplified in the general formula (1).

A ³ represents an oxygen atom, a sulfur atom or -N(R ²¹ )-, and Z represents an oxygen atom, a sulfur atom or -N(R ²² )-. R ²¹ and R ²² may be the same as those in the formula (1).

G ³ represents a divalent organic group, and preferably an alkylene group which may have a substituent. Preferably, an alkylene group having a substituent of 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms which may have a substituent, and a substituent having a carbon number of 6 to 20 may be mentioned. Aromatic group or the like, wherein the carbon number which may have a substituent is 1 to 10 a linear or branched alkylene group, a cycloalkylene group having a substituent of 3 to 10 carbon atoms, an aromatic group having a carbon number of 6 to 12 and having a substituent, and strength, developability, etc. It is better in terms of performance.

Here, examples of the substituent of G ³ include a hydroxyl group and a substituent other than a substituent (for example, an amine group, a thiol group, or a carboxyl group) having a hetero atom bonded to a hydrogen atom other than a hydroxyl group.

The structural unit represented by the above formula (3) is preferably a case where R ¹³ and R ¹⁴ are each a hydrogen atom, R ¹⁵ is a hydrogen atom or a methyl group, and R ¹⁶ to R ²⁰ are a hydrogen atom or an alkoxycarbonyl group. An alkyl group which may have a substituent or an aryl group which may have a substituent, A ³ is an oxygen atom, a sulfur atom or -N(R ²¹ )-, and Z is an oxygen atom, a sulfur atom or -N(R ²² )-, R ²¹ and R ²² are an alkyl group, and G ³ is a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, and a cycloalkylene group having a carbon number of 3 to 10 which may have a substituent. An aromatic group which may have a substituent or a carbon number of 6 to 12.

The synthesis of the polymer compound in which the above-mentioned "structural unit (first structural unit) represented by any one of the general formulae (1) to (3) is contained in the above-mentioned "unsaturated double bond" can be formed by a known method, for example, Japan The paragraph number of the patent publication No. 2003-262958 is carried out by the synthesis method described in the paragraphs [0027] to [0057]. Among them, it is preferred to carry out the synthesis method 1) in the above publication.

The above "polymer compound having an unsaturated double bond" is preferred The resin obtained by the synthesis method of the following [1] or [2].

[1] A base is allowed to act on a polymer synthesized by using a compound represented by the following formula (5) as one of the copolymerization components, and a proton is removed to separate L, thereby obtaining the above formula. (1) A method of the desired polymer compound of the structural unit represented.

In the above formula (5), L represents an anionic leaving group, and preferably a halogen atom, an alkyl group or an arylsulfonyloxy group is exemplified. R ³ to R ⁶ , A ¹ , G ¹ and X have the same meanings as in the above formula (1).

Any of an inorganic compound and an organic compound can be used as the base for causing the detachment reaction. Further, the details and preferred aspects of the above method are described in paragraphs [0028] to [0033] of JP-A-2003-262958.

Preferred examples of the inorganic compound base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, and potassium hydrogencarbonate. Examples of the organic compound base include sodium methoxide and ethanol. A metal alkoxide such as sodium or potassium t-butoxide; or an organic amine compound such as triethylamine, pyridine or diisopropylethylamine.

[2] A polymer synthesized by using a compound represented by the following formula (6) as a copolymerization component, which causes a specific functional group to undergo a detachment reaction by alkaline treatment, and removes X ¹ to obtain a radical (radical) a method of reactive groups.

In the above formula (6), A ⁴ represents an oxygen atom, a sulfur atom or -N(R ²⁷ )-, and A ⁵ represents an oxygen atom, a sulfur atom or -NR ²⁸ -, R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ each independently represent hydrogen or a monovalent organic group, X ¹ represents a group removed by a desorption reaction, and G ⁴ represents an organic bonding group. n represents an integer of 1 to 10.

