JP2004170952A - Positive red color photosensitive composition and color filter using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive red color photosensitive composition which forms a pattern having the film thickness less than 1.5 μm and excellent selectivity for transmitting light with a small quantity of exposure light, and shows a favorable film residual rate by development and high solvent resistance. <P>SOLUTION: The positive color photosensitive composition contains a dye, a photosensitive agent, a hardening agent and a solvent, and further may contain an alkali soluble resin. The composition contains 55.0 to 63.0 pts.mass of the dye content, 10.0 to 30.0 pts.mass of the photosensitive agent content, 10.0 to 25.0 pts.mass of the hardening agent content, and ≤10.0 pts.mass of the alkali soluble resin content with respect to the total 100 pts.mass of the solid content. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a positive red colored photosensitive composition.

In a solid-state imaging device using a CCD, a band-like pattern (FIG. 2), a mosaic-like (lattice-like) pattern (FIG. 3) and the like are formed on the same plane of a support substrate (1) as shown in FIG. A color filter (2) in which a large number of red pixels (R), green pixels (G), and blue pixels (B) are collected is used.
In these color filters, it is required that each pixel selectively transmits only light in the wavelength range of each color and selectively transmits light that reliably blocks visible light in other wavelength ranges. In these color filters, each color pattern pixel needs a sufficient color density.
Further, with the miniaturization and higher definition of CCD, finer pattern pixels are required for these color filters.
That is, by reducing the size of each pattern of the color filter, the size of the CCD equipped with the color filter can be reduced, and the number of pixels of the color filter can be increased to obtain higher-resolution image information.
On the other hand, when the size of the color filter pattern is reduced, it is desired to reduce the thickness of the color filter. A color filter having a small thickness allows light incident obliquely to the CCD to reach a photosensitive portion below the color filter, thereby increasing the aperture ratio of the CCD.
That is, the obliquely incident light on the CCD can pass through the color filter and reach the CCD photosensitive portion.

As a method of manufacturing such a color filter, a method of manufacturing by a photolithography method using a colored photosensitive composition in which a photosensitive composition represented by a photoresist contains a pigment such as a pigment or a dye has been developed. Have been. (See, for example, Patent Documents 1 to 3.)
A specific method for manufacturing a color filter is shown in FIG. 4, for example. First, a light receiving element is formed on the surface of a substrate such as a silicon wafer (20). Subsequently, an electrode for transferring electrons of the light receiving element is formed on the surface of the silicon wafer (30). In forming a color filter on the solid-state imaging device forming substrate (substrate on which the light receiving portion and the transfer electrode are formed on the surface of the silicon wafer) formed in this manner, a flattening film (40) is used to flatten the substrate surface. ) Is formed. Next, on the substrate, the colored photosensitive composition of the present invention is applied, pattern projection exposure, pattern development, and heat curing to form a pixel (50a; color pixel (1)) of a color filter. This process is repeated for each color, and three color filters (50a; color pixel (1), 50b; color pixel (2) and 50c; color pixel (3)) are placed on the same plane of the solid-state imaging device forming substrate. Form. Further, a protective film (60) is formed for protecting the surface of the color filter.
According to the above-described manufacturing method, a color filter is formed, which is an aggregate of fine pattern regions colored in three primary colors of light (red, green, and blue) by a pigment such as a pigment or a dye.
However, the color filter formed using the conventional colored photosensitive composition has a large film thickness, and if each pattern region forming the color filter is reduced, incident light cannot be sufficiently utilized, and a clear image can be obtained. There is a problem that it is difficult to record.
Therefore, when a color filter having a film thickness of less than 1.5 μm is formed using a conventional colored photosensitive composition, there is a problem that a color filter having a sufficient color density cannot be obtained.

Here, in order to obtain a sufficient color density even when the film thickness is thinner than 1.5 μm, when the dye density is increased in a conventionally used positive-type colored photosensitive composition using a dye, pattern projection is performed. There was a problem that the pattern formed in the developing step after exposure was eluted, and the pattern could not be formed.
Due to the elution of this pattern, the formed color filter cannot exhibit the expected color density, and the color density does not become uniform within the pixel, causing color unevenness in the image input from the CCD or color reproduction of the image data. There were problems such as deterioration in performance. In particular, in forming a red color filter, it is difficult to obtain a sufficient color density when forming a thin film because the molecular absorption coefficient of the red dye is lower than that of green and blue, and the balance of red, green, and blue There was a problem that it was difficult to take.

