JP2013117645A - Photosensitive coloring composition for color filter used in solid state imaging device and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition for a color filter used in a solid state imaging device, allowing a pattern shape to be kept in a vertical shape, low exposure dependency in pattern formation, and good film uniformity, and a color filter using the same.SOLUTION: A photosensitive coloring composition for a color filter used in a solid state imaging device contains (A) a photopolymerizable monomer, (B) an oxime ester initiator, (C) a colorant and (D) a solvent, where the (A) photopolymerizable monomer contains a (meth)acrylic compound having 3 or less unsaturated bond groups in a molecule in an amount of 50 mass% or more and 80 mass% or less based on the total amount of the photopolymerizable monomer.

Description

  The present invention relates to a color filter photosensitive coloring composition for a solid-state imaging device used for a color filter formed on a photoelectric conversion element typified by a CMOS or CCD, and a color filter formed on the photoelectric conversion element.

  In recent years, imaging devices have been widely used with the expansion of the contents of image recording, communication, and broadcasting. Although various types of imaging devices have been proposed, imaging devices using solid-state imaging devices that are small, lightweight, and capable of stably producing multi-color high performance devices are becoming popular. .

  The solid-state image sensor includes a plurality of photoelectric conversion elements that receive an optical image from a subject and convert incident light into an electrical signal. The types of photoelectric conversion elements are roughly classified into CCD (charge coupled device) type and CMOS (complementary metal oxide semiconductor) type. There are two types of photoelectric conversion element arrangements: linear sensors (line sensors) in which photoelectric conversion elements are arranged in one row, and area sensors (surface sensors) in which photoelectric conversion elements are two-dimensionally arranged in rows and columns. It is divided roughly into. In any sensor, as the number of photoelectric conversion elements (number of pixels) increases, the captured image becomes more precise.

  In addition, a color sensor that can obtain color information of an object by providing various color filters that transmit light of a specific wavelength in the path of light incident on the photoelectric conversion element is also widespread. As the color of the color filter, three primary colors composed of three hues of red (R), blue (B), and green (G), or cyan (C), magenta (M), and yellow A complementary color system composed of three hues (Y) is common.

  As a method for forming a color filter of a solid-state imaging device, a method of forming a pattern by a photolithography process is common (see, for example, Patent Document 1). In other words, pattern exposure, development, and hardening treatment, if necessary, are performed on the coating film coated with a colored photosensitive resin of a predetermined color, leaving the colored photosensitive resin at a predetermined site, and using the residue as a colored layer It is a method. When forming color filters with colored layers of different colors, use colored photosensitive resins of different colors, and perform steps such as resin coating formation, pattern exposure to the resin coating, development, and hardening treatment as necessary. Repeat as many times as necessary.

  One important issue regarding the performance required for a solid-state imaging device is to improve the sensitivity to incident light. Further, in order to increase the amount of information of a photographed image, it is necessary to miniaturize and highly integrate a photoelectric conversion element serving as a light receiving unit. However, when the photoelectric conversion element is miniaturized, the area of each photoelectric conversion element is reduced and the area for capturing light is also reduced, so that the amount of light that can be captured by the photoelectric conversion element is reduced. Moreover, in a solid-state imaging device provided with a color filter, when light passes through the color filter, light having a predetermined wavelength is separated and passed, but when the light passes, light absorption by the color filter occurs. The amount of light incident on the photoelectric conversion element decreases. Therefore, the sensitivity to light decreases as a solid-state imaging device.

  As a means for preventing such a decrease in the sensitivity of the solid-state imaging device, in order to efficiently capture light into the photoelectric conversion element (light receiving unit), the light incident from the object is condensed and the photoelectric conversion element A technique for forming a microlens leading to a (light receiving portion) has been proposed (see Patent Document 2). By condensing light with a microlens and guiding it to a photoelectric conversion element (light-receiving part), it becomes possible to increase the apparent aperture ratio (area) of the light-receiving part and improve the sensitivity of the solid-state image sensor. Is possible.

  In recent years, the demand for high-definition CCD image sensors with more than 6 million pixels has increased, and the pixel size of the color filter associated with these high-definition CCDs has also increased to a level below 2 μm × 2 μm. There is a problem that the pattern shape defect or residue of the formed color filter adversely affects the characteristics of the solid-state imaging device. Such insufficient pattern shape appears as uneven color at a pixel size of 2.5 μm or less or in the vicinity of 1.5 μm. Also, as the pixel size is reduced, the aspect ratio is increased (thickness is greater than the width), so the portion that should be removed (the non-effective portion of the pixel) cannot be completely removed, and the residue and pattern shape Tapering occurs. The residue of the resist that has been previously colored remains in the pixel portions of other colors, so that noise is increased in the reproduced image of the solid-state imaging device, and the roughness is conspicuous and the image quality is impaired.

  In order to improve the problem of the residue, studies have been made to introduce a carboxyl group into a photocurable compound for improving alkali developability (Patent Documents 3 and 4).

  Further, as the pattern becomes finer, the exposure dose dependency on the pattern dimension increases. Further, as the exposure amount increases, the resolution tends to decrease, for example, the corners of the pattern are rounded. In order to reduce the exposure dose dependency of pattern dimensions, addition of a polymerization inhibitor or the like has been studied (Patent Document 5).

  In order to improve the above problem, as a means for forming a fine pattern in a color filter for an image sensor, Patent Documents 3 and 4 have an acidic functional group and / or an alkyleneoxy chain having 2 or more carbon atoms in a photopolymerizable monomer. The use of polyfunctional photopolymerizable monomers has been studied. However, when a photopolymerizable monomer is used in this way, the time required for developing a coating film formed by adding an acidic functional group and / or an alkyleneoxy chain having 2 or more carbon atoms is shortened. There is a problem that sensitivity is low.

  Therefore, it is necessary to irradiate a large amount of exposure, the exposure time becomes long, and the yield in manufacturing is significantly reduced.

  Further, as the resolution of the solid-state imaging device is improved, the problem in forming the color filter has become apparent as described above as the pixel size is reduced. Important issues include the pattern pixel shape and the exposure dose dependence on the pattern dimensions. The pigment-dispersed colored coating film applied on the substrate is exposed through a photomask, developed, and patterned to form a pattern, but the pattern line width becomes narrower, and the taper of the pattern shape becomes longer. When light is incident on the light, the light is scattered and becomes noise.

