JP2010224308A - Color filter and manufacturing method thereof - Google Patents

Abstract

【選択図】なしProvided is a color filter having rectangular square pixels with small roundness at the corners of each pixel on the filter surface, and having a rectangular shape with small roundness at the corners of the square pixels. .
A support having a plurality of light receiving elements, a light transmittance of light having a wavelength of 365 nm, including a pigment and a compound represented by the following general formula (I), provided on the light receiving element forming surface side of the support. Is 0.1% or more and 10.0% or less, more preferably 0.1% or more and 5.0% or less, and a colored pixel having a pattern size of 0.5 μm or more and 1.2 μm or less [R. ^{1 to} R ² : H, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (does not simultaneously represent H. R ¹ and R ² may form a cyclic amino group together with N) R ³ : electron withdrawing group; R ⁴ : electron withdrawing group].

[Selection figure] None

Description

  The present invention relates to a color filter containing a pigment as a colorant and a method for producing the same.

  In recent years, with the miniaturization of pixels of solid-state image pickup devices, pattern formation by exposure and development, that is, pattern formation by so-called photolithographic method, spectral characteristics and pattern formation of color filters in response to the demand for miniaturization and thinning of color filters It is becoming difficult to balance sex.

  A color filter for a solid-state imaging device is required to have a high number of pixels for the purpose of improving the resolution of a solid-state imaging device such as a CCD or CMOS. For example, the number of pixels of a digital camera, which was about 400,000 pixels at the time of 1995, has reached 3 million pixels in 2000 and more than 10 million pixels in recent years. With the increase in the number of pixels, the size of one pixel of the color filter, which was about 5 μm in the late 1990s, has recently been reduced to 1.5 μm or less. As the pixel size becomes smaller in this way, a technical problem regarding the shape of a pixel formed by the photolithography method has become apparent.

  That is, when manufacturing a color filter using a photolithographic method, generally, a pixel pattern is exposed through a photomask on a photoresist film coated and formed on a substrate and colored with a dispersed pigment, and a pixel is formed by alkali development. However, as the pixel size becomes smaller, the pattern edges and corners (rounds) become rounder, and the ratio of the area where gaps are formed between pixels increases. In recent years, many pixel shapes have been adopted in CCDs and the like. It is difficult to form square pixels. As the pixel size becomes smaller, the shape of the entire pixel itself becomes closer to a round shape due to the roundness of edges and corners of the pattern, and image characteristics such as color balance and contrast when an image is displayed as a device are degraded.

  Further, with the thinning of the solid-state imaging device, the coloring pattern has also been made thinner, and for example, a thickness of 1 μm or less has been demanded. As the film thickness decreases, the relative amount of pigments and other colorants in the film increases. On the other hand, the amount of components other than colorants that contribute to photolithographic properties tends to decrease relatively. This is also one of the factors that make it difficult to form square pixels.

  In relation to the above, as a method for eliminating the rounding of the shape of the fine pattern, a technique for forming a pattern by a dry etching method is disclosed (for example, see Patent Documents 1 to 4).

JP 2008-77038 A JP 2008-122890 A JP 2008-122891 A JP 2008-129430 A

  Although pattern formation technology by dry etching is being studied, the photolithographic method is suitable for the production of color filters for large screens and high-definition color displays with high positional accuracy of the formed pattern, and the manufacturing cost. However, since it is advantageous also in terms of manufacturability, a method for producing a color filter by a photolithography method is still mainstream. For this reason, a technique for forming a fine pattern with higher accuracy than before is expected by a photolithography method that has been widely used conventionally.

  The present invention has been made in view of the above, and has a square square pixel in which the roundness of the corner of each pixel on the filter surface is small, and the roundness of the corner of the square pixel is also small. Color filters formed in a rectangular shape and line width and other shape variations at low illuminance (especially low illuminance of 95% or less of high illuminance) are kept small, development residue is small, and fine (0.5 μm to 1.2 μm) It is an object of the present invention to provide a color filter manufacturing method capable of forming a square pixel pattern with high resolution while maintaining the object.

Specific means for achieving the above object are as follows.
<1> A support having a plurality of light receiving elements, and a light having a wavelength of 365 nm, including a pigment and a compound represented by the following general formula (I), provided on the support (preferably on the light receiving element forming surface side) A colored pixel having a transmittance of 0.1% to 10.0% and a pattern size of 0.5 μm to 1.2 μm.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ¹ and R ² may be the same or different from each other, but do not represent a hydrogen atom at the same time, and R ¹ and R ² may form a cyclic amino group together with a nitrogen atom. R ³ and R ⁴ each independently represents an electron withdrawing group.

  <2> A support having a plurality of light-receiving elements (preferably the light-receiving element), comprising a photosensitive coloring composition containing at least a compound represented by a pigment, a polymerizable monomer, a photopolymerization initiator, and the general formula (I). The coated layer formed by coating is exposed to light and developed, whereby the transmittance of light having a wavelength of 365 nm is 0.1% to 10.0% and the pattern size is 0.5 μm. This is a method for producing a color filter for forming a colored pattern having a size of 1.2 μm or less.

  <3> The color filter according to <1>, wherein a transmittance of light having a wavelength of 365 nm is 0.1% to 5.0%.

  <4> The method for producing a color filter according to <2>, wherein the transmittance of light having a wavelength of 365 nm is 0.1% to 5.0%.

  <5> The content ratio of the photopolymerization initiator is in the range of 1.5 to 10% by mass with respect to the total solid content of the photosensitive coloring composition, <2> or <4> The manufacturing method of the color filter as described in above.

According to the present invention, a color filter having a rectangular square pixel with a small roundness at the corner of each pixel on the filter surface and a rectangular shape with a small roundness at the corner of the square pixel. Can be provided. Also,
According to the present invention, the shape variation at low illuminance (particularly low illuminance of 95% or less of high illuminance) is suppressed, the development residue is small, and the resolution is fine (pattern size of 0.5 μm or more and 1.2 μm or less). It is possible to provide a color filter manufacturing method capable of forming a highly square pixel pattern.