In the formula (6), A ^{4 is} preferably an oxygen atom, and A ^{5 is} preferably an oxygen atom. Further, R ^{24 is} preferably a methyl group, R ²⁵ , R ²⁶ , R ²⁹ and R ^{30 are} preferably a hydrogen atom, and R ^{31 is} preferably a methyl group or a hydrogen atom. Further, X ^{1 is} preferably a bromine atom, and G ^{4 is} preferably an ethylene group.

The details and preferred aspects of the above method are described in detail in Japanese Laid-Open Patent Publication No. 2003-335814.

The polymer compound described in the above-mentioned Japanese Patent Publication No. 2003-335814, specifically, for example, (i) a polyethylene-based polymer compound, (ii) Polyurethane-based polymer compound, (iii) polyurea-based polymer compound, and (iv) poly(urethane-urea) system a polymer compound, (v) a polyester-based polymer compound, (vi) a polyamine-based polymer compound, (vii) an acetal-modified polyvinyl alcohol-based polymer compound, and a polymer Each of the specific compounds obtained is described.

Specific examples of the compound represented by the above formula (5) include the following compounds (M-1) to (M-12), but the present invention is not limited to these compounds.

The compounds represented by the above formula (6) include the following compounds (i-1) to ((i-52), but the present invention is not limited to these compounds.

The resin in the composition of the present invention preferably has at least one acid group selected from the group consisting of COOH, SO ₃ H, PO ₃ H ₂ , OSO ₃ H, and OPO ₂ H ₂ from the viewpoint of performing alkali development. . Further, the acid value of the resin in the present invention is preferably from 5 mgKOH/g to 70 mgKOH/g, more preferably from 7.5 mgKOH/g to 60 mgKOH/g, further preferably from 10 mgKOH/g. A range of 50 mg KOH/g. When the acid value exceeds 70 mgKOH/g, pattern peeling tends to occur during development. Further, when the acid value is less than 5 mgKOH/g, the alkali developability is lowered.

In particular, the acid group of the resin in the composition of the present invention preferably has a second structural unit represented by the following formula (4). This is in the fine pattern It is effective in terms of residue suppression and rectangular pattern formability.

In the above formula (4), R _A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R _B represents a divalent bonding group.

The above R _{A is} preferably a hydrogen atom or a methyl group.

The above R _{B may} be a divalent bonding group, and examples thereof include a substituted alkylene group having 1 to 12 carbon atoms, and -U-R _C -V- (wherein U and V are independently and independently Represents a single bond or an alkylene group having a carbon number of 1 to 3, Rc represents a cyclohexyl ring, a benzene ring or a naphthalene ring which may be substituted, or -R _D -X-R _E - (wherein R _D and R _E Respectively represent a substituted alkylene group having a carbon number of 1 to 10, a substituted benzene ring or a naphthalene ring, and X represents an ester bond, a guanamine bond, a urethane bond, an ether bond, a thioether. A bond, a carbonate bond, a urea bond or a quinone bond, etc., among them, R _B is preferably a divalent bond group having a carbon number of 1 to 6.

In the present invention, the acid value can be calculated, for example, from the average content of the acid groups in the resin molecule. Further, a resin having a desired acid value can be obtained by changing the content of a monomer unit containing an acid group constituting the resin.

The resin of the present invention is preferably a resin obtained by copolymerizing a component containing a guanamine bond in a resin from the viewpoint of developing residue of the unexposed portion.

In order to suppress pattern collapse due to overheating in post bake, the resin which may be contained in the composition of the present invention is preferably the following structure The ratio of the second structural unit represented by the above formula (4), which is 1.5 times or 1.5 times or more (mole ratio), is represented by any one of the above formulas (1) to (3). 1 structural unit. From the viewpoint of the sclerosing property, the above-mentioned general formula (1) to (3) is more preferably 2.0 or more times the ratio of the second structural unit represented by the above formula (4). The first structural unit shown is preferably 3.0 times or more. In addition, the resin which can be contained in the composition of the present invention is preferably selected from the above range in a range of 35 mol% or more and 95 mol% or less in one molecule in terms of improving the hardenability and reducing the development residue. The compound of at least one of the first structural units represented by any one of the general formulae (1) to (3) is more preferably 37 mol% or more and 90 mol% or less, further preferably more than 90 mol%. A range equal to 40 mol% and less than or equal to 85 mol%. In particular, the resin containing the structural unit represented by the above formula (1) in a range of 40 mol% or more and 85 mol% or less in one molecule is preferable.