JP-A-2-127602, page 6, lower right column, line 15 to page 25 lower left column, line 14 JP-A-4-283701, page 2, right column, line 38 to page 3, right column, line 43 JP-A-2002-14220, page 3, right column, line 19 to page 11, right column, line 15

  An object of the present invention is to provide a positive type red color having a film thickness of less than 1.5 μm, having excellent selectivity of transmitted light, forming a pattern with a small amount of exposure, having a good residual film ratio of development, and having good solvent resistance. It is to provide a photosensitive composition.

The present inventors have conducted intensive studies to solve the above-described problems, and as a result of using a colored photosensitive composition containing a dye, a photosensitizer and a curing agent at a specific ratio, and further including an alkali-soluble resin. It has been found that a positive red-colored photosensitive composition capable of forming a pattern with a small amount of exposure, having a good residual film ratio and solvent resistance, and forming a film thinner than 1.5 μm can be obtained.
That is, the present invention includes a dye, a photosensitizer, a curing agent, and a solvent, and further contains a dye in a positive-type colored photosensitive composition that may further include an alkali-soluble resin, based on 100 parts by mass of the total solid content. Is 55.0 to 63.0 parts by mass, the content of the photosensitive agent is 10.0 to 30.0 parts by mass, the content of the curing agent is 10.0 to 25.0 parts by mass, and the content of the alkali-soluble resin is Provided is a positive red-colored photosensitive composition of 10.0 parts by mass or less, a color filter including pixels formed using the positive red-colored photosensitive composition, and a solid-state imaging device using the color filter. .

  According to the positive-type red-colored photosensitive composition of the present invention, a pattern can be formed even with a color filter having a thickness of less than 1.5 μm and a small exposure amount, and the pattern film can be reduced during pattern development. And the solvent resistance is good, so that the color unevenness of the image can be reduced. This color filter can be suitably used for a solid-state imaging device using a CCD. In particular, when the preferred dye described in the present invention is used, it is possible to obtain a color filter having a red pixel having excellent selective transmission performance at a red wavelength.

Hereinafter, the present invention will be described in detail.
The positive-type red-colored photosensitive composition of the present invention contains a dye as a coloring component. As the pigment, a dye is preferably used. The dye is selected according to the desired red color tone, and the red dye alone, a mixture of a plurality of red dyes, or a mixture of a red dye and a dye of another hue, such as a yellow dye or an orange dye, is used. You can also.
The desired dye has a sufficient solubility in the solvent constituting the positive-type red-colored photosensitive composition, and further has a sufficient solubility in a developing solution in a developing step at the time of pattern formation, and forms a red pattern. You can do it.
As the dye used in the present invention, a dye represented by the general formula (IV) is preferably used.

[In the formula, D represents at least one kind of pigment matrix selected from the group consisting of xanthene, azo, anthraquinone, and pyrazolone.
n represents an integer of 1 to 4.
R ¹ is an aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclohexyl group, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, or 3 to 24 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms. An aliphatic alkoxyalkyl group, an aliphatic ester group having 3 to 24 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. (The arylalkyl group is an arylalkyl group having 7 to 20 carbon atoms substituted with at least one aryl group selected from the group consisting of an optionally substituted phenyl group and an optionally substituted naphthyl group. Represents a group.)
However, when n is an integer of 2 to 4, R ¹ may be the same or different.
Specifically, examples of the aliphatic hydrocarbon group include a propyl group, a hexyl group, an octyl group, a dexyl group, a 1-methylbutyl group, a 1,1,3,3-tetramethylbutyl group, and a 1,5-dimethylhexyl group. 1,6-dimethylheptyl group, 2-ethylhexyl group and 1,1,5,5-tetramethylhexyl group
Examples of the alkylcyclohexyl group include a 2-methylcyclohexyl group and a 2-ethylcyclohexyl group.
Examples of the aliphatic alkoxyalkyl group include an ethoxypropyl group, an i-propoxypropyl group, an octoxypropyl group, a 3-ethoxy-n-propyl group, and a 3- (2-ethylhexyloxy) propyl group.
Examples of the aliphatic ester group include a propoxycarbonylpropyl group, an ethoxycarbonylbutoxy group, a propionyloxyethyl group, and a butyryloxybutyl group.
Examples of the arylalkyl group include a benzyl group, a phenethyl group and a 1-methyl-3-phenylpropyl group. ]

  Among the dyes represented by the general formula (IV), particularly preferred dyes include a compound represented by the general formula (I) or a salt thereof.