  Further, the line width greatly changes with respect to the light irradiation exposure amount in the exposure process. As a result, there is no margin for exposure, and the manufacturing yield deteriorates.

JP 2005-5419 A JP 2004-200360 A Japanese Patent Laid-Open No. 10-62986 JP 2009-244807 A JP 2009-98686 A

  The problem to be solved by the present invention is that the pattern shape can be maintained in a vertical shape, the exposure dependency at the time of pattern formation can be reduced, and the coating film has a uniform uniform coating for a color filter used for a solid-state imaging device. The object is to provide a photosensitive coloring composition and a color filter using the same.

  As a result of intensive studies, the present inventors have developed a photosensitivity including a photopolymerizable monomer containing 50% by mass or more and 80% by mass or less of a (meth) acrylic compound having 3 or less unsaturated bond groups in one molecule. It has been found that by using the colored composition for a color filter for a solid-state imaging device, the taper of the pattern shape can be prevented from becoming longer as the pattern becomes finer, and the shape can be made vertical. The present invention has been made based on such findings.

  That is, the first aspect of the present invention is a photosensitive coloring composition for a color filter comprising (A) a photopolymerizable monomer, (B) an oxime ester initiator, (C) a coloring agent, and (D) a solvent. And (A) the photopolymerizable monomer contains a (meth) acryl compound having 3 or less unsaturated bond groups in one molecule of 50% by mass to 80% by mass of the total amount of the photopolymerizable monomer. The photosensitive coloring composition for color filters used for a solid-state image sensor characterized by these is provided.

  In such a photosensitive coloring composition, (A) the photopolymerizable monomer may further contain a (meth) acryl compound having 5 or 6 unsaturated bonding groups in one molecule.

  Moreover, the (meth) acryl compound which has 3 or less of said unsaturated bond groups in 1 molecule shall have a molecular weight of 300-540.

  In the second aspect of the present invention, the photosensitive coloring composition for a color filter used in the above solid-state imaging device is applied on a substrate, dried, and then (1) exposed by an ultraviolet exposure device. There is provided a color filter for a solid-state imaging device obtained by a step of developing with an alkaline aqueous solution, and a step of (3) thermal baking.

  ADVANTAGE OF THE INVENTION According to this invention, the taper length of the pattern which becomes long when the pixel dimension of a color filter becomes fine can be controlled, and the photosensitive coloring composition for color filters used for a solid-state image sensor with favorable resolution. Things can be provided. In addition, it is possible to provide a photosensitive coloring composition for a color filter that can be used for a solid-state imaging device, which can reduce a change in line width with respect to an exposure amount and has a wide production exposure margin. Furthermore, a color filter using the same can be provided.

It is sectional drawing which shows roughly an example of the solid-state imaging device which can be manufactured with the technique which concerns on 1 aspect of this invention. It is a top view which shows roughly the color filter 4 which comprises the solid-state imaging device 1 of FIG. It is a figure which shows the upper base line width and lower base line width of the formed pattern part about the shape of the formed pattern. Evaluation is performed by SEM, and when observed from the top of the pattern, a difference in shading can be confirmed between the upper bottom portion and the tapered portion of the pattern.

  Hereinafter, the photosensitive coloring composition for color filters used for a solid-state image sensor and the color filter using the photosensitive coloring composition which concern on one Embodiment of this invention are explained in full detail.

First, a method for manufacturing an image sensor will be described in detail with reference to the drawings. Note that, throughout all the drawings, the same reference numerals are given to components that exhibit the same or similar functions, and redundant descriptions are omitted.
FIG. 1 is a cross-sectional view schematically illustrating an example of a solid-state imaging device to which a photosensitive coloring composition and a color filter according to an embodiment of the present invention are applied. FIG. 2 is a plan view schematically showing the color filter 4 constituting the solid-state imaging device 1 of FIG.

  A solid-state imaging device 1 illustrated in FIG. 1 is a two-dimensional image sensor such as a CCD image sensor or a CMOS image sensor. The solid-state imaging device 1 includes a semiconductor chip 2, a planarization layer 3, a color filter 4, and a microlens array 5.

  The semiconductor chip 2 includes a plurality of pixels arranged two-dimensionally in plan view. Each pixel includes a photoelectric conversion element 21 that generates a signal charge corresponding to the amount of incident light. The photoelectric conversion element 21 is, for example, a photodiode including a pixel electrode, a counter electrode, and a semiconductor layer interposed therebetween.

  The semiconductor chip 2 further includes a read circuit (not shown). The readout circuit reads out the electric charge generated by the photoelectric conversion element 21. The photoelectric conversion element 21 can be constituted by, for example, a CCD or a CMOS device.

  A planarization layer 3 is formed on the semiconductor chip 2. The planarizing layer 3 is formed to provide a flat base for the color filter 4. The planarizing layer 3 has light transparency and is typically colorless and transparent. Further, typically, the planarization layer 3 has ultraviolet absorption characteristics. The planarization layer 3 is made of a transparent resin, for example. The thickness of the planarizing layer 3 is, for example, 0.8 μm or less. Note that the planarization layer 3 can be omitted when the semiconductor chip 2 is excellent in surface flatness or when it is desired to reduce the thickness of the solid-state imaging device 1.

  In addition, the board | substrate of this invention points out the thing which formed the planarization layer on the semiconductor chip or a semiconductor chip.

  The color filter 4 is installed on the flattening layer 3 and includes a plurality of green colored layers G, blue colored layers B, and red colored layers R, as shown in FIG.

  In the present embodiment, the plurality of green colored layers G form a checkered array pattern in plan view. The plurality of blue colored layers B are spaced apart from each other with the green colored layer G interposed therebetween, and form a square lattice-like arrangement pattern. The red colored layers R are spaced apart from each other with the green colored layer G interposed therebetween, and form a square lattice array pattern.

  The green colored layer G, the blue colored layer B, and the red colored layer R are adjacent to each other in the in-plane direction, and here, a square arrangement is adopted. The green colored layer G, the blue colored layer B, and the red colored layer R constituting these color filters respectively face the pixels of the semiconductor chip 2.