Further, from the viewpoint of suppressing pattern peeling and developability at the time of development, the weight average molecular weight of the resin in the composition of the present invention is preferably 30,000 to 300,000, more preferably 40,000 to 250,000, still more preferably 50,000. ~200,000, especially good is 50,000~100,000.

Further, the weight average molecular weight of the above resin can be measured, for example, by Gel Permeation Chromatography (GPC).

The content of the resin in the colored photosensitive composition of the present invention relative to the total solid content is from the viewpoint of suppressing pattern peeling and suppressing development residue. It is preferably 0.01 wt% to 20 wt%, more preferably 1 wt% to 10 wt%, still more preferably 3 wt% to 7 wt%.

(D) Polymeric compound

The composition of the present invention preferably contains a polymerizable compound (polymerizable monomer). The polymerizable monomer is preferably a compound having a boiling point of 100 ° C or more at normal pressure and having at least one ethylenically unsaturated group capable of undergoing addition polymerization.

Examples of the above polymerizable monomer include polyethyleneglycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Monofunctional acrylate or methacrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate ( Neopentylglycol di(meth)acrylate), pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(methyl) ) acrylate, hexanediol (meth) acrylate, trimethylolpropane tris(propylene methoxypropyl) ether, tris(propylene methoxyethyl) isocyanurate, glycerol or trishydroxyl a (meth) acrylate obtained by adding (meth) acrylate to ethylene oxide or propylene oxide after addition of an ethylene oxide or a propylene oxide, and Japanese Patent Publication No. Sho 48-41708, Japanese Patent Propylene described in each of the publications of Japanese Patent Laid-Open Publication No. SHO-50-63193 Amino acrylates, epoxies and epoxies described in Japanese Laid-Open Patent Publication No. SHO-49-43183, Japanese Patent Publication No. SHO-49-43191, and Japanese Patent Publication No. Sho 52-30490 Methyl)acrylic acid The product is a polyfunctional acrylate or methacrylate such as an epoxy acrylate and a mixture of these (meth) acrylates. Further, Japanese Unexamined Association Publication No. Vol. 20, No. 7 on pages 300 to 308 is described as a photocurable monomer and an oligomeric polymerizable monomer.

In addition to the above polymerizable monomer, a carboxyl group-containing radical polymerizable monomer of the following general formulae (III-1) and (III-2) can be suitably used. Further, in the general formulae (III-1) and (III-2), when T or G is an oxyalkylene group, the terminal on the carbon atom side is bonded to R, X and W.

R: , X: , T: -CH ₂ -, -OCH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ CH ₂ - Z: -O-, G: -CH ₂ -, -OCH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ CH ₂ -

In the above formula (III-1), n is 0 to 14 and m is 1 to 8. In the above formula (III-2), W is the same R or X as the formula (III-1), and among 6 pieces of W, three or more of W are R. p is 0~14, and q is 1~8. A plurality of R, X, T, and G existing in one molecule may be the same or different.

Specific examples of the radical polymerizable monomer represented by the above formulas (III-1) and (III-2) include the monomers shown below.

The content of the polymerizable monomer in the coloring photosensitive composition is preferably from 10% by weight to 45% by weight, more preferably from 12% by weight to 40% by weight, based on the total solid content of the composition. Good is 15 wt% ~ 35 wt%. When the content is in the above range, the sufficient degree of curing and the elution property of the unexposed portion can be maintained, and the degree of curing of the exposed portion can be sufficiently maintained, and the elution property of the unexposed portion can be prevented from being remarkably lowered.