[In the formula, R ^{10 to} R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
R ^{14 to} R ¹⁶ each independently represent a sulfonic acid group or a substituent represented by the general formula (I-1). However, at least one of R ^{14 to} R ¹⁶ represents a substituent represented by the general formula (I-1).
—SO ₂ NHR ¹⁷ (I-1)
Wherein R ¹⁷ is an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, and 2 carbon atoms. An alkyl group having 2 to 12 carbon atoms substituted with an alkoxyl group having from 12 to 12, an alkylcarboxylalkyl group represented by the general formula (I-1-1),
L ¹ -CO-OL ^2- (I-1-1)
(Wherein, L ¹ represents an alkyl group having 2 to 12 carbon atoms,
L ² represents an alkylene group having 2 to 12 carbon atoms. )
An alkyloxycarbonylalkyl group represented by the general formula (I-1-2),
^{L 3 -O-CO-L 4} - (I-1-2)
(Wherein L ³ represents an alkyl group having 2 to 12 carbon atoms;
L ⁴ represents an alkylene group having 2 to 12 carbon atoms. )
A phenyl group substituted with an alkyl group having 1 to 20 carbon atoms,
Or an alkyl group having 1 to 20 carbon atoms substituted with a phenyl group. )
Represents a substituent represented by ]

In the compound represented by the general formula (I) or a salt thereof (hereinafter, sometimes referred to as “dye (I)”), the alkyl group having 1 to 3 carbon atoms represented by substituents R ^{10 to} R ¹³ includes Examples thereof include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.
The alkyl group having 2 to 20 carbon atoms in the substituent R ^17, ethyl, n- propyl, i- propyl, n- hexyl, n- nonyl, n- decyl group, n- dodecyl group, 2 -Ethylhexyl, 1,3-dimethylbutyl, 1-methylbutyl, 1,5-dimethylhexyl, 1,1,3,3-tetramethylbutyl and the like.
Examples of the cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain include a cyclohexylethyl group, a 3-cyclohexylpropyl group, and an 8-cyclohexyloctyl group.
Examples of the alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain include a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group, and a 2- (n-butyl) cyclohexyl group.
Examples of the alkyl group having 2 to 12 carbon atoms substituted with an alkoxyl group having 2 to 12 carbon atoms include a 3-ethoxy-n-propyl group, a propoxypropyl group, a 4-propoxy-n-butyl group, and a 3-methyl-n- Examples include a hexyloxyethyl group and a 3- (2-ethylhexyloxy) propyl group.
Examples of the phenyl group substituted with an alkyl group having 1 to 20 carbon atoms include an o-isopropylphenyl group.
Examples of the alkyl group having 1 to 20 carbon atoms substituted with a phenyl group include a DL-1-phenylethyl group, a benzyl group, and a 3-phenyl-n-butyl group.
Examples of the alkyl group having 2 to 12 carbon atoms in the substituents L ¹ and L ² include an ethyl group, a propyl group, an n-hexyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, a 2-ethylhexyl group, , 3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group and the like.
Examples of the alkylene group having 2 to 12 carbon atoms in the substituents L ³ and L ⁴ include a dimethylene group and a hexamethylene group.

The dye (I) may be a compound represented by the general formula (I) or a salt of the compound. Examples of the salt include a hydrogen atom and an alkali metal salt with an alkali metal such as lithium, sodium, and potassium. These salts can form a salt with the sulfonic acid group when the substituents R ¹⁴ , R ¹⁵ , and R ^{16 of the} compound represented by the general formula (I) are each independently a sulfonic acid group.

  Among the compounds represented by the general formula (I), preferred examples include the compound (50).

  The compound (50) is described in, for example, JP-A-6-230210, JP-A-7-242651 and the like.

  Preferred dyes used in the colored photosensitive composition for forming a red pixel include, in addition to the compound represented by the general formula (IV), a compound represented by the general formula (II) or a salt thereof, and a compound represented by the general formula (III) )).