  The vertical and horizontal dimensions of the green colored layer G, the blue colored layer B, and the red colored layer R in a plan view are, for example, in the range of about 1 μm to about 10 μm, and typically about 1.5 μm to about 2.5 μm. Is in range. In addition, the dimension of the colored pixel in a general liquid crystal display device is several hundreds of micrometers. As is clear from these comparisons, color filters for solid-state imaging devices are required to have much higher dimensional accuracy and shape accuracy than color filters for display devices.

  A microlens array 5 is formed on the color filter 4. The microlens array 5 has, for example, a structure in which a plurality of cylindrical lenses are arranged corresponding to the rows or columns of pixels, or a structure in which a plurality of hemispherical lenses are arranged corresponding to the pixels. Yes.

  The solid-state imaging device 1 configured as described above can be manufactured, for example, by the following method.

  First, the planarization layer 3 is formed on the semiconductor chip 2 having the photoelectric conversion element 21 inside.

  Next, a green colored layer G is formed on the planarizing layer 3. That is, a photosensitive coloring composition containing a green pigment is applied on the flattening layer 3, the coating film is subjected to pattern exposure, and then the coating film is developed, and further baked at a temperature of about 220 ° C., for example. For example, ultraviolet light is used for pattern exposure, and an alkali developer is used for development. Thereby, the green coloring layer G in which the part made into the unexposed part at the time of pattern exposure became an opening part is obtained. The shape of the green colored layer G in a plan view is generally a checkered pattern as shown in FIG.

  Next, a blue colored layer B and a red colored layer R are formed on the planarizing layer 3 by the same method as that for forming the green colored layer G. Either the blue colored layer B or the red colored layer R may be formed first.

  The color filter 4 is obtained as described above.

  Thereafter, a microlens array 5 is formed on the color filter 4 thus obtained, and the solid-state imaging device 1 shown in FIG. 1 is completed.

  Note that human visual sensitivity is higher for green light than for blue light and red light. Therefore, the dimensional accuracy and shape accuracy of the patterned green colored layer G have a greater influence on the image quality of the reproduced image than the dimensional accuracy and shape accuracy of the blue colored layer B and the red colored layer R. Therefore, the green colored layer G is formed first here.

  When the green colored layer G is formed, when the size of the green colored layer G is reduced to about 1.5 μm, when light from the mask opening reaches the coating film surface, it hits the edge of the mask opening due to the influence of light interference. The light intensity is reduced in the area. Therefore, the length of the curved portion of the green colored layer G is also long, and the shape is rounded. When light enters the photoelectric conversion element from the rounded portion, noise is generated.

  Moreover, by making it fine, the width of the light irradiated to the coating film becomes wider than the opening width of the mask pattern due to the interference of the light passing through the mask. For this reason, the change of the pattern line width becomes larger with respect to the irradiation exposure amount. For this reason, when a certain pattern is formed, it is difficult to control the exposure amount and the productivity is deteriorated.

  This invention provides the photosensitive coloring composition for color filters used for a solid-state image sensor which solves such a problem.

  Below, the photosensitive coloring composition for color filters used for the solid-state image sensor based on this embodiment is demonstrated.

  The photosensitive coloring composition for color filters according to this embodiment contains (A) a photopolymerizable monomer, (B) an oxime ester-based initiator, (C) a coloring agent, and (D) a solvent.

<< (A) Photopolymerizable monomer >>
The color filter photosensitive coloring composition according to the present embodiment includes (A) a photopolymerizable monomer having (meth) acrylic compounds having 3 or less unsaturated bond groups in one molecule as a photopolymerizable monomer in a total amount of 50 photopolymerizable monomers. It is contained in an amount of 80% to 80% by mass.

  (Meth) acrylic compounds having 3 or less unsaturated bond groups in one molecule are polyfunctional acrylates and / or polyfunctional methacrylate (meth) acrylic acid esters having 3 or less unsaturated bond groups in one molecule. Kind.

  Specifically, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, EO-modified phthalic acid (meth) acrylate, PO-modified phthalic acid (meth) acrylate, acrylated isocyanurate, bis (acrylate) Roxyneopentyl glycol) adipate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, tetraethylene glycol di (meth) acrylate, EO modified trimethylolpropane triacrylate, PO modified trimethylolpropane tri (meta) ) Acrylate, tripropylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone modified tris (acrylo) Shiechiru) isocyanurate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate.

  These commercially available products include KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R712, KAYARAD R-604, KAYARAD R-684, manufactured by Nippon Kayaku Co., Ltd. KAYARAD GPO-303, KAYARAD TMPTA, and Toa Gosei M210, M220, M225, M305, M309, M325, M350, Osaka Organic Chemicals V # 310HP, V # 335HP, V # 700, V # 295, V # 330 , V # 360, V # GPT, etc. can be suitably used.

  These (meth) acrylic compounds can be used singly or as a mixture of two or more at any ratio as required.

  Moreover, it is preferable that the molecular weight of the (meth) acryl compound which has 3 or less unsaturated bond groups in 1 molecule is the range of 300-540. When the molecular weight is smaller than 300, the pattern is easily scraped in the developing process after the exposure process, which may be one of the factors of the film thickness variation of the pattern formation. On the other hand, when the molecular weight is larger than 540, the change in film thickness with respect to the exposure amount may become large.

  The molecular weight and average molecular weight of the monomer specified in the present specification are expressed by theoretical values converted from atomic weights. The first decimal place was calculated as a significant figure, and the calculated value was rounded off to exclude the minority.

  Moreover, it is preferable that the coloring composition which concerns on this embodiment contains the (meth) acryl compound which has further 5 or 6 unsaturated bond groups in 1 molecule as a photopolymerizable monomer.

  By including the (meth) acrylic compound, a color filter having good flatness and pattern shape can be produced. Further, when forming the pattern, it is preferable because a change in the line width of the pattern with respect to the irradiation exposure amount can be suppressed to be small, and a color filter that can deal with high definition with little residue is preferable.

  Examples of the (meth) acrylic compound having 5 or 6 unsaturated bonding groups in one molecule include dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta ( And (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  Examples of these commercially available products include KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, and Nippon Kayaku Co., Ltd. KAYARAD DPCA-120, Toa Gosei Co., Ltd. M-402, Osaka Organic V # 400, etc. can be used suitably.

  These (meth) acrylic compounds can be used singly or as a mixture of two or more at any ratio as required.