(E) Photopolymerization initiator

The colored photosensitive composition of the present invention preferably contains at least one of photopolymerization initiators. The photopolymerization initiator is not particularly limited as long as it polymerizes a polymerizable monomer, and is preferably selected from the viewpoints of characteristics, initial efficiency, absorption wavelength, availability, cost, and the like.

The photopolymerization initiator may be exemplified by at least one active halide selected from the group consisting of halomethyl oxadiazole compounds and halomethyl-s-triazine compounds. Base-substituted coumarin compound, lophine dimer, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron Complex compounds and salts thereof, lanthanide compounds and the like.

Examples of the active halide such as a halomethyl oxadiazole include a 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound described in Japanese Patent Publication No. Sho 57-6096, or 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole , 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, and the like.

The photopolymerization initiator of the halomethyl-triazine-based compound is exemplified by the vinyl halomethyl-s-triazine compound described in Japanese Patent Publication No. Sho 59-1281, and Japanese Patent Laid-Open No. 53-133428 2-(naphthalen-1-yl)-4,6-bis(halomethyl)-s-triazine compound and 4-(p-aminophenyl)-2,6-bis(halomethyl) described in the publication )-s-triazine compound.

Other examples include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,6-bis(trichloromethyl)-4-(3,4- Methylenedioxyphenyl)-1,3,5-triazine, 2,6-bis(trichloromethyl)-4-(4-methoxyphenyl)-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine, 2-trichloromethyl- 4-Amino-6-p-methoxystyryl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4- Methoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxy-naphthalen-1-yl)-4,6-bis (three Chloromethyl)-s-triazine, 2-(4-butoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-[4-(2-A Oxyethyl)-naphthalen-1-yl]-4,6-bis(trichloromethyl)-s-triazine, 2-[4-(2-ethoxyethyl)-naphthalen-1-yl] -4,6-bis(trichloromethyl)-s-triazine, 2-[4-(2-butoxyethyl)-phenol-1-yl]-4,6-bis(trichloromethyl) -s-triazine, 2-(2-methoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(6-methoxy-5-methyl -naphthalen-2-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(6-methoxy-naphthalen-2-yl)-4,6-bis(trichloromethyl) )-s-triazine, 2-(5-methoxy-naphthalene- 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4,7-dimethoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl) )-s-triazine, 2-(6-ethoxy-naphthalen-2-yl)-4,6-bis(trichloromethyl)s-triazine, 2-(4,5-dimethoxy-naphthalene -1-yl)-4,6-bis(trichloromethyl)s-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis ( Trichloromethyl)-s-triazine, 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-all Pyrazine, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-methyl-p-N,N- Bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-(p-N-chloroethylaminophenyl)-2,6-bis (three Chloromethyl)-s-triazine, 4-(p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-[N,N - bis(phenyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-bis ( Trichloromethyl)-s-triazine, 4-[p-N-(p-methoxy Phenyl) Carbonylaminophenyl]2,6-bis(trichloromethyl)-s-triazine, 4-[inter-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-double (trichloromethyl)-s-triazine, 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)- Triazine, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-fluoro -N-N-N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-bromo-p-N,N-bis ( Ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)amine Phenyl-2,6-bis(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6- Bis(trichloromethyl)-s-triazine, 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine , 4-[o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N,N -bis(chloroethyl)aminophenyl] -2,6-bis(trichloromethyl)-s-triazine, 4-[m-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl) )-s-triazine, 4-[m-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-fluoro -N-N-N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-(m-bromo-p-N-ethoxycarbonylmethylamine) Phenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloro) Methyl)-s-triazine, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(o-bromo -p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(o-chloro-p-N-ethoxycarbonylmethylaminobenzene -2,6-bis(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethane) -s-triazine, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(m-chloro-p-N- Chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-chloroethylaminophenyl)-2,6-di(three Chloromethyl)-s-triazine, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(o-chloro-pair N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-double (Trichloromethyl)-s-triazine and the like.