[Wherein, R ²¹ and R ²² each independently represent a hydroxyl group or a carboxyl group;
R ^20, R ²³ ~R ²⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a sulfonic acid group or a nitro group. ]

[Wherein, R ³⁰ represents an alkyl group having 2 to 10 carbon atoms;
R ³¹ , R ³² and R ³⁴ each independently represent a hydrogen atom, a methyl group, a hydroxyl group or a cyano group;
R ³³ represents an alkyl group having 1 to 4 carbon atoms. ]

In the compound represented by the general formula (II) or a salt thereof (hereinafter sometimes referred to as “dye (II)”), the halogen atom represented by the substituents R ²⁰ , R ^{23 to} R ²⁵ is a fluorine atom, A chlorine atom, a bromine atom and the like; a C1-4 alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group; and a C1-4 alkoxyl group such as a methoxy group, an ethoxy group and a propoxy group. , Butoxy group and the like.

The dye (II) may be a compound represented by the general formula (II) or a salt of the compound. Examples of the salt include an alkali metal salt with an alkali metal such as lithium, sodium, and potassium, and a mixture thereof. These salts, when substituents R ²³ to R ²⁶ of the compound represented by the general formula (II) is a sulfonic acid group, usually form salts with part of the sulfonic acid groups.
Further, the dye (II) may be coordinated with a metal atom to form a complex. By forming a complex with a metal atom, light resistance is further improved. Examples of the metal atom include a transition metal atom, and among them, a chromium atom is preferable.

  Among the dyes (II), preferred dyes include C.I. I. Solvent Yellow 82, C.I. I. Solvent Orange 56 and the like.

In the compound represented by the general formula (III) (hereinafter sometimes referred to as “dye (III)”), the alkyl group having 2 to 10 carbon atoms represented by the substituent R ³⁰ includes an ethyl group and a propyl group. , N-hexyl group, n-nonyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1 , 3,3-tetramethylbutyl group and the like.
The alkyl group having 1 to 4 carbon atoms represented by R ^33, a methyl group, an ethyl group, a propyl group and a butyl group are exemplified, respectively.

Further, the compound represented by the general formula (III) can be produced, for example, by a production method described in JP-A-50-28530.
Among the dyes (III), preferred dyes include C.I. I. Solvent Yellow 162 and the like.

  Further, in addition to the compound represented by the general formula (IV), examples of the dye that can be used include a sulfonamide derivative of an acid dye and an oil-soluble dye.

  Above all, as a combination of dyes used for forming a red pixel, specifically, compound (50) /C.I. I. Solvent Yellow 162, Compound (50) /C.I. I. Solvent Yellow 162 / C.I. I. Solvent Yellow 82, compound (50) /C.I. I. Solvent Yellow 162 / C.I. I. Solvent Orange 56, Compound (50) /C.I. I. Solvent Yellow 162 / C.I. I. Solvent Yellow 82 / C.I. I. Solvent Orange 56, among others, Compound (50) /C.I. I. Solvent Yellow 162 / C.I. I. Solvent Yellow 82 is preferred.

The content of the dye in the present invention is such that the content of the dye (I) is 25 to 40 parts by mass and the content of the dye (II) is 25 to 40 parts by mass when the total amount of the dyes used is 100 parts by mass. And the content of the dye (III) is preferably 25 to 40 parts by mass. Furthermore, it is preferable that the content of the dye (I) is 35 to 40 parts by mass, the content of the dye (II) is 30 to 35 parts by mass, and the content of the dye (III) is 30 to 35 parts by mass. More preferably, the amount is 35 to 40 parts by mass. When the content of the dye is within the above range, the necessary color density of the color filter can be secured, and when the red pixel pattern of the color filter is formed with the positive-type red coloring photosensitive composition, the photosensitive layer in the developing and dissolving portion is exposed. This is preferred in that no residue of the reactive composition is generated.
The total amount of the dye used in the present invention is 55.0 to 63.0 parts by mass, preferably 59.0 to 63.0 parts by mass, based on 100 parts by mass of the solid content of the positive-type red colored photosensitive composition. If the amount is less than 55.0 parts by mass, the color density tends to be insufficient when forming a thin film, which is not preferable. On the other hand, if the amount is more than 63.0 parts by mass, the pattern is eluted in the developing step, and the eluted portion is likely to become a defect when formed into a color filter, which is not preferable.

  As the photosensitive agent contained in the positive coloring photosensitive composition of the present invention, for example, an ester of a phenol compound and an o-naphthoquinonediazidosulfonic acid compound can be used. Examples of the phenol compound include di, tri, tetra, and pentahydroxybenzophenone, and the compound represented by the chemical formula (21). Xinonediazide-4-sulfonic acid and the like are each exemplified.