  The content of the (meth) acrylic compound having 3 or less unsaturated bonding groups in one molecule is 50% by mass or more and 80% by mass or less in the total amount of the photopolymerizable monomer. When it is more than 80% by mass, the sensitivity is lowered. When the amount is less than 50% by mass, the line width change amount and the film thickness change amount with respect to the exposure amount become large when the coating film is formed.

  In addition, when a photopolymerizable monomer consists only of the (meth) acryl compound which has more than three unsaturated bond groups in 1 molecule, the line | wire width change amount with respect to an exposure amount will become large.

  (A) It is preferable that content of a photopolymerizable monomer is 5.0 mass% or more and 40.0 mass% or less in 100 mass% of total solid content of the photosensitive coloring composition. More preferably, it is the range of 10.0 mass% or more and 30.0 mass% or less. (A) When the content of the photopolymerizable monomer is less than 5.0% by mass, the exposure sensitivity is lowered, the productivity is deteriorated, and the taper length of the pattern shape is increased. is there. On the other hand, when the amount is more than 40.0% by mass, the amount of the photopolymerizable monomer is increased in the solid content, the addition amount of the resin binder is decreased in the photosensitive coloring composition, and when the coating film is formed, The film thickness variation may increase.

<< (B) Oxime ester initiator >>
As the oxime ester-based initiator used in the photosensitive coloring composition according to this embodiment, a known compound known as a photopolymerization initiator for a photosensitive coloring composition for use in electronic parts or the like may be used. it can. For example, JP-A-57-116047, JP-A-61-2558, JP-A-62-2201859, JP-A-62-286961, JP-A-7-278214, JP-A-2000- No. 80068, JP-A No. 2001-233842, JP-A No. 2004-534797, JP-A No. 2002-538241, JP-A No. 2004-359639, JP-A No. 2005-97141, JP-A No. 2005-220097 Selected from the compounds described in each of the patent publications such as Japanese Patent Publication, International Publication No. 05/080337 pamphlet, Japanese Patent Publication No. 2002-519732, Japanese Patent Laid-Open No. 2001-235858, Japanese Patent Laid-Open No. 2005-227525, etc. it can.

  Preferred oxime ester initiators include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), 1,2- And octadione-1- [4- (phenylthio)-, 2- (O-benzoyloxime)].

In combination with an oxime ester initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 Acetophenone photopolymerization initiators such as -one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin Benzoin photopolymerization initiators such as ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated Benzophenone photopolymerization initiators such as zophenone and 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthone photopolymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-y ) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl Triazine photopolymerization initiators such as-(piperonyl) -6-triazine and 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazoles A system photopolymerization initiator or the like may also be used.
As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalo A compound such as phenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone may be used in combination.

<< (C) Colorant >>
As a colorant used in the photosensitive coloring composition according to the present embodiment, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 168, 177, 178, 179, 184, 185, 187, 192, 200, 202, 208, 210, Red pigments such as 216, 220, 223, 224, 226, 240, 254, 255, 264, and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red photosensitive resin composition.

  When forming a green colored layer, green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58 can be used. A yellow pigment can be used in combination with the green photosensitive resin composition.

  In the case of forming a blue colored layer, blue pigments such as C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 64, and 80 can be used. A purple pigment can be used in combination with the blue photosensitive resin composition.

  When forming a yellow colored layer, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177 It can be used yellow pigments such 179,180,181,182,185,187,188,193,194,198,199,213,214.

  In the case of forming a purple colored layer, pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used.

  When forming a magenta colored layer, CI Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 146, Pigments such as 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272 can be used. A yellow pigment can be used in combination with the magenta photosensitive resin composition.

  In the case of forming a cyan colored layer, pigments such as C.I. Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, and 80 can be used.

  In the case of forming an orange colored layer, pigments such as C.I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 can be used.

<< (D) Solvent >>
In the photosensitive coloring composition according to the present embodiment, the dye is sufficiently dispersed in the dye carrier, and is applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 3.0 μm. In order to make it easy to form each colored layer, an organic solvent is blended. Preferred organic solvents include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl -N amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, etc., depending on the monomer composition, type of polymerization initiator used, etc. Can be used alone or in combination.

<Resin binder>
Moreover, the photosensitive coloring composition for color filters used for the solid-state image sensor of the invention may contain a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin as a resin binder.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
As the active energy ray-curable resin, a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

《Polyfunctional thiol》
Moreover, the photosensitive coloring composition for color filters used for the solid-state image sensor which concerns on this embodiment can contain the polyfunctional thiol which has an effect | action as a chain transfer agent.

  The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, penta Erythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination of two or more.

  The amount of the polyfunctional thiol used is preferably 0.1% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 20% by mass or less based on the total solid content of the photosensitive coloring composition. If it is less than 0.1% by mass, the effect of adding a polyfunctional thiol is insufficient, and if it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

<Storage stabilizer>
In addition, the photosensitive coloring composition according to this embodiment may contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.

<< Preparation Method of Pigment Dispersion >>
The pigment dispersion as a colorant used in the photosensitive coloring composition according to this embodiment can be obtained by dispersing a dye in a dye carrier. Examples of a method for finely dispersing the pigment in the pigment carrier include a method using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. Moreover, you may mix what each disperse | distributed finely in the pigment | dye carrier separately. When the dye is dispersed in the dye carrier, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a dye derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing reaggregation of the pigment after dispersion, when a colorant formed by dispersing the pigment in the dye carrier using the dispersion aid is used. A color filter having excellent transparency can be obtained.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and acts to stabilize the dispersion of the pigment on the dye carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactants such as: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as nylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.

  The photosensitive coloring composition for color filters according to this embodiment is prepared by uniformly mixing the components described above. In this case, coarse particles having a particle size of 5 μm or more, preferably coarse particles having a particle size of 1 μm or more, more preferably, coarse particles having a particle size of 0.3 μm or more and mixed dust are removed by means of centrifugation, a sintered filter, a membrane filter, or the like. It is preferable to carry out.

  A color filter used for a solid-state imaging device can be formed by applying, exposing, developing, and heat-treating the photosensitive coloring composition described above. This color filter comprises at least one red colored layer, at least one green colored layer, and at least one blue colored layer.

  By using the photosensitive coloring composition for color filters used in the solid-state imaging device according to this embodiment, a color filter having excellent flatness can be formed. When the flatness of the color filter is high, there is an advantage that it is easy to improve the effective sensitivity of the pixel as compared with the case where the flatness is low.