In the cross section of a coloring pattern, it is a conceptual diagram for demonstrating the shape at the time of (a) reverse taper, and (b) forward taper.

Hereinafter, the color filter of the present invention and the manufacturing method thereof will be described in detail.
The color filter of the present invention is a color filter of a solid-state imaging device in which a color filter (colored pixel) is disposed on a support having a plurality of light receiving elements (for example, on the light receiving element forming surface side). In addition, the transmittance of light having a wavelength of 365 nm is 0.1% to 10.0%, preferably 0.1% to 5.0%, and the pattern size is 0.5 μm to 1. It is configured by providing colored pixels having a size of 2 μm or less.

  In the present invention, the color filter contains an ultraviolet absorber having a specific structure, and the transmittance of light having a wavelength of 365 nm is 0.1% to 10.0% (preferably 0.1% to 5.0%). In other words, patterning with a pattern size of 0.5 μm or more and 1.2 μm or less by photolithography is performed in the presence of an ultraviolet absorber having a specific structure, and the transmittance of light with a wavelength of 365 nm is 10.0% or less (preferably Since the variation in shape is suppressed to a small size while being a fine pattern size of 0.5 μm or more and 1.2 μm or less, each pixel observed from the normal direction of the filter surface A color filter having a rectangular square shape with a small rounded corner portion and a rectangular cross section with a small rounded corner portion is obtained.

-Support-
Examples of the support include a photoelectric conversion element substrate used for an imaging element or the like, such as a silicon substrate, a complementary metal oxide semiconductor (CMOS) substrate, or the like. It can also be used for backside illumination elements. Etc. In CMOS substrate, colored pixels are preferably formed on the protective film formed on the CMOS sensor, as the protective film SiN, SiON, and inorganic film such as _{SiO 2.} There are no particular restrictions on the inorganic film. Furthermore, it is conceivable that the protective film in the pixel formation region functions as an inner lens so that the surface has irregularities, and the protective film is an organic film such as polyimide. In the case where the protective film is an organic film as a planarizing layer, a composition in which Si, Ti, Zr, Ta, Ca or the like is further dispersed is thermoset to function as an etching stopper. The transparent layer formed by (1) may further be included.

-Colored pixels-
The color filter of the present invention has a colored pixel on a support having a plurality of light receiving elements (for example, on the light receiving element forming surface side), for example, a pattern in which colored pixels, a black matrix, etc. are regularly arranged. Can have. The colored pixel in the present invention contains at least a pigment and an ultraviolet absorber, and the transmittance of light having a wavelength of 365 nm is 0.1% to 10.0%, preferably 0.1% to 5.0%, The pattern size is 0.5 μm or more and 1.2 μm or less.

The transmittance of the 365 nm wavelength light of the color filter of the present invention is 0.1% to 10.0% (preferably 0.1% to 5.0%). A transmittance of 0.1% or more means that the film has light absorption at a wavelength of 365 nm because it actively contains an ultraviolet absorber. Further, when this transmittance exceeds 10.0%, that is, when the transmittance of the coating film forming the color filter exceeds 10.0%, the corner (cad) of each pixel observed from the normal direction of the filter surface. In addition to being unable to prevent the rounding of the part and the rounding of the corners observed in the pixel cross section, the frequency of the development residue is further deteriorated.
Note that the change in transmittance can be ignored between the coating film made of the photosensitive coloring composition forming the coloring pattern and the coloring pattern after patterning the coating film by exposure and development.
Among these, the transmittance for 365 nm wavelength light is preferably 0.1 to 5.0% for the same reason as described above.

  The transmittance of 365 nm wavelength light of the color filter is obtained by using a spectrophotometer (MCPD-2000, manufactured by Otsuka Electronics Co., Ltd.) to obtain the ratio of the amount of light transmitted through the film to the amount of light incident on the film. Value.

  The size of the colored pixels constituting the color filter is preferably small from the viewpoint of miniaturization of the device and high-speed operation of the solid-state imaging device, and the colored pixels constituting the color filter of the present invention are arranged in a quadrilateral shape. The pattern size (distance of one side of the rectangle of each pixel viewed from the normal direction of the filter surface) is 0.5 μm or more and 1.2 μm or less. While the pixel size is within this range, roundness is suppressed in the corner portion of each pixel observed from the normal direction of the filter surface and / or the corner portion observed in the pixel cross section. .

-Pigment-
As the pigment, conventionally known various inorganic pigments or organic pigments can be used. Regardless of whether the pigment is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a small particle size and a small particle size as much as possible in consideration of handling properties. Then, it is preferably a pigment having an average primary particle diameter of 0.01 to 0.3 μm, more preferably 0.01 to 0.15 μm.

  When the average primary particle diameter is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast. The average primary particle diameter is obtained by observing with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating the average value. It is done.

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

Examples of the organic pigment include:
CIPigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279;
CIPigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214;
CIPigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73;
CI Pigment Green 7, 10, 36, 37;
CIPigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH thing,
CIPigment Violet 1, 19, 23, 27, 32, 37, 42;
CIPigment Brown 25, 28:
CIPigment Black 1, 7;

  Among these, preferable pigments include CIPigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; CIPigment Orange 36, 71; CIPigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264; CIPigment Violet 19, 23, 32; CIPigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; CIPigment Green 7, 36, 37; CIPigment Black 1, 7, and the like. However, the present invention is not limited to these.

  In the present invention, a fine and sized organic pigment can be used as necessary. The refinement of the pigment is a process of grinding as a highly viscous liquid composition together with the pigment, the water-soluble organic solvent, and the water-soluble inorganic salts. Specifically, it is described in paragraph numbers [0030] to [0032] of JP-A-2007-112934. Then, as described in paragraph [0034] of the same publication, the ground mixture is dissolved in warm water at 80 ° C. together with a water-soluble organic solvent and water-soluble inorganic salts, filtered, washed with water, and dried in an oven. A fine pigment can be obtained.

The organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as red pigments, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene pigments A mixture of a red pigment, an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred.
The mass ratio of the red pigment to the other color pigment is preferably 100: 5 to 100: 80. When the mass ratio is 100: 5 or more, the light transmittance of 400 nm to 500 nm can be suppressed and the color purity can be increased, and when it is 100: 80 or less, the color developing power is good. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

Further, as the green pigment, one kind of halogenated phthalocyanine pigment may be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment may be used. it can. As such an example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. When the mass ratio is 100: 5 or more, the light transmittance of 400 to 450 nm can be suppressed, and the color purity can be increased. When the mass ratio is 100: 200 or less, the main wavelength is not shifted from the long wavelength by the NTSC target hue. Can be avoided. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable.
The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

  The pigment content in the colored pixels constituting the color filter is not particularly limited, but is preferably 25% by mass or more based on the total solid content of the composition from the viewpoint of color separation. More preferably, it is 30 mass% or more, and 40 mass% or more is especially preferable. The upper limit of the pigment content is preferably 60% by mass.

  The color filter may further contain a pigment dispersant and a pigment derivative for dispersing the pigment. Details of these will be described later.

<Compound represented by formula (I)>
The color filter of the present invention contains at least one compound represented by the following general formula (I), which is a conjugated diene compound, as an ultraviolet absorber. The use of this conjugated diene compound suppresses subsequent development performance fluctuations, especially when low-illuminance exposure is performed. Therefore, exposure illuminance dependence related to pattern formability such as pattern line width, film thickness, and spectral spectrum Can be suppressed.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² May be the same as or different from each other, but do not represent a hydrogen atom at the same time.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-hexyl group, a cyclohexyl group, and n-decyl. Group, n-dodecyl group, n-octadecyl group, eicosyl group, methoxyethyl group, ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group, N, N-diethylaminopropyl group, cyanoethyl group, phenethyl group Group, benzyl group, pt-butylphenethyl group, pt-octylphenoxyethyl group, 3- (2,4-di-t-amylphenoxy) propyl group, ethoxycarbonylmethyl group, 2- (2-hydroxyethoxy) ) Ethyl group, 2-furylethyl group and the like, and methyl group, ethyl group, propyl group, n-butyl group and n-hexyl group are preferred. There.
The alkyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent of the alkyl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, Acyloxy group, halogen atom, acylamino group, acyl group, alkylthio group, arylthio group, hydroxy group, cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkyl A sulfonyl group, an arylsulfonyl group, etc. are mentioned.

The aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² may be a single ring or a condensed ring, and is any of a substituted aryl group having a substituent or an unsubstituted aryl group. There may be. For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group, fluorenyl group, etc. can be mentioned. Examples of the substituent of the substituted aryl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, an acyl group, an alkylthio group, an arylthio group, and a hydroxy group. Cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, arylsulfonyl group and the like. Of these, a substituted or unsubstituted phenyl group, 1-naphthyl group, and 2-naphthyl group are preferable.

R ¹ and R ² may form a cyclic amino group together with the nitrogen atom. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.

Among the above, R ¹ and R ² are each a lower alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl). , 2-ethylhexyl, tert-octyl, etc.) or a substituted or unsubstituted phenyl group (for example, tolyl group, phenyl group, anisyl group, mesityl group, chlorophenyl group, 2,4-di-t-amylphenyl group, etc.) preferable. It is also preferred that R ¹ and R ² are combined to form a ring (for example, a piperidine ring, a pyrrolidine ring, a morpholine ring) containing the nitrogen atom represented by N in the formula.

In the general formula (I), R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is preferably an electron withdrawing group having a Hammett's substituent constant σ _p value (hereinafter simply referred to as “σ _p value”) of 0.20 or more and 1.0 or less. More preferably, it is an electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less.
Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. . Substituent constants obtained by Hammett's rule include a σ _p value and a σ _m value, and these values are described in many general books. For example, the JA Dean edition “Lange's Handbook of Chemistry” "Twelfth edition, 1979 (Mc Graw-Hill)" and "Chemical domain special issue", 122, 96-103, 1979 (Nanedo), Chemical Reviews, 91, 165-195, 1991 detailed. In the present invention, it does not mean that the values known in the literature described in these documents are limited to only certain substituents, but within the range when measured based on Hammett's law even if the value is unknown. Of course, it is included as long as it is included.

Specific examples of the electron-withdrawing group having a σ _p value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, Dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, at least An alkyl group substituted with two or more halogen atoms, an alkoxy group substituted with at least two halogen atoms, an aryloxy group substituted with at least two halogen atoms, or at least two halogen atoms Substituted alkyl Amino group, at least two an alkylthio group substituted with a halogen atom, sigma _p value of 0.20 or more other electron-withdrawing aryl group substituted with group, a heterocyclic group, a chlorine atom, a bromine atom, an azo group Or a selenocyanate group. Of these substituents, the group that can further have a substituent may further have a substituent as described above.

Among the above, in the present invention, R ³ is preferably a group selected from a cyano group, —COOR ⁵ , —CONHR ⁵ , —COR ⁵ , —SO ₂ R ⁵ , and R ⁴ is a cyano group. A group selected from the group, —COOR ⁶ , —CONHR ⁶ , —COR ⁶ , —SO ₂ R ⁶ is preferred. R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ⁵ and R ^{6 have the same} meanings as those in R ¹ and R ² , and the preferred embodiments are also the same.
Among these, as R ³ and R ⁴ , acyl group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, sulfamoyl group are preferable. In particular, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferable.
R ³ and R ⁴ may be bonded to each other to form a ring.