  As the curing agent contained in the positive-type red colored photosensitive composition of the present invention, a heat curing agent that is cured by heating is used. Examples of the heat curing agent include compounds represented by the general formula (31).

[Wherein, Q ^{1 to} Q ⁴ each independently represent a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms substituted with an alkoxyl group having 1 to 4 carbon atoms. ,
Z is a phenyl group or a general formula (32)
Q ⁵ Q ⁶ N- (32)
(In the formula, Q ⁵ and Q ⁶ each independently represent a hydrogen atom, a C 1-4 hydroxyalkyl group or a C 1-4 alkyl group substituted with a C 1-4 alkoxyl group. Do.)
Represents a substituent represented by Provided that at least one of Q ¹ to Q ⁶ is an alkyl group having 1 to 4 carbon atoms which is substituted with a hydroxyalkyl group or an alkoxyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms. ]
In the compound, the hydroxyalkyl group having 1 to 4 carbon atoms includes a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, etc., each having 1 to 4 carbon atoms substituted with an alkoxyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and a propoxybutyl group. Examples of the compound represented by the general formula (32) include hexamethoxymethylmelamine.

  Examples of the alkali-soluble resin that can be used for the positive-type red colored photosensitive composition in the present invention include a novolak resin and a polyvinyl resin. As the novolak resin, para-cresol novolak resin, meta-cresol novolak resin, novolak resin of para-cresol and meta-cresol, general formula (11)

And a novolak resin having a structure represented by the following formula: Examples of the polyvinyl resin include poly-p-vinylphenol and a copolymer of styrene and p-vinylphenol. The weight average molecular weight in terms of polystyrene of each resin is preferably in the range of 3,000 to 14,000, and more preferably in the range of 5,500 to 13,500.

The positive-type red-colored photosensitive composition of the present invention has a pigment content of 55.0 to 63.0 parts by mass and an alkali-soluble resin content of 10.0 parts by mass based on 100 parts by mass of the solid content. Or less, it is preferable that the content of the photosensitive agent is 10.0 to 30.0 parts by mass and the content of the curing agent is 10.0 to 25.0 parts by mass.
If the content of the dye is less than 55.0 parts by mass, the color filter becomes thin when a thin film is formed, so that the function as a color filter is lost. On the other hand, when the content of the dye is more than 63.0 parts by mass, the film of the color filter is reduced in the developing step of the pattern formation, and the color unevenness of the image is generated.
When the content of the photosensitive agent is 10.0 to 30.0 parts by mass, color unevenness of an image is less likely to occur without causing a reduction in the thickness of a color filter in a developing process. This is preferable because the projection exposure time during pattern formation does not become long and the production efficiency does not deteriorate.
When the content of the curing agent is 10.0 to 25.0 parts by mass, the mechanical strength when the formed color filter pattern is cured by heating is sufficient, and the color filter film is reduced in the developing process. This is preferable because color unevenness of an image is less likely to occur.
When the content of the alkali-soluble resin is 10 parts by mass or less, and more preferably 1 part by mass or less, the solubility in an alkali developing solution is sufficient and a pattern can be formed. This is preferable since color unevenness tends to hardly occur.
The photosensitive agent in the positive-type red-colored photosensitive composition of the present invention, the curing agent and the number of parts by weight of the alkali-soluble resin, respectively, the pattern projection exposure, the pattern film reduction during development, depending on the mechanical strength of the pattern, It can be adjusted appropriately.

The positive-type red-colored photosensitive composition of the present invention contains a solvent. The solvent is the dye contained in the positive-type colored photosensitive composition, the solubility of the photosensitizer and the curing agent, and the solubility of the alkali-soluble resin that may be contained in the positive-type colored photosensitive composition, among other dyes It is appropriately selected and used according to the solubility.
Examples of the solvent include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, and γ. -Butyrolactone, dimethylsulfoxide, N, N'-dimethylformamide, cyclohexanone, ethyl acetate, ethyl n-butylpyruvate, ethyl lactate and the like. These solvents are used alone or in combination of two or more.
The amount of the solvent to be used is generally 230 to 400 parts by mass, preferably 250 to 300 parts by mass, per 100 parts by mass of the solid component of the positive-type red colored photosensitive composition.
When the content of the solvent is from 230 to 400 parts by mass, coating unevenness when a thin film is formed on the substrate using the positive-type red-colored photosensitive composition tends to be small, which is preferable.