  The present invention is not limited to the above embodiment. The said embodiment is an illustration and what show | plays the same effect is included by the technical scope of this invention.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

  In Examples and Comparative Examples, 11 types of samples (Examples 1 to 7 and Comparative Examples 1 to 4) were prepared for the photosensitive green coloring composition for a color filter used in a typical solid-state imaging device.

  First, acrylic varnish A used in Examples and Comparative Examples was synthesized to prepare a green pigment dispersion.

<Synthesis of acrylic varnish A>
Place 370 parts of propylene glycol monomethyl ether acetate in a reaction vessel and heat to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 12.3 parts of methacrylic acid, 49.2 parts of benzyl methacrylate, paracumylphenol ethylene A mixture of 24.2 parts of oxide-modified acrylate (“Aronix M-110” manufactured by Toagosei Co., Ltd.) and 14.3 parts of 2-hydroxyethyl methacrylate was added dropwise over 1 hour to conduct a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of propylene glycol monomethyl ether acetate was added, and further reacted at 80 ° C. for 1 hour. Subsequently, an acrylic resin solution was obtained.

  The weight average molecular weight of the obtained acrylic resin was about 30000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes, the nonvolatile content was measured, and propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Ether acetate was added to obtain an acrylic varnish A solution.

<Preparation of green pigment dispersion>
[Green pigment dispersion 1]
Halogenated copper phthalocyanine green pigment 12.0 parts (CI Pigment Green 36)
Acrylic varnish A (solid content 20%) 35.0 parts PGMAC 52.0 parts Resin type dispersant 1.0 part (EFKA4300)
[Green pigment dispersion 2]
Except for replacing the halogenated copper phthalocyanine green pigment (CI Pigment Green 36) with the halogenated copper phthalocyanine green pigment (CI Pigment Green 7),
Green pigment dispersion 2 was obtained in the same manner as the preparation of green pigment dispersion 1.

Example 1
[Green coloring composition 1]
A mixture having the composition shown below was stirred and mixed to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 1.

Green coloring dispersion 1 42.5 parts by mass Photopolymerizable monomer (unsaturated bond group number: 2) 3.4 parts by mass (Nippon Kayaku KAYARAD R-684 molecular weight: 304)
Photopolymerizable monomer (unsaturated bond group number: 5 to 6) 3.2 parts by mass (M-402, manufactured by Toagosei Co., Ltd.)
-Acrylic varnish A (solid content 20%) 3.9 parts by mass-Photopolymerization initiator 1.0 part by mass (Ciba Specialty Chemicals "OXE-02": oxime ester initiator)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part by mass PGMAC 45.9 parts by mass << Example 2 >>
[Green coloring composition 2]
The mixture having the composition shown below was stirred and mixed so as to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 2.

Green colored dispersion 1 10.8 parts by mass Green colored dispersion 2 43.1 parts by mass Photopolymerizable monomer (unsaturated bond group number: 3) 2.3 parts by mass (M-350, manufactured by Toagosei Co., Ltd. Molecular weight: 428)
Photopolymerizable monomer (unsaturated bond group number: 5 to 6) 2.3 parts by mass (M-402, manufactured by Toagosei Co., Ltd.)
-Acrylic varnish A (solid content 20%) 2.7 parts by mass-Photopolymerization initiator 1.0 part by mass (Ciba Specialty Chemicals "OXE-02": oxime ester initiator)
-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part by mass-PGMAC 37.8 parts by mass << Example 3 >>
[Green coloring composition 3]
A mixture having the composition shown below was stirred and mixed to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 3.

Green colored dispersion 1 12.8 parts by weight Green colored dispersion 2 51.0 parts by weight Photopolymerizable monomer (unsaturated bond group number: 2) 0.9 parts by weight (KAYARAD R-684 manufactured by Nippon Kayaku) Molecular weight: 304)
・ Photopolymerizable monomer (unsaturated bond group number: 5-6) 0.5 part by mass (M-402, manufactured by Toagosei Co., Ltd.)
・ Acrylic varnish A (solid content 20%) 8.6 parts by mass ・ Photopolymerization initiator 1.0 part by mass (“OXE-02” manufactured by Ciba Specialty Chemicals Co., Ltd .: oxime ester initiator)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part by mass PGMAC 25.1 parts by mass << Example 4 >>
[Green coloring composition 4]
A mixture having the composition shown below was stirred and mixed to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 4.

-Green colored dispersion 1 42.5 parts by mass-Photopolymerizable monomer (unsaturated bond group number: 3) 3.4 parts by mass (M-325, molecular weight: 537, manufactured by Toagosei Co., Ltd.)
Photopolymerizable monomer (unsaturated bond group number: 5 to 6) 3.2 parts by mass (M-402, manufactured by Toagosei Co., Ltd.)
-Acrylic varnish A (solid content 20%) 3.9 parts by mass-Photopolymerization initiator 1.0 part by mass (Ciba Specialty Chemicals "OXE-02": oxime ester initiator)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part by mass PGMAC 45.9 parts by mass << Example 5 >>
[Green coloring composition 5]
A mixture having the composition shown below was stirred and mixed to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 5.

Green colored dispersion 1 10.8 parts by mass Green colored dispersion 2 43.1 parts by mass Photopolymerizable monomer (unsaturated bond group number: 3) 3.6 parts by mass (M-350, manufactured by Toagosei Co., Ltd. Molecular weight: 428)
-Photopolymerizable monomer (unsaturated bond group number: 5-6) 0.9 part by mass (M-402, manufactured by Toagosei Co., Ltd.)
-Acrylic varnish A (solid content 20%) 2.7 parts by mass-Photopolymerization initiator 1.0 part by mass (Ciba Specialty Chemicals "OXE-02": oxime ester initiator)
-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part by mass-PGMAC 37.8 parts by mass << Example 6 >>
[Green Coloring Composition 6]
A mixture having the composition shown below was stirred and mixed to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 6.