Moreover, at least one of the above R ¹ , R ² , R ³ , and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. Moreover, the copolymer with another monomer may be sufficient.
In the case of the copolymer, examples of other monomers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (for example, esters derived from acrylic acids such as methacrylic acid, preferably lower alkyl esters). And amides (eg, acrylamide, methacrylamide, t-butyl acrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, Octyl methacrylate, lauryl methacrylate, methylenebisacrylamide, etc.)), vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl laurate, etc.), acrylonitrile, meta Acrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives such as vinyl toluene, divinylbenzene, vinyl acetophenone, sulfostyrene, styrene sulfinic acid, etc.), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl Examples include ethers (eg, vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine, 2- and 4-vinyl pyridine, and the like.
Of these, acrylic acid esters, methacrylic acid esters, and aromatic vinyl compounds are particularly preferable.
Two or more comonomer compounds can be used together. For example, n-butyl acrylate and divinylbenzene, styrene and methyl methacrylate, methyl acrylate and methacrylate acid, and the like can be used.

  Hereinafter, preferable specific examples [Exemplary compounds (1) to (14)] of the compound represented by the general formula (I) are shown. However, the present invention is not limited to these.

  The compounds represented by the general formula (I) are disclosed in JP-B 44-29620, JP-A 53-128333, JP-A 61-169831, JP-A 63-53543, JP It can be synthesized by the methods described in JP-A 63-53544 and JP-A 63-56651.

Hereinafter, specific methods for synthesizing representative compounds of the present invention will be described.
-Synthesis Method of Exemplary Compound (1)-
3-Anilinoacrolein anil (13.3 g) and ethylphenylsulfonylacetate (14.3 g) are heated in acetic anhydride (40 ml) to 85-90 ° C. for 2 hours. Acetic anhydride is removed under reduced pressure, ethanol (40 ml) and di-n-hexylamine (24.1 g) are added and refluxed for 2 hours. Ethanol is removed, the residue is subjected to column chromatography, purified, and recrystallized from ethanol to obtain the desired product (melting point = 95 to 96 ° C.).

  The content of the conjugated diene compound represented by the general formula (I) in the colored pixel constituting the color filter is the angle at the filter surface of the colored pixel and the pixel cross section (cross section cut by a plane orthogonal to the filter surface). 0.1-10 mass% or more is preferable with respect to the total solid of a colored pixel at the point which suppresses roundness of (cad) and improves rectangularity, and it is still more preferable that it is 1.0-5.0 mass%. .

  The change in pattern as described above becomes noticeable in a magenta or red photosensitive coloring composition that absorbs less light with respect to ultraviolet rays such as g-line, h-line, and i-line as exposure light sources. Therefore, the compound represented by the general formula (I) (conjugated diene compound) is particularly effective when a magenta or red photosensitive coloring composition or colored pixel is formed.

  The colored pixel in the present invention may further contain other components such as a photopolymerization initiator, a polymerizable monomer, a pigment dispersant and / or a pigment derivative, and an alkali-soluble resin in addition to the above components.

The colored pixel in the present invention can be suitably produced using, for example, a photosensitive coloring composition containing a pigment, an ultraviolet absorber, a photopolymerization initiator, and a polymerizable monomer. Specifically, a photosensitive coloring composition containing at least a pigment, a polymerizable monomer, a photopolymerization initiator, and a compound represented by the general formula (I) (conjugated diene compound) has a plurality of light receiving elements. The light transmittance at a wavelength of 365 nm is 0.1% or more by applying to the light receiving element forming surface side of the support, exposing the applied coating layer (preferably via a photomask), and developing. A colored pattern (colored pixel) that is 10.0% or less (preferably 0.1% or more and 5.0% or less) and has a pattern size of 0.5 μm or more and 1.2 μm or less is formed. Thereby, a color filter is produced.
The photosensitive coloring composition generally uses a solvent, and can be constituted by using other components such as a pigment dispersant and / or a pigment derivative and an alkali-soluble resin as necessary.

  By constructing a photosensitive composition containing a pigment as a colorant using an ultraviolet absorber having a specific structure represented by the general formula (I), the illuminance dependency during exposure, particularly low illuminance ( For example, when a fine colored pattern having a pattern size of 0.5 μm or more and 1.2 μm or less is formed, the development performance fluctuation when developing by performing pattern exposure at a high illuminance of 95% or less) Variations in the shape such as the remaining film ratio after development, variation in development residue, and variation in pattern width can be suppressed, and a pattern having a desired rectangular size and high rectangularity can be stably formed.

The details of the pigment and the ultraviolet absorber are as described above, and the preferred embodiments are also the same.
As content in the photosensitive coloring composition of a pigment, 25 mass% or more is preferable with respect to the total solid content (mass) of this composition, 25-60 mass% is more preferable, 30-60 mass% is Further preferred. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.
The content of the ultraviolet absorber (particularly the conjugated diene compound represented by the general formula (I)) in the photosensitive coloring composition is preferably 0.01 to 10% by mass with respect to the total solid content of the composition. 0.1-7.5 mass% is more preferable, and 1.0-5.0 mass% is especially preferable. When the content of the ultraviolet absorber, particularly the conjugated diene compound, is 0.01% by mass or more, the light shielding ability at the time of exposure is good and the pattern is not thickened due to excessive progress of polymerization. It is easy to obtain and the generation of peripheral residues is further suppressed. On the other hand, when it is 10% by mass or less, the light shielding ability at the time of exposure is not too strong, and the polymerization proceeds more favorably.

<Pigment dispersant>
The photosensitive coloring composition may contain a pigment dispersant for dispersing the pigment in addition to the pigment described above. By containing the pigment dispersant, the dispersibility of the pigment in the composition can be improved. As the pigment dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many types of compounds can be used as the pigment dispersant. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc .; Nonionic surfactants such as phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Agent: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants such as 26000, 28000 (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108 L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Industries, Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 1 63, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  As content in the photosensitive coloring composition of a pigment dispersant, 1-100 mass% is preferable with respect to the mass of the above-mentioned pigment, and 3-70 mass% is more preferable.