In addition, it can also be used effectively: TAZ series manufactured by MIDORI Chemical Co., Ltd., TAL-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123; PANCHIM The company's T series, T-OMS, T-BMP, T-R, T-B; Ciba Specialty Chemicals' Irgacure series and Darocure series, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, Darocure 11734; 4'-bis(diethylamino)-benzophenone, 2-(O-benzylidenehydrazide)-1-[4-(benzene Thio)phenyl]-1,2-octanedione, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indole Zyrid-3-yl]ethanone, 2-benzyl-2-dimethylamino-4-morpholinyl phenylbutanone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimerization , 2-(p-dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimerization , 2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer, benzoin isopropylether, and the like.

Among the above initiators, preferred are lanthanoid compounds, and most preferred is 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-octyl Diketone, 1-(O-ethylhydrazinyl)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone. Commercial products of the above-mentioned best oxime-based photopolymerization initiators include CGI-124 and CGI-242 (the above is manufactured by Ciba Specialty Chemicals Co., Ltd.).

In the composition of the present invention, other known photopolymerization initiators may be used in addition to the above photopolymerization initiator.

Specifically, the vicinal polyketolaldonyl compound disclosed in the specification of U.S. Patent No. 2,367,660, the α-carbonyl compound disclosed in the specification of U.S. Patent Nos. 2,367,661 and 2,367,670, U.S. Patent No. 2,448,828 The alpha-hydrocarbon-substituted aromatic alcohol ketone compound disclosed in the specification of the specification disclosed in the specification, U.S. Patent No. 2,722,512, the polynuclear ruthenium compound disclosed in the specification of U.S. Patent Nos. 3,046,127 and 2,951,758, The combination of the triallyl imidazole dimer/p-aminophenyl ketone disclosed in the specification of Japanese Patent No. 3,549,367, the benzothiazole compound/trihalide disclosed in Japanese Patent Publication No. Sho 51-48516 A methyl-s-triazine-based compound or the like.

A sensitizer or a light stabilizer may be further used in combination with these photopolymerization initiators.

Specific examples of the above sensitizer or light stabilizer include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, and 9 - 9-anthrone, 2-bromo-9-fluorenone, 2-ethyl-9-fluorenone, 9,10-fluorene, 2-ethyl-9,10-fluorene, 2- Tributyl-9,10-蒽醌, 2,6- Dichloro-9,10-fluorene, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone (thioxanthone), 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzil, dibenzalacetone, P-(dimethylamino)phenylstyryl ketone, p-(dimethylamino)phenyl-p-methylstyrylone, benzophenone, p-(dimethylamino)benzol Ketone (or Michler's ketone), p-(diethylamino)benzophenone, benzophenone, etc., or a benzothiazole compound described in Japanese Patent Publication No. Sho 51-48516 , or TINUVIN 1130, TINUVIN 400, etc.

The amount of the above photopolymerization initiator to be used is preferably from 1.0 wt% to 40.0 wt%, more preferably from 2.5 wt% to 30.0 wt%, particularly preferably from 5.0 wt% to 20.0, based on the total solid content. Wt%. When the amount of the photopolymerization initiator used is less than 1.0% by weight, it is difficult to carry out polymerization, and if it exceeds 40.0% by weight, the polymerization rate is increased, but the molecular weight is lowered and the film strength is weakened.

(F) solvent

The colored photosensitive composition of the present invention preferably contains a solvent. When the solvent satisfies the solubility and coatability of the composition, it is basically not particularly limited, and it is particularly preferable to select the dye, the solubility of the binder, the coatability, and the safety.

The solvent used in the preparation of the composition of the present invention is preferably an ester such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyrate. Ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl oxyacetate, ethyl oxyacetate, Butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, Ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2 Methyloxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropanoate, 2-oxy-2-methylpropane Ethyl acetate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvic acid Propyl ester, ethyl acetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene Alcohol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate (ethylene glycol) Methyl ether acetate), ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, two Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol diethyl ether acetate, propylene glycol ethyl ether An acid ester or the like; a ketone such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone or the like; an aromatic hydrocarbon such as toluene or xylene.