-Green colored dispersion 1 42.5 parts by mass-Photopolymerizable monomer (unsaturated bond group number: 2) 3.4 parts by mass (Nippon Kayaku KAYARAD DEGDA molecular weight: 214)
Photopolymerizable monomer (unsaturated bond group number: 5 to 6) 3.2 parts by mass (M-402, manufactured by Toagosei Co., Ltd.)
-Acrylic varnish A (solid content 20%) 3.9 parts by mass-Photopolymerization initiator 1.0 part by mass (Ciba Specialty Chemicals "OXE-02": oxime ester initiator)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part by mass PGMAC 45.9 parts by mass << Example 7 >>
[Green coloring composition 7]
A mixture having the composition shown below was stirred and mixed so as to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 7.

Green coloring dispersion 1 42.5 parts by mass Photopolymerizable monomer (unsaturated bond group number: 3) 3.4 parts by mass (Nippon Kayaku KAYARAD D-330 molecular weight: 584)
Photopolymerizable monomer (unsaturated bond group number: 5 to 6) 3.2 parts by mass (M-402, manufactured by Toagosei Co., Ltd.)
-Acrylic varnish A (solid content 20%) 3.9 parts by mass-Photopolymerization initiator 1.0 part by mass (Ciba Specialty Chemicals "OXE-02": oxime ester initiator)
-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part by mass-PGMAC 45.9 parts by mass << Comparative Example 1 >>
[Green coloring composition 8]
A mixture having the composition shown below was stirred and mixed to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 8.

-Green colored dispersion 1 42.5 parts by mass-Photopolymerizable monomer (unsaturated bond group number: 5-6) 6.6 parts by mass (M-402, manufactured by Toagosei Co., Ltd.)
-Acrylic varnish A (solid content 20%) 3.9 parts by mass-Photopolymerization initiator 1.0 part by mass (Ciba Specialty Chemicals "OXE-02": oxime ester initiator)
-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part by mass-PGMAC 45.9 parts by mass << Comparative Example 2 >>
[Green Coloring Composition 9]
A mixture having the composition shown below was stirred and mixed to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 9.

Green coloring dispersion 1 42.5 parts by mass Photopolymerizable monomer (unsaturated bond group number: 4) 3.4 parts by mass (ditrimethylolpropane tetraacrylate molecular weight: 466)
Photopolymerizable monomer (unsaturated bond group number: 5 to 6) 3.2 parts by mass (M-402, manufactured by Toagosei Co., Ltd.)
-Acrylic varnish A (solid content 20%) 3.9 parts by mass-Photopolymerization initiator 1.0 part by mass (Ciba Specialty Chemicals "OXE-02": oxime ester initiator)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part by mass PGMAC 45.9 parts by mass << Comparative Example 3 >>
[Green Coloring Composition 10]
A mixture having the composition shown below was stirred and mixed so as to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 10.

-Green color dispersion 1 42.5 parts by mass-Photopolymerizable monomer (unsaturated bond group number: 2) 6.6 parts by mass (Nippon Kayaku KAYARAD R-684 molecular weight: 304)
-Acrylic varnish A (solid content 20%) 3.9 parts by mass-Photopolymerization initiator 1.0 part by mass (Ciba Specialty Chemicals "OXE-02": oxime ester initiator)
-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part by mass-PGMAC 45.9 parts by mass << Comparative Example 4 >>
[Green Coloring Composition 11]
A mixture having the composition shown below was stirred and mixed to be uniform, and then filtered through a 0.45 μm filter to obtain a green colored composition 11.

Green coloring dispersion 1 42.5 parts by mass Photopolymerizable monomer (unsaturated bond group number: 2) 3.4 parts by mass (Nippon Kayaku KAYARAD R-684 molecular weight: 304)
Photopolymerizable monomer (unsaturated bond group number: 5 to 6) 3.2 parts by mass (M-402, manufactured by Toagosei Co., Ltd.)
Acrylic varnish A (solid content 20%) 3.9 parts by mass Photopolymerization initiator 1.0 part by mass (“Irg379” manufactured by Ciba Specialty Chemicals: α-aminoalkylphenone initiator)
・ Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 parts by mass PGMAC 45.9 parts by mass <Evaluation of colored composition>
About the above coloring composition, the following method evaluated the shape, the residual film rate, exposure sensitivity, exposure dose dependency, the film thickness uniformity of a pattern, and residue evaluation. The results are shown in Table 1 below.

[Pattern formation]
On a 6-inch silicon wafer, a flattening film resist solution (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) was applied by a spin coating method, and pre-baked for 6 minutes with a 100 ° C. hot plate. Furthermore, it processed in 230 degreeC oven for 1 hour, the coating film was hardened, and the planarizing film with a film thickness of 1.0 micrometer was formed.

  The green photosensitive coloring composition thus obtained was applied onto a silicon wafer with a flattening film by a spin coater, and heat-treated for 1 minute on a hot plate at 100 ° C. as a prebake. The film thickness after pre-baking was adjusted to 0.9 μm.

  Next, using an I-line stepper (FPA-5510iZ manufactured by Canon), exposure was performed with a focal length of −0.6 μm through a 1.1 μm square pixel pattern mask. The exposure amount was 5,000 J.

  The exposed coating film was developed with an organic alkaline developer (OD210 manufactured by ADEKA) for 1 minute, washed with paddle water for 1 minute, spin-dried, and the substrate was dried. After developing and washing with water, a green colored pattern was obtained. The obtained green coloring pattern was heat-treated for 4 minutes on a hot plate at 230 ° C. The thickness of the green colored pattern after the heat treatment was 0.85 μm. The film thickness was measured with an AFM (Atomic Force Microscope) manufactured by Toyo Technica (i-nano).

[Shape evaluation]
About the shape of the formed pattern, the shape for 32 pixels from the frame of the image sensor was observed and evaluated with a length measurement SEM (scanning electron microscope) (manufactured by KLA-Tenor: eCD2-XP). As shown in FIG. 3, when the difference 33 between the upper base line width 31 and the lower base line width 32 of the formed pattern portion is 0.20 μm or less, it is ◯, when the difference 33 is 0.21 μm or more and 0.24 μm or less, In the case of 25 μm or more, it was set as x.

  As shown in FIG. 3, when observed from the top of the pattern with a length measurement SEM, a difference in shading can be confirmed between the upper bottom portion and the tapered portion of the pattern.

[Residual film rate evaluation]
The film thickness change rate when the film thickness after coating and pre-baking is A, the film thickness after exposure, development, and baking at 230 ° C. for 4 minutes is B (residual film ratio = B / A × 100). When it was 85% or more, it was evaluated as ◯, when it was 78% or more and 84% or less, Δ, and less than 78% was rated as x.