<Pigment derivative>
The photosensitive coloring composition can add a pigment derivative with the said pigment dispersant as needed. A pigment derivative having an affinity for the pigment dispersant or a polar group introduced is adsorbed on the surface of the pigment, and this is used as an adsorption point for the pigment dispersant, whereby the pigment is formed into fine particles as a photosensitive coloring composition. It can be dispersed to prevent re-aggregation, and is effective in constructing a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced as a substituent in the side chain. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzimidazo And Ron pigments. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the photosensitive coloring composition of a pigment derivative, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content is within the above range, it is possible to achieve good dispersion while keeping the viscosity low, improve the dispersion stability after dispersion, and obtain excellent color characteristics with high transmittance. Moreover, when producing a color filter, it can be comprised by the high contrast which has a favorable color characteristic.

  The dispersion method is, for example, using a bead disperser using zirconia beads or the like (for example, a disperse mat made by GETZMANN Co., Ltd.), in which a pigment and a pigment dispersant are mixed in advance and dispersed in advance using a homogenizer or the like Can be done by finely dispersing. The dispersion time is preferably about 3 to 6 hours.

<Photoinitiator>
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US Pat. No. US Pat. No. 4,318791 and European Patent Publication EP-88050A, described in US Pat. No. 4,1994,420 Aromatic ketone compounds such as benzophenones, (thio) xanthones or acridine compounds described in Fr-2456541, compounds such as coumarins or lophine dimers described in JP-A-10-62986, JP-A Sulfonium organoboron such as in Japanese Patent No. 8-015521 Body, etc., etc. can be mentioned.

  Examples of the photopolymerization initiator include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarins, lophine dimers, biphenyl Imidazole type, oxime ester type and the like are preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.

  Preferable examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy-cyclohexyl. -Phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl- s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl- 2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-to Azine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be preferably exemplified.

  Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3. , 4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 A preferred example is 4-oxodiazole.

  Preferred examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s Preferred examples include -triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.

  Preferable examples of the biimidazole photopolymerization initiator include 2-mercaptobenzimidazole, 2,2′-benzothiazolyl disulfide and the like.

  Examples of the oxime ester photopolymerization initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (Phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) ) -1- [4- (phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- ( O-benzoyloxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethyl) Phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-prop-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyl) Oxime) -1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethi -6- (2-butylbenzoyl) -9H-carbazol-3-yl] ethanone, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 '-(benz Preferred examples include mercapto) benzoyl-hexyl-ketoxime.

  In addition to the above, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-trialkylphenylphosphonium salt and the like can be mentioned.

  Among them, an oxime ester compound is preferable in that it can be highly sensitive by addition in a small amount when used in combination with the conjugated diene compound represented by the general formula (I), and 2- (O-benzoyloxime) -1 -[4- (Phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Ethanone is most preferred.

  As content in the photosensitive coloring composition of a photoinitiator, 1.5 mass% or more is preferable with respect to the total solid of this composition, 1.5-10.0 mass% is preferable, More Preferably it is 1.5-8.0 mass%. When the content of the photopolymerization initiator is 1.5% by mass or more, the color pattern can be formed more rectangularly while adjusting the transmittance of the coating film to 10.0% or less, preferably 5.0% or less. it can.

  Examples of the photopolymerization initiator include sensitizers and light stabilizers described in paragraphs [0105] to [0107] and [0109] of JP-A-2008-292548, other known photopolymerization initiators, A thermal polymerization inhibitor may be used in combination.

<Polymerizable monomer>
As the polymerizable monomer, a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. By containing the polymerizable monomer together with the photopolymerization initiator and the like, the photosensitive coloring composition in the present invention can be constituted in a negative type.

Examples of polymerizable monomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylol Ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxye) (I) A polyfunctional alcohol such as isocyanurate, glycerin or trimethylolethane, which is added with ethylene oxide or propylene oxide and then (meth) acrylated; JP-B-48-41708, JP-B-50-6034, JP Urethane acrylates as described in JP-A-51-37193; polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be mentioned. Among these, as the polymerizable monomer, a polyfunctional (meth) acrylic compound is preferable.

  10-80 mass% is preferable with respect to the total solid of a composition, and, as for content in the photosensitive coloring composition of a polymerizable monomer, 10-40 mass% is more preferable. When the content is within the above range, a sufficient degree of cure and elution of the unexposed area can be maintained, and the degree of cure of the exposed area can be sufficiently maintained, and the elution of the unexposed area is significantly reduced. Can be prevented.

<Alkali-soluble resin>
The photosensitive coloring composition in the present invention can be constituted using an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble resin is preferably a linear organic high molecular polymer and soluble in an organic solvent and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.

  In addition to the above, alkali-soluble resins include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinyl Pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful.

  Further, the linear organic polymer may be a copolymer of hydrophilic monomers. Examples of hydrophilic monomers include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, and dialkyl. Aminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) Examples thereof include acrylate, branched or linear butyl (meth) acrylate, and phenoxyhydroxypropyl (meth) acrylate. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and groups derived from salts thereof, morpholinoethyl group, etc. Including monomers are also useful.

  Further, the alkali-soluble resin may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the polymer having a polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

Among these various alkali-soluble resins, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins. Examples of acrylic resins include copolymers obtained by polymerization of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available products. KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable. The alkali-soluble resin is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ from the viewpoints of developability, liquid viscosity, and the like, and is preferably 2000 to 1 × 10 ⁵ . A polymer is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

  The content of the alkali-soluble resin in the photosensitive coloring composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total solid content of the composition, from the viewpoint of developability and the like. -70 mass% is especially preferable.