  By using the positive-type red-colored photosensitive composition of the present invention, a color filter having a thickness smaller than 1.5 μm and consisting of red pixels having a pattern of about 2 to 20 μm in length and width independently of each other can be obtained. Can be.

  In order to obtain a color filter, it may be operated by a photolithography method in the same manner as a usual colored photosensitive composition, for example, providing a coating comprising the positive red colored photosensitive composition of the present invention on a support, After exposing the film, a pattern may be formed by developing. Examples of the support include a silicon wafer on which a CCD is formed, a transparent glass plate, a quartz plate, and the like.

  In order to form a coating on the support, for example, the positive type red-colored photosensitive composition of the present invention is applied by a usual coating method such as a spin coating method, a dip method, a casting coating method, a roll coating method, and a slit & spin coating method. It may be applied to a support by a method, and then volatile components such as a solvent may be removed by heating or the like. Thus, a layer composed of the solid content of the colored photosensitive composition is formed on the support or the like.

  The coating is then exposed. A mask pattern composed of a pattern corresponding to a target pattern is used for the exposure, and a light beam may be irradiated through the mask pattern. As a light beam used for exposure, for example, g-line, i-line, or the like can be used, and exposure may be performed using an exposure device such as a g-line stepper or an i-line stepper. The irradiation amount of the light beam in the irradiation region is appropriately selected depending on the type and content of the photosensitizer, the type and content of the curing agent, the weight average molecular weight in terms of polystyrene of the alkali-soluble resin, the monomer ratio, the content, and the like. Further, the coating film thus formed may be heated. By heating, the used curing agent is cured, and the mechanical strength of the coating tends to be improved, which is preferable. The heating temperature when heating is, for example, 80 to 150 ° C.

  After exposure, develop. The development may be performed by immersing the support provided with the coating film in a developing solution as in the case of using a normal positive photosensitive composition. As the developing solution, the same developing solution as used when a pattern is formed using a usual photosensitive composition can be used. By pulling up the support from the developing solution and then washing with water to remove the developing solution, a color filter in which red pixels are formed in a desired pattern can be obtained. In some cases, the support is pulled up from the developing solution, then rinsed with a rinsing solution, and washed with water. By this rinsing, residues of the colored photosensitive composition remaining on the support during development can be removed.

  The positive-type red-colored photosensitive composition of the present invention may be subsequently irradiated with ultraviolet rays. By irradiating with ultraviolet rays, the remaining photosensitive agent can be decomposed. After washing with water, the mechanical strength of the formed color filter pattern can be improved by heating. The heating temperature is usually about 160 ° C. or more and 220 ° C. or less. When the temperature is 160 ° C. or more and 220 ° C. or less, curing is sufficiently advanced by the curing agent, and the dye is not decomposed, which is preferable.

  Thus, the red pixel of the color filter is formed with the target pattern. By repeating the pattern forming process of the color filter for each of the different colors, for example, three colors such as a red pixel, a green pixel, and a blue pixel are obtained. Of pixels are formed on the same support. Note that the order of forming the pixels of each color can be arbitrarily changed.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the appended claims, and includes all modifications within the scope and meaning equivalent to the claims. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1
Chemical formula (50) as pigment