Among these solvents, more preferred are methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethicone. Ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate (diethylene glycol monoethyl ether acetate), Butyl carbitol acetate (diethylene glycol monobutyl ether acetate), propylene glycol methyl ether, propylene glycol methyl ether acetate, and the like.

(G) Other additives

In the composition of the present invention, various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, a coagulation inhibitor, and the like may be blended as needed.

Specific examples of such additives include fillers such as glass and alumina; and other resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyacrylic acid fluoroalkyl ester. Polymer compound; surfactant such as nonionic, cationic or anionic; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N -(2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-amino Propyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl) Ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyl An adhesion promoter such as trimethoxy decane; an antioxidant such as 2,2-thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol; 2-(3) - the first An ultraviolet absorber such as tributyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or an alkoxybenzophenone; and an aggregation inhibitor such as sodium polyacrylate.

Further, when the alkali solubility of the unexposed portion is promoted to further improve the developability of the composition of the present invention, an organic carboxylic acid may be added to the composition of the present invention, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1,000 or less. . Specific examples thereof include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid, and the like. Aliphatic monocarboxylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid Pimelic acid), suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, Aliphatic dicarboxylic acid such as dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, methyl citraconic acid; 1,2,3-propane tricarboxylic acid (tricarballylic acid) ), aconitic acid, fatty acid tricarboxylic acid such as camphoronic acid; benzoic acid, toluic acid, cumic acid, 3,4-dimethylbenzene An aromatic monocarboxylic acid such as hemellitic acid or 3,5-dimethylbenzoic acid; phthalic acid, isophthalic acid, terephthalic acid, and benzoic acid Aromatic polycarboxylic acid such as trimellitic acid, trimesic acid, 1,2,3,5-benzenetetracarboxylic acid, pyromellitic acid ; phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, sub-cinnamon Cinnamylidene acetic acid, coumaric acid Acid), other carboxylic acids such as umbellic acid.

<Color filter and method of manufacturing the same>

The color filter of the present invention is formed by using the above-described colored photosensitive composition of the present invention. Specifically, the colored photosensitive composition of the present invention is applied onto a support by a coating method such as spin coating, cast coating, or roll coating to form a colored photosensitive composition layer. Then, the colored photosensitive composition layer formed on the support is exposed through a predetermined mask pattern, and then developed with a developer. Thereby, a colored pattern is formed on the support, whereby a color filter can be manufactured. Further, the method of manufacturing the color filter of the present invention may include a step of hardening the resist pattern by heating and/or exposure as needed.

The radiation used at this time is particularly preferably an ultraviolet ray such as g-ray, h-ray or i-ray.

Examples of the support include a soda glass used in a liquid crystal display device, a borosilicate glass (Pyrex (R) glass, etc.), a quartz glass, and a support in which a transparent conductive film is adhered to the glass. Or a photoelectric conversion element substrate used in an imaging element or the like, for example, a germanium substrate or the like, or a complementary metal oxide semiconductor (CMOS) or the like. These supports also have a black stripe that separates the pixels.

Further, an undercoat layer may be provided on the support as needed in order to improve the adhesion to the upper layer, prevent the substance from diffusing, or flatten the surface of the substrate.

The developer used in the method for producing a color filter of the present invention is such that it can dissolve the composition of the present invention and does not dissolve the radiation irradiation portion. For the composition, any developer can be used. Specifically, a combination of various organic solvents or an aqueous alkaline solution can be used.

The organic solvent may, for example, be the above solvent used in the preparation of the composition of the present invention.

The alkaline aqueous solution can be used, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, hydrogen. Alkaline compounds such as tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene are oxidized to a concentration of 0.001% by weight to 10% by weight. %, preferably an alkaline aqueous solution obtained by dissolving in an amount of 0.01% by weight to 1% by weight. Further, when a developer containing the above aqueous alkaline solution is used, it is usually washed with water after development.