<Organic solvent>
Generally the photosensitive coloring composition in this invention can be comprised using an organic solvent. The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the photosensitive coloring composition, but particularly considers the solubility, applicability, and safety of the UV absorber and binder. Are preferably selected. Moreover, when preparing the photosensitive coloring composition in this invention, it is preferable that at least 2 type of organic solvent is included.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And as ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone and aromatic hydrocarbons such as toluene, Xylene and the like are preferred.

  It is also preferable to mix two or more kinds of these organic solvents from the viewpoints of solubility of the ultraviolet absorber and the alkali-soluble resin, improvement of the coating surface condition, and the like. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The content of the organic solvent in the photosensitive coloring composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. 10 to 50% by mass is particularly preferable.

<Other additives>
In the photosensitive coloring 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 anti-aggregation agent and the like are blended as necessary. I can do it. Specific examples of additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic, Anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane Adhesion promoters such as 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6- (t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; and anti-aggregation agents such as sodium polyacrylate.

The photosensitive coloring composition of the present invention is an organic carboxylic acid, preferably a molecular weight of 1000, in order to promote alkali solubility in the ultraviolet-irradiated part of the photosensitive coloring composition and to further improve the developability. The following low molecular weight organic carboxylic acids can be contained.
Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid Aliphatic dicarboxylic acids such as acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid Acid; Aliphatic tricarboxylic acid such as tricarballylic acid, aconitic acid, and camphoronic acid; Aromatic monocarboxylic acid such as benzoic acid, toluic acid, cumic acid, hemellitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellito Aromatic polycarboxylic acids such as acids, trimesic acid, merophanoic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid It is done.

  In the color filter of the present invention, the transmittance of light having a wavelength of 365 nm on the support is 0.1% to 10.0%, preferably 0.1% to 5.0%. A plurality of colored or non-colored patterns having a pattern size of 0.5 μm or more and 1.2 μm or less are arranged and formed, for example, on the light receiving element forming surface side of the support having a plurality of light receiving elements, The plurality of colored or non-colored patterns are produced by a method capable of forming an array. In this invention, Preferably, it produces using the photosensitive coloring composition containing at least the compound represented by a pigment, a polymerizable monomer, a photoinitiator, and the said general formula (I).

Specifically, the photosensitive coloring composition is applied, for example, directly on the light receiving element forming surface of the support having a plurality of light receiving elements or via another layer (preferably dried thereafter). ) A coating layer is formed (hereinafter, this may be referred to as a “coating film forming step”), and the coating layer formed by coating is image-like through a photomask (preferably with ultraviolet rays such as i-line). Exposure (hereinafter, sometimes referred to as “exposure step”) and development of the exposed coating layer with a developer (for example, an alkali developer) (hereinafter also referred to as “development step”). Thus, a colored pattern can be formed. Moreover, in this invention, the process (henceforth a "post-baking process") which heat-processes the coloring pattern after image development processing as needed can be further provided.
Moreover, in the manufacturing method of the color filter of this invention, the hardening process hardened by further heating and / or exposing the pattern after exposure and image development can be further provided as needed.

  In the coating film forming step, the photosensitive coloring composition is applied on a support by a coating method such as spin coating, cast coating, roll coating, slit coating, etc. (preferably dried afterwards). Forming a colored composition layer (coating layer).

  In the exposure step, the coating layer formed in the coating film forming step is exposed by irradiating actinic rays or radiation in an image-like manner with a specific pattern (via a photomask). Examples of the actinic ray or radiation include infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, etc., but at least ultraviolet rays are preferable, and in particular, g rays, h rays, i rays, etc. Ultraviolet rays are preferably used. In the case of a color filter for a solid-state image sensor, the exposure is preferably exposure using mainly i-line in a stepper exposure machine.

The exposure illuminance is preferably 10 mW / cm ² or more, more preferably 20 mW / cm ² or more, and more preferably 30 mW from the viewpoint of throughput in the proximity exposure apparatus and mirror projection exposure apparatus used for the production of color filters for liquid crystal display devices. / Cm ² or more is particularly preferable. The stepper exposure machine used for manufacturing a color filter for a solid-state imaging device, also in view of the throughput is preferably 300 mW / cm ² or more, more preferably 500 mW / cm ² or more, 1000 mW / cm ² or more is particularly preferable. The exposure amount is also from the viewpoint of throughput, generally preferably 1000 mJ / cm ² or less, more preferably 500 mJ / cm ² or less, particularly preferably 300 mJ / cm ² or less.

In the developing step, the exposed coating layer is developed with a developer to reveal a pattern.
Any developer can be used as long as it dissolves the unexposed portion of the photosensitive coloring composition and hardly dissolves the exposed portion (radiation irradiated portion). Specifically, various organic solvents and combinations thereof, and alkaline aqueous solutions can be used.

  As said organic solvent, the above-mentioned solvent which can be used when preparing a photosensitive coloring composition can be mentioned.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and the like.

  As the developer, it is preferable to use an alkaline aqueous solution adjusted so that the alkali concentration is preferably pH 11 to 13, more preferably pH 11.5 to 12.5. When the alkali concentration is pH 13 or less, pattern roughness, peeling, and reduction in the remaining film ratio can be avoided, and when the alkali concentration is pH 11 or more, the development speed is good and the generation of residues can be prevented.

  In the development process, development is performed using a developer such as an alkaline aqueous solution. Examples of the development method include a dipping method, a spray method, and a paddle method. The development temperature is preferably 15 to 40 ° C. Further, after development, washing is generally performed with running water.

  Furthermore, in the method for producing a color filter of the present invention, it is preferable that a heat treatment is performed by providing a post-baking step in order to sufficiently cure the coated layer after development. 100-300 degreeC is preferable and the heating temperature in a post-baking process has more preferable 150-250 degreeC. The heating time is preferably about 10 minutes to 1 hour, more preferably about 5 minutes to 30 minutes.