And 2.2 parts by mass of a compound represented by the formula: I. Solvent Orange 56 (2.1 parts by mass), C.I. I. 1.6 parts by mass of Solvent Yellow 162, 2.6 parts by mass of an ester of a phenolic compound represented by the chemical formula (21) and o-naphthoquinonediazide-5-sulfonic acid as a photosensitive agent, and hexamethoxymethylmelamine as a curing agent. After mixing 1.6 parts by mass, 20.0 parts by mass of ethyl lactate and 9.0 parts by mass of N, N-dimethylformamide as a solvent, the mixture was filtered through a membrane filter having a pore size of 0.1 μm, and then the mixture was filtered into a positive red-colored photosensitive composition. I got something.
Next, a silicon wafer was spin-coated with Sumitomo Chemical Co., Ltd. Sumiresist PR-1300Y-PG as a flattening film forming material, and heated at 100 ° C. for 1 minute to remove volatile components to form a 0.5 μm film. A thick coating was formed. Next, the silicon wafer was heated at 230 ° C. for 15 minutes to cure the film and form a support. The positive coloring photosensitive composition prepared above was spin-coated on this support (silicon wafer with a flattening film) and heated at 100 ° C. for 1 minute to remove volatile components to form a coating. . Next, using an exposure machine [“Nikon NSR i7A” (manufactured by Nikon Corporation)], i-rays are irradiated through a mask pattern to expose at an exposure amount of 1,300 mJ, and then a developing solution [“SOPD” (Sumitomo) (Manufactured by Chemical Industry Co., Ltd., 23 ° C.) for 30 seconds to develop. After the development, the film was rinsed with a rinse solution (a solution in which 0.15% by mass of polyoxyethylene nonylphenyl ether was added to a 1.9% by mass TMAH aqueous solution), washed with water, dried, and irradiated with ultraviolet rays. C. for 3 minutes to obtain a color filter having red pixels formed in a band-shaped pattern having a line width of 3.0 .mu.m and a thickness of 1.1 .mu.m.
Next, a color filter having red pixels formed of a mosaic pattern having a line width of 3.0 μm and a thickness of 1.1 μm was obtained in the same manner as above except that the mask pattern was changed.
Next, a color filter having a red pixel formed with a thickness of 1.1 μm over the entire surface was obtained in the same manner as above except that development was performed without exposure using a transparent glass plate as a support. .

Comparative Example 1
Chemical formula (50) as pigment

2.4 parts by mass of the compound represented by I. Solvent Orange 56 (2.2 parts by mass) and C.I. I. 2.0 parts by mass of Solvent Yellow 162, 1.5 parts by mass of an ester of a phenol compound represented by the chemical formula (21) and o-naphthoquinonediazide-5-sulfonic acid as a photosensitive agent, and a chemical formula (11) as an alkali-soluble resin

, 0.4 parts by mass of a novolak resin (weight average molecular weight in terms of polystyrene of 13,500), 1.6 parts by mass of hexamethoxymethylmelamine as a curing agent, 23.0 parts by mass of ethyl lactate as a solvent, and N, After N'-dimethylformamide was mixed at 10.0 parts by mass, the mixture was filtered through a membrane filter having a pore size of 0.1 μm to obtain a positive red-colored photosensitive composition.
Next, a silicon wafer was spin-coated with Sumitomo Chemical Co., Ltd. Sumiresist PR-1300Y-PG as a flattening film forming material, and heated at 100 ° C. for 1 minute to remove volatile components to form a 0.5 μm film. A thick coating was formed. Next, the silicon wafer was heated at 230 ° C. for 15 minutes to cure the film and form a support. The positive coloring photosensitive composition prepared above was applied onto this support (silicon wafer with a flattening film) by spin coating, and heated at 100 ° C. for 1 minute to evaporate the solvent to form a coating. Next, using an exposure machine [“Nikon NSR i7A” (manufactured by Nikon Corporation)], i-rays are irradiated through a mask pattern to expose at an exposure amount of 1,300 mJ, and then a developing solution [“SOPD” (Sumitomo) (Manufactured by Chemical Industry Co., Ltd., 23 ° C.) for 30 seconds to develop. After the development, the film was rinsed with a rinse solution (a solution in which 0.15% by mass of polyoxyethylene nonylphenyl ether was added to a 1.9% by mass TMAH aqueous solution), washed with water, dried, and irradiated with ultraviolet rays. C. for 3 minutes to obtain a color filter having red pixels formed in a band-shaped pattern having a line width of 3.0 .mu.m and a thickness of 1.0 .mu.m.
Next, a color filter having red pixels formed of a mosaic pattern having a line width of 3.0 μm and a thickness of 1.0 μm was obtained in the same manner as described above except that the mask pattern was changed.
Next, a color filter having red pixels formed with a thickness of 1.0 μm over the entire surface was obtained in the same manner as described above except that development was performed without exposure using a transparent glass plate as a support. .