Further, the color filter of the present invention can be suitably used for a solid-state image sensor such as a CCD, and can be suitably used in a high-resolution CCD element or CMOS element of more than 5 million pixels. The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion constituting each pixel of the CCD and a microlens for collecting light.

[Examples]

Hereinafter, the present invention will be specifically described by the examples, but the present invention is not limited to the following examples as long as they do not deviate from the gist of the invention. In addition, unless otherwise indicated, "part" is a weight basis.

(Example 1)

1) Preparation of primer solution

The photoresist is prepared by mixing and dissolving the following materials:

[40% PGMEA solution of benzyl methacrylate/methacrylic acid/-2-hydroxyethyl methacrylate copolymer (Morby = 60:22:18)]

2) Fabrication of a wafer substrate (support) with an undercoat layer

A 6 inch wafer was placed in an oven and heat treated at 200 ° C for 30 minutes. Then, the photoresist was applied onto the wafer to have a dry film thickness of 1 μm, and further dried in an oven at 220 ° C for 1 hour to form an undercoat layer, thereby obtaining a primer layer. Wafer substrate.

3) Preparation of coloring photosensitive composition (constitution of the present invention)

The compound of the following composition A-1 was mixed and dissolved to prepare a colored photosensitive resin composition A-1. Further, dipentaerythritol hexaacrylate is purified by using a column beforehand.

<composition A-1>

4) Forced time-lapse of coloring photosensitive composition (age) The forced time-lapse test was carried out by allowing the colored photosensitive resin composition A-1 prepared in the above 3) to stand in an oven at 40 ° C for 7 days.

5) Coating, Exposure, and Development of Coloring Photosensitive Composition The composition obtained in the above 4) is applied onto the undercoat layer of the undercoat-coated ruthenium wafer substrate obtained in the above 2) to form Photocurable coating film. Further, heat treatment (prebake) was performed for 120 seconds using a hot plate at 100 ° C so that the dried film thickness of the coating film was 0.5 μm. Then, using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon), an island pattern mask having a pattern of 1.2 μm square was used at a wavelength of 365 nm at 100 mJ/ cm ² ~ 2500 mJ / exposure amount of 50 mJ / cm ² and changes the irradiation units in the range of cm ^2. Thereafter, the tantalum wafer substrate on which the irradiated coating film was formed was placed on a horizontal rotating table of a Spin Shower developing machine (DW-30 type; manufactured by Chemitronics), using CD-2000 ( Fuji Film Electronics Materials (manufactured by Fuji Film Electronics Materials Co., Ltd.) performed puddle development at 23 ° C for 60 seconds to form a colored pattern on the tantalum wafer substrate.

The germanium wafer substrate on which the colored pattern is formed is fixed to the horizontal rotating platform by a vacuum chuck method, and the germanium wafer substrate is rotated at a rotation speed of 50 rpm by a rotating device while being rotated from the center of the rotation The pure water was supplied in a shower form by a nozzle (nozzle), and rinsed, and then spray-dried to obtain a color filter.

6) Evaluation of pattern adhesion after development The minimum amount of exposure (mJ/cm ² ) necessary for confirming the residual of all the patterns was confirmed by observing the color filter obtained by the above with an optical microscope at 100 times. .

7) Evaluation of developability of unexposed parts The development of the unexposed portion was evaluated by using a scanning electron microscope (SEM), and the developed pattern was observed at 10,000 times, and evaluated according to the following evaluation criteria.

- Evaluation criteria -

◎: The unexposed portion can be completely removed.

○: There is a slight residue, but it is within the allowable range.

×: There are many residues and it is not allowed.