  The color filter of the present invention is used for a solid-state imaging device such as a CCD or a CMOS, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

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

Example 1
-Preparation of pigment dispersion composition-
(Preparation of red pigment dispersion composition R-1)
Ingredients having the following composition were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
<Composition>
Pigment Red 254 (pigment): 10 parts Pigment Yellow 139 (pigment): 2.5 parts Polymer dispersing agent BYK-161 (by Big Chemie): 2.5 parts Propylene glycol monomethyl Ether acetate (manufactured by Daicel Chemical Industries, product name: MMPGC) 35 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2,000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a red pigment dispersion composition R-1.

(Preparation of green pigment dispersion composition G-1)
In the preparation of the red pigment dispersion composition R-1, a mixed solution was prepared and dispersed in the same manner as the red pigment dispersion composition except that the composition was changed to the following.
<Composition>
Pigment Green 36 (pigment): 10 parts Pigment Yellow 139 (pigment): 2.5 parts Polymer dispersing agent BYK-161 (by Big Chemie): 2.5 parts Propylene glycol monomethyl Ether acetate (manufactured by Daicel Chemical Industries, product name: MMPGC) 35 parts

(Preparation of blue pigment dispersion composition B-1)
In the preparation of the red pigment dispersion composition R-1, a mixed solution was prepared and dispersed in the same manner as the red pigment dispersion composition except that the composition was changed to the following.
<Composition>
Pigment Blue 15: 6 (pigment) 12.5 parts Polymer dispersing agent BYK-161 (by Big Chemie) 2.5 parts propylene glycol monomethyl ether acetate (by Daicel Chemical Industries, product) Name: MMPGAC) 35 parts

-Preparation of resist solution for planarization film-
The components in the following composition were mixed and stirred with a homogenizer stirrer to prepare a flattening film resist solution.
<Composition>
Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (45%, weight average molecular weight 30000, manufactured by Fujikura Kasei Co., Ltd., product name: Acrybase FF-187 ) 22 parts dipentaerythritol pentaacrylate 6.5 parts (Nippon Kayaku Co., Ltd., product name: KAYARAD DPHA)
Propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd., product name: MMPGAC) 13.8 parts Ethyl-3-ethoxypropionate (manufactured by Nagase Sangyo Co., Ltd.) 12.3 parts Triazine compound (Compound I below; Triazine PP (product name) manufactured by PANCHIM) 0.3 parts

-Fabrication of planarization film-
A CMOS substrate having a PPX film (polyperoxyxylene) formed as a device sealing film on a CMOS sensor was prepared using the obtained flattening film resist solution, and was applied onto the CMOS substrate by spin coating. . Next, heat treatment was performed on a hot plate at a surface temperature of 120 ° C. for 120 seconds on the surface of the coating film to obtain a uniform coating film having a thickness of about 2 μm on the CMOS substrate. Next, the coating film was cured in an oven at 220 ° C. for 1 hour to form a flattened film.

-Preparation of photosensitive coloring composition-
Next, using the pigment dispersion obtained by kneading and dispersing the red pigment dispersion composition R-1 with a sand mill disperser, components having the following composition were mixed to prepare a photosensitive coloring composition.
<Composition>
・ Resin A: 8.54 parts
(Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer propylene glycol monomethyl ether acetate solution [30% by mass, weight average molecular weight 30000, manufactured by Fujikura Kasei Co., Ltd., product name: Acrybase FF- 187])
Monomer A 3.33 parts (product name: KAYARAD DPHA, manufactured by Nippon Kayaku; dipentaerythritol pentaacrylate)
Red pigment dispersion composition R-1 27.88 parts Solvent A (organic solvent) 55.78 parts (propylene glycol monomethyl ether acetate; manufactured by Daicel Chemical Industries, product name: MMPGC)
Initiator A (compound II below; manufactured by Ciba Specialty Chemicals Co., Ltd., product name: IRGACURE OXE01) 0.235 parts. Compound III (UV absorber represented by general formula (I))・ ・ ・ 0.755 part ・ Surfactant A ・ ・ ・ 0.36 part (Fluorosurfactant; manufactured by Dainippon Ink & Chemicals, product name: MegaFuck F-144)
・ Polymerization inhibitor A (manufactured by Kanto Chemical Co., Inc .; p-methoxyphenol): 0.001 part

-Production of coating film-
After applying the photosensitive coloring composition obtained above by spin coating on the flattening film of the CMOS substrate, the coating film surface temperature is 100 ° C. for 120 seconds, heat treatment is performed on a hot plate, and then dried. A coating film having a thickness of 0.6 μm after drying was formed.

−Preparation of color filter pixel pattern−
Next, an i-line stepper (FPA-manufactured by Canon Inc.) is passed through a mask pattern in which 1.0 μm square pixels are arranged in a 4 mm × 3 mm region on the substrate with respect to the dried coating film. 3000 i5 +) and an exposure amount of 100 mJ / cm ² .

The pattern-exposed coating film was subjected to paddle development for 60 seconds at room temperature using a 60% aqueous solution of an organic alkaline developer CD-2000 (Fuji Film Electronics Materials Co., Ltd.), and then spin showered for another 20 seconds. And rinsed with pure water. Thereafter, it was further washed with pure water. Thereafter, water droplets were blown with high-pressure air, the substrate was naturally dried, and post-baked with a hot plate at 220 ° C. for 300 seconds to form a colored pattern (colored resin film) on the CMOS substrate.
As described above, a color filter for a solid-state imaging device was produced.

-Evaluation-
The following evaluation and measurement were performed on the color filter for a solid-state imaging device obtained from the above. The results of evaluation and measurement are shown in Table 2 below.

-1. Pixel pattern shape
(1-1) Evaluation on Filter Surface The shape of the 1.0 μm square pixel pattern of the obtained color filter was measured on a CMOS substrate using a length measurement SEM (S-4800H, manufactured by Hitachi High-Technologies Corporation). Observation was performed at a magnification of 30,000 from above the color filter (from the normal direction of the filter surface), and the shape of the corner of each pixel adjacent to the pixel was evaluated according to the following evaluation criteria. In addition, since the shape of the corner is different from the pattern shape of other adjacent colors, it is measured as a color mixture and noise during image recognition, and the hue and contrast of the display image are lowered, and as a result Worsen the performance.
<Evaluation criteria>
◯: Corners were not round and a good rectangle was obtained.
Δ: Corners were rounded, but were practically acceptable.
X: The corner was rounded like a fan, and a rectangle was not obtained.