[Exposure sensitivity]
Using an i-line stepper (Canon FPA-5510iZ), through a 1.1 μm square pixel pattern mask, with a focal length of −0.6 μm, an exposure range of 1,000 J to 12,000 J is 1,000 J When the exposure sensitivity is less than 5,000 J, the exposure amount at which the bottom line width is 1.1 μm after exposure irradiation, development at an interval or 100 J interval, development, and baking at 230 ° C. for 4 minutes. △ J is less than 9,000J, and △ is more than 9,000J.

[Exposure dose dependency]
Using an i-line stepper (Canon FPA-5510iZ) and a 1.1μm square pixel pattern mask with a focal length of -0.6μm, an exposure range of 1,000J to 10,000J When the amount of change in the lower bottom line width with respect to the exposure amount after exposure irradiation at intervals, development, and baking at 230 ° C. for 4 minutes is 0.20 μm or less, when it is greater than 0.20 μm and less than 0.25 μm Δ, x greater than 0.25 μm.

[Pattern thickness uniformity]
There is a step at the end of one chip of the solid-state imaging device. Due to such a step, the film thickness may increase at the end of one chip. Therefore, for the film thickness uniformity, the film thickness change was measured at the pixel 31 where 33 was omitted from the frame of one chip. The case where the measured change amount of the film thickness was 0.05 μm or less was rated as “◯”, the case where it was larger than 0.05 μm and 0.07 μm or less was Δ, and the case where it was larger than 0.07 μm was marked as “X”.

[Residue evaluation]
The exposed coating film was developed, washed with water, and the dried substrate was dried. The substrate part where the substrate pattern was not formed was observed with a length measuring SEM (scanning electron microscope).

The evaluation results of the above characteristics are shown in Table 1 below.

  As shown in Table 1 above, Examples 1 to 7 containing a (meth) acrylic compound having 3 or less unsaturated bonding groups in one molecule in a total amount of the photopolymerizable monomer of 50 to 80% by mass. The coloring composition shows satisfactory results in all of the properties of shape, residual film ratio, irradiation exposure sensitivity, exposure dose dependency, film thickness uniformity, and residue. Therefore, it can be said that the colored compositions of Examples 1 to 7 can be applied to high-definition solid-state imaging devices. Moreover, the solid-state image sensor provided with the color filter obtained using the photosensitive coloring composition of these Examples 1-7 improved the taking-in efficiency of incident light more than before.

  In addition, the photosensitive coloring composition of Example 6 using a (meth) acryl compound having a molecular weight of less than 300 as a (meth) acrylic compound having 3 or less unsaturated bond groups in one molecule has a molecular weight of 300 or more and 540 or less ( Compared to the photosensitive coloring compositions of Examples 1 to 5 using a (meth) acrylic compound, the shape and the remaining film ratio are slightly inferior, but all other properties are excellent.

  The photosensitive coloring composition of Example 7 using a (meth) acrylic compound having a molecular weight of more than 540 as a (meth) acrylic compound having 3 or less unsaturated bonding groups in one molecule has a molecular weight of 300 or more and 540. Compared with the photosensitive coloring compositions of Examples 1 to 5 using the (meth) acrylic compound as described below, the exposure dose dependency and the film thickness uniformity are slightly inferior, but all other properties are excellent.

  On the other hand, the photosensitive coloring composition of Comparative Example 1 in which the photopolymerizable monomer (A) is composed only of (meth) acrylic compounds having 5 or 6 unsaturated bond groups in one molecule has a shape, a residual The film rate and irradiation exposure sensitivity are excellent, but the exposure dose dependency, film thickness uniformity and residue are inferior.

  (A) The photosensitive coloring composition of Comparative Example 2 in which the photopolymerizable monomer is composed only of a (meth) acrylic compound having four unsaturated bond groups in one molecule has a shape, a remaining film ratio, irradiation exposure sensitivity, The film thickness uniformity and residue are excellent, but the exposure dose dependency is poor.

  (A) The photosensitive coloring composition of Comparative Example 3 in which the photopolymerizable monomer is composed only of a (meth) acrylic compound having two unsaturated bond groups in one molecule has exposure dose dependency, film thickness uniformity, and Although the residue is excellent, the shape, the remaining film rate and the irradiation exposure sensitivity are inferior. In particular, the irradiation exposure amount required 12000J.

  As the photopolymerization initiator, (B) the photosensitive coloring composition of Example 4 that does not use the oxime ester-based initiator is excellent in exposure dose dependency, film thickness uniformity, and residue, but the shape and Irradiation exposure sensitivity is inferior. In particular, the irradiation exposure amount required 12000J.

<Preparation of blue pigment dispersion>
[Blue pigment dispersion 1]
A mixture having the following composition was uniformly stirred and mixed, and then dispersed in a sand mill using glass beads having a diameter of 1 mm for 5 hours, and then filtered through a 5 μm filter to prepare a blue pigment dispersion 1.

Blue pigment: C.I. I. Pigment Blue 15: 6 12.0 parts by mass (“Rionol Blue ES” manufactured by Toyo Ink Manufacturing Co., Ltd.)
・ Dispersant 1.0 part by mass (“Sols Birds 20000” manufactured by Zeneca) ・ Acrylic varnish (solid content 20%)
Acrylic varnish A (solid content 20%) 35.0 parts by mass PGMAC 52.0 parts by mass Then, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 0.45 μm filter to give a blue color. Composition 1 was obtained.

Blue colored dispersion 1 63.8 parts by mass Photopolymerizable monomer (unsaturated bond group number: 3) 1.3 parts by mass (M-325, molecular weight: 537, manufactured by Toagosei Co., Ltd.)
-Photopolymerizable monomer (unsaturated bond group number: 5 to 6) 1.3 parts by mass (M-402, manufactured by Toagosei Co., Ltd.)
-Acrylic varnish A (solid content 20%) 2.8 parts by mass-Photopolymerization initiator 1.1 parts by mass (Ciba Specialty Chemicals "OXE-01": oxime ester initiator)
-PGMAC 29.8 parts by mass <Preparation of red coloring composition>
[Red coloring composition 1]
A mixture having the following composition was stirred and mixed uniformly, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a red pigment dispersion 1.