(Examples 2 to 10, Comparative Examples 1 to 4)

In Example 1, the type and amount (content) of the thermal polymerization inhibitor using the coloring agent, the resin, and the 0.1% cyclohexanone solution in the composition A-1 were changed to the coloring shown in Table 1 below. A color filter was produced in the same manner as in Example 1 except that the coloring photosensitive composition A-2 to A-13 formed of the agent and the resin was used instead of the coloring photosensitive composition A-1. The minimum exposure amount (mJ/cm ² ) necessary for the pattern adhesion after development was evaluated, and the developability of the unexposed portion was evaluated. In addition, each content in Table 1 is a value which opposes all the components (total solid content) after solvent removal.

(Examples 11 to 12, Comparative Examples 5 to 6)

In the first embodiment, in accordance with the description of Table 2, the colored photosensitive compositions A-14 to A-17 having the compositions shown below were used instead of the colored photosensitive composition A-1, and In the same manner as in Example 1, a color filter was produced and evaluated. The results are shown in Table 2.

<Composition A-14>

<Composition A-15>

<Composition A-16>

<Composition A-17>

According to Tables 1 and 2, it is understood that the colored pattern formed by using the colored photosensitive composition of the present invention exhibits good adhesion with a low exposure amount even after passing through room temperature or room temperature, and is not exposed. The developability is also good.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (10)

A coloring photosensitive composition for a solid-state image sensor, characterized in that the coloring photosensitive composition contains 50% by weight or more and 80% by weight or less of a coloring agent, and greater than or equal to the total solid content. 1.0 to 10 - ^{5 by} weight and less than or equal to 1.0 × 10 ^{-3 by} weight of a thermal polymerization inhibitor of a phenolic compound. The colored photosensitive composition for a solid-state image sensor according to claim 1, wherein the coloring agent is a dye soluble in an organic solvent. The colored photosensitive composition for a solid-state image sensor according to claim 1, wherein the resin further comprises a resin containing an unsaturated double bond, which is selected from the following general formulae (1) to (3) At least one structural unit and acid group in the first structural unit group represented by any one of the formulas, and at least one structural unit selected from the second structural unit group represented by the following general formula (4), and the above 1 the molar ratio of the structural unit to the second structural unit is 1.5 times or more, In the above formulae (1) to (3), A ¹ , A ² and A ³ each independently represent an oxygen atom, a sulfur atom or -N(R ²¹ )-, and R ²¹ represents a hydrogen atom or may have a substituent. Alkyl; G ¹ , G ² and G ³ each independently represent a divalent organic group; X and Z each independently represent an oxygen atom, a sulfur atom or -N(R ²² )-, and R ²² represents a substitutable Alkyl group; Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent or -N(R ²³ )-, and R ²³ represents a hydrogen atom or an alkyl group which may have a substituent; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ And R ²⁰ each independently represents a monovalent substituent; and in the above formula (4), R _A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R _B represents a divalent bonding group. The colored photosensitive composition for a solid-state image sensor according to claim 3, wherein the resin has a weight average molecular weight of 30,000 or more and 300,000 or less. The colored photosensitive composition for a solid-state image sensor according to claim 1, which further contains a ruthenium initiator. The colored photosensitive composition for a solid-state image sensor according to the first aspect of the invention, wherein the photopolymerization initiator is further contained in an amount of 1.0% by weight to 40.0% by weight based on the total solid content. The colored photosensitive composition for a solid-state image sensor according to claim 1, wherein the coloring agent is a phthalocyanine dye. The colored photosensitive composition for a solid-state image sensor according to the first aspect of the invention, wherein the amount of the thermal polymerization inhibitor of the phenolic compound is 3.0 × 10 or more, based on the total solid content. ^-5 wt% and less than or equal to 5.0 x 10 ^-4 wt%. A method of producing a color filter for a solid-state image sensor, comprising: applying a coloring photosensitive composition for a solid-state image sensor according to any one of claims 1 to 8 to a support; The step of forming a colored photosensitive composition layer; and exposing and developing the colored photosensitive composition layer by a photomask to form a pattern on the support. A color filter for a solid-state image pickup device, which is used for a solid-state image pickup device according to any one of claims 1 to 8. It is formed by coloring a photosensitive composition.