(1-2) Evaluation in Pixel Cross Section Color filter on CMOS substrate using SEM (S-4800H, manufactured by Hitachi High-Technologies Corporation) as the shape of the 1.0 μm square pixel pattern of the obtained color filter A cut surface cut along a plane perpendicular to the filter surface was observed at a magnification of 20,000, and the shape of the cut surface was evaluated according to the following evaluation criteria. In the case where the shape of the cut surface is an inverse taper as shown in FIG. 1A, the hue of the formed pattern is not uniform, the hue and contrast of the display image are impaired, and the device performance is deteriorated. In addition, since the forward taper shown in FIG. 1B is different from the pattern shape of other adjacent colors, it is measured as a color mixture and noise during image recognition, and the hue and contrast of the display image are lowered. Degrading device performance.
<Evaluation criteria>
○: The cut surface was rectangular.
(Triangle | delta): Although it is a grade which is accept | permitted practically, the cut surface was a little forward taper shape.
X: The cut surface was a reverse taper or a forward taper.

-2. Peripheral residue
The post-baking color filter pixel pattern was observed at a magnification of 30,000 times from above the color filter on the CMOS substrate using a length measuring SEM (S-7800H, manufactured by Hitachi, Ltd.). The presence or absence of was evaluated according to the following evaluation criteria.
<Evaluation criteria>
○: There was no development residue.
Δ: A slight amount of development residue was observed, but was practically acceptable.
X: The generation | occurrence | production of the residue was remarkable.

-3. Pattern size
The shape of the pixel pattern of the color filter after post-baking was observed at a magnification of 30,000 times from above the color filter on the CMOS substrate using a length measurement SEM (S-7800H, manufactured by Hitachi, Ltd.). The pattern size was evaluated according to the following evaluation criteria from the viewpoint of the degree of shift of the side length from the 1.0 μm square pixel of the mask pattern (suitable dimension).
<Evaluation criteria>
A: The pattern size was 0.90 μm or more and less than 1.10 μm.
X: The pattern size was less than 0.90 μm or more than 1.10 μm.

-4. 365 nm light transmittance-
After the photosensitive coloring composition was applied to a glass substrate (Corning 1737) by spin coating, the surface temperature of the coating film surface was set to 100 ° C., and was heated for 120 seconds on a hot plate and dried. Light having a wavelength of 365 nm was incident on the 0 μm film, and the transmittance was measured with a spectrophotometer (device name: MCPD-2000, manufactured by Otsuka Electronics Co., Ltd.).

(Examples 2 to 20)
In Example 1, except that the composition of the photosensitive coloring composition was changed as shown in Table 1 below, a photosensitive coloring composition was prepared and a color filter was prepared in the same manner as in Example 1, Evaluation was performed. The results of evaluation and measurement are shown in Table 2 below.

(Comparative Examples 1-15)
In Example 1, except that the composition of the photosensitive coloring composition was changed as shown in Table 1 below, a photosensitive coloring composition was prepared and a color filter was prepared in the same manner as in Example 1, Evaluation was performed. The results of evaluation and measurement are shown in Table 2 below.

Hereafter, the structure of the compound as described in the column of the ultraviolet absorber etc. of the said Table 1 is shown.

As shown in Table 2, in the example using the ultraviolet absorber represented by the general formula (I), the transmittance of 365 nm wavelength light after coating was suppressed to 10.0% or less, and the pattern shape variation Was suppressed, there was little residue, and a favorable rectangular pattern could be formed. On the other hand, in the comparative example, the pattern forming property of the desired size was poor and the rectangularity of the colored pattern was inferior.
Moreover, as shown in Example 1, Examples 3-9, Examples 11-15, and Examples 17-20, when the transmittance of 365 nm wavelength light after coating is 5.0% or less, The shape was even better.

Claims (5)

A support having a plurality of light receiving elements; a pigment provided on the support; and a compound represented by the following general formula (I): a transmittance of light having a wavelength of 365 nm is 0.1% or more and 10.0% And a colored pixel having a pattern size of 0.5 μm or more and 1.2 μm or less.

[In General Formula (I), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ¹ and R ² may be the same or different from each other, but do not represent a hydrogen atom at the same time, and R ¹ and R ² may form a cyclic amino group together with a nitrogen atom. R ³ and R ⁴ each independently represents an electron withdrawing group. ] A photosensitive coloring composition containing at least a pigment, a polymerizable monomer, a photopolymerization initiator, and a compound represented by the following general formula (I) is applied to a support having a plurality of light receiving elements, and is formed by coating. A color that forms a colored pattern in which the transmittance of light having a wavelength of 365 nm is 0.1% to 10.0% and the pattern size is 0.5 μm to 1.2 μm by exposing and developing the layer A method for manufacturing a filter.

[In General Formula (I), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ¹ and R ² may be the same or different from each other, but do not represent a hydrogen atom at the same time, and R ¹ and R ² may form a cyclic amino group together with a nitrogen atom. R ³ and R ⁴ each independently represents an electron withdrawing group. ]   The color filter according to claim 1, wherein a transmittance of light having a wavelength of 365 nm is 0.1% or more and 5.0% or less.   The color filter manufacturing method according to claim 2, wherein a transmittance of light having a wavelength of 365 nm is 0.1% or more and 5.0% or less.   The color filter according to claim 2 or 4, wherein a content ratio of the photopolymerization initiator is in a range of 1.5 to 10% by mass with respect to a total solid content of the photosensitive coloring composition. Manufacturing method.

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