-Red pigment: C.I. I. Pigment Red 254 10.0 parts by mass (“Rionol Blue ES” manufactured by Toyo Ink Manufacturing Co., Ltd.)
-Red pigment: C.I. I. Pigment Red 177 2.0 parts by mass (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals)
・ Dispersant 1.0 part by mass (“Ajisper PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.)
-Acrylic varnish (solid content 20%) 35.0 parts by mass-Propylene glycol monomethyl ether acetate (PGMAC)
52.0 parts by mass Thereafter, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 0.45 μm filter to obtain a red colored composition 1.

-Red colored dispersion 1 63.8 parts by mass-Photopolymerizable monomer (unsaturated bond group number: 3) 1.9 parts by mass (M-325, molecular weight: 537, manufactured by Toagosei Co., Ltd.)
・ Photopolymerizable monomer (unsaturated bond group number: 5 to 6) 0.6 part by mass (M-402, manufactured by Toagosei Co., Ltd.)
-Acrylic varnish A (solid content 20%) 2.8 parts by mass-Photopolymerization initiator 1.1 parts by mass (Ciba Specialty Chemicals "OXE-01": oxime ester initiator)
-PGMAC 29.8 parts by mass <Manufacture of color filter for solid-state imaging device>
[Color filter 1 for solid-state image sensor]
On a 6-inch silicon wafer, a planarization film resist solution (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) was applied by a spin coating method, and heat-treated for 6 minutes on a hot plate at 100 ° C. as a prebake. Furthermore, it processed in 230 degreeC oven for 1 hour, the coating film was hardened, the 1.0 micrometer planarizing film was formed, and the wafer with a planarizing film was obtained.

  The green coloring composition 1 was applied onto a silicon wafer with a flattening film by a spin coater, and pre-baked and heat-treated with a hot plate at 100 ° C. for 1 minute. The film thickness after pre-baking was adjusted to 0.9 μm.

  Next, using an i-line stepper (FPA-5510iZ manufactured by Canon), irradiation was performed at an exposure amount of 4,000 J through a 1.1 μm square pixel pattern mask with a focal length of −0.6 μm.

  The exposed coating film was developed with an organic alkaline developer (OD210 manufactured by ADEKA) for 1 minute, washed with paddle water for 1 minute, spin-dried, and the substrate was dried. After development and washing with water, a green colored pattern was obtained. The obtained green coloring pattern was heat-treated with a hot plate at 230 ° C. for 1 hour. The film thickness of the green pattern after the heat treatment was 0.80 μm. The line width of the green pattern was 1.23 μm. The difference between the upper base line width and the lower base line width of the green pattern was 0.12 μm. The amount of change in film thickness from the one chip frame to within 32 pixels was 0.04 μm. The film thickness was measured with an AFM (Atomic Force Microscope) manufactured by Toyo Technica (i-nano).

  The blue coloring pattern and the red coloring pattern were also formed in the same manner as the green coloring pattern except for the exposure amount to obtain a color filter. The amount of exposure was set to 8,000 J for the blue coloring pattern and 4,000 J for the red wearing pattern. The formed blue colored pattern had a thickness of 0.87 μm, and the red colored pattern had a thickness of 0.87 μm.

  A planarizing layer was provided on the color filter formed as described above. The planarization layer was formed, for example, by applying a planarization film resist solution (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.). A transparent resin layer was formed on the planarizing layer using, for example, an acrylic resin coating solution. Next, on the transparent resin layer, for example, a lens matrix material made of, for example, phenol resin having alkali solubility, photosensitivity, and heat flow was applied.

  Next, using a known photolithography process, the lens matrix material was patterned so as to leave a region serving as the lens matrix. The remaining lens matrix material was heat-treated and thermally reflowed, and transformed into a hemispherical shape to form a lens matrix. By setting the reflow amount to an appropriate amount of about 0.1 μm on one side, a smooth hemisphere having a gap between the unit lens molds of, for example, about 0.24 μm could be achieved.

Thereafter, a transfer process of the shape of the lens matrix was performed on the transparent resin layer by dry etching using a mixed gas of CF ₄ and C ₄ F ₈ using the lens matrix as a mask to form a microlens. If the lens matrix and the transparent resin layer are uniformly etched from above, the etching proceeds downward while maintaining the shape of the lens matrix, so the transparent resin layer is etched to the same shape as the lens matrix. Can do. The microlens can be formed to have a height of 1 μm and a gap between unit lenses of 0.04 μm.

  The color filter for a solid-state imaging device thus manufactured had a good pattern shape, was flat, and had no step between colored pixels. As a result, it was possible to manufacture a solid-state imaging device with a color filter with good efficiency of light incident on the photoelectric conversion device.

  DESCRIPTION OF SYMBOLS 1 ... Solid-state imaging device, 2 ... Semiconductor chip, 3 ... Flattening layer, 4 ... Color filter, 5 ... Micro lens array, 21 ... Photoelectric conversion element, 31 ... Pattern upper base, 32 ... Pattern lower Bottom, 33 ... Pattern taper.

Claims (4)

  (A) A photopolymerizable monomer, (B) an oxime ester initiator, (C) a colorant, and (D) a photosensitive coloring composition for a color filter, which comprises (A) a photopolymerizable monomer. However, it is used for a solid-state imaging device characterized by containing a (meth) acrylic compound having 3 or less unsaturated bonding groups in one molecule in an amount of 50 to 80% by mass of the total amount of the photopolymerizable monomer. Photosensitive coloring composition for color filters.   (A) The photopolymerizable monomer further contains a (meth) acrylic compound having 5 or 6 unsaturated bonding groups in one molecule, wherein the color used in the solid-state imaging device according to claim 1 Photosensitive coloring composition for filters.   The molecular weight of the (meth) acrylic compound having 3 or less unsaturated bond groups in one molecule is 300 or more and 540 or less, for a color filter used for a solid-state imaging device according to claim 1 or 2 Photosensitive coloring composition.   A step of applying a photosensitive coloring composition for a color filter used in the solid-state imaging device according to any one of claims 1 to 3 on a substrate and drying, and then (1) exposing with an ultraviolet exposure device, A color filter for a solid-state imaging device, which is obtained by (2) a step of developing with an alkaline aqueous solution, and (3) a step of thermal baking.

Images