Comparative Example 2
Chemical formula (50) as pigment

1.4 parts by mass of the compound represented by I. 0.9 parts by mass of Solvent Orange 56, C.I. I. Solvent Yellow 82 in an amount of 0.8 parts by mass and C.I. I. 0.8 parts by mass of Solvent Yellow 162, 3.3 parts by mass of an ester of a phenol compound represented by the chemical formula (21) and o-naphthoquinonediazide-5-sulfonic acid as a photosensitizer, and a chemical formula (11) as an alkali-soluble resin

0.5 part by mass of a novolak resin (weight average molecular weight in terms of polystyrene of 13,500) represented by the following formula: 2.3 parts by mass of hexamethoxymethyl melamine as a curing agent, 16.3 parts by mass of ethyl lactate as a solvent, and N, After mixing N'-dimethylformamide at 7.0 parts by mass, the mixture was filtered through a membrane filter having a pore size of 0.1 μm to obtain a positive red-colored photosensitive composition.
Next, a silicon wafer was spin-coated with Sumitomo Chemical Co., Ltd. Sumiresist PR-1300Y-PG as a flattening film forming material, and heated at 100 ° C. for 1 minute to remove volatile components to form a 0.5 μm film. A thick coating was formed. Next, the silicon wafer was heated at 230 ° C. for 15 minutes to cure the film and form a support. The positive coloring photosensitive composition prepared above was applied on this support (silicon wafer with a flattening film) by spin coating, and heated at 100 ° C. for 1 minute to remove volatile components to form a coating. Next, using an exposure machine [“Nikon NSR i7A” (manufactured by Nikon Corporation)], i-rays are irradiated through a mask pattern to expose at an exposure amount of 1,300 mJ, and then a developing solution [“SOPD” (Sumitomo) (Manufactured by Chemical Industry Co., Ltd., 23 ° C.) for 30 seconds to develop. After the development, the film was rinsed with a rinse solution (a solution of 0.15% by mass of polyoxyethylene nonylphenyl ether added to a 1.9% by mass aqueous solution of TMAH), washed with water, dried, and irradiated with ultraviolet rays. C. for 3 minutes to obtain a color filter having red pixels formed in a band-shaped pattern having a line width of 3.0 .mu.m and a thickness of 1.3 .mu.m.
Next, a color filter having red pixels formed of a mosaic pattern having a line width of 3.0 μm and a thickness of 1.3 μm was obtained in the same manner as described above except that the mask pattern was changed.
Next, a color filter having red pixels formed with a thickness of 1.0 μm over the entire surface was obtained in the same manner as described above except that development was performed without exposure using a transparent glass plate as a support. .

Evaluation (1) Transmitted Light Selection Performance Wavelengths of 450 nm, 540 nm, and 650 nm of the color filters having red pixels formed over the entire surface of the glass substrate obtained in Examples 1 and 2 and Comparative Examples 1 and 2 above. Was measured for light transmittance. Table 1 shows the results.

(2) Pattern Projection Exposure In Examples 1 and 2 and Comparative Examples 1 and 2, when the exposure amount was varied to form a 3.0 μm line & space pattern, the exposure resulted in a line width of 3.0 μm. The amount was measured. Table 2 shows the results.

(3) Residual film development ratio In Examples 1 and 2 and Comparative Examples 1 and 2, the film thickness of the solid layer of the positive-type colored photosensitive composition was measured before and after alkali development at the time of forming the color filter pattern. And compared. Table 3 shows the results.

(4) Solvent resistance The positive red colored photosensitive composition obtained in Example 1 and Comparative Examples 1 and 2 was applied to the entire surface of a silicon wafer, irradiated with ultraviolet light, and heated to 180 ° C. for 3 minutes. And hardened. The silicon wafer with the coating film was mixed with a mixed solution of ethyl lactate and N, N-dimethylformamide (ethyl acetate 70%, N, N-dimethylformamide 30%) as a solvent composition of the positive-type red colored photosensitive composition. ) For 3 minutes, and the change in film thickness before and after the immersion was measured. Table 4 shows the results.

  When the positive-type red colored photosensitive composition of the present invention is used, a color filter having a high color density and having red pixels can be formed.

It is a schematic diagram which shows the cross section of the color filter which provided the red pixel, the green pixel, and the blue pixel on the same plane on a support body. It is a plane schematic diagram of a color filter provided with a red pixel, a green pixel, and a blue pixel in a strip pattern. It is a plane schematic diagram of a color filter provided with a red pixel, a green pixel, and a blue pixel in a mosaic pattern. FIG. 3 is a schematic cross-sectional view of a solid-state imaging device in which a color filter is formed on a light receiving unit.

Explanation of reference numerals

1: substrate 2: color filter R: red pixel G: green pixel B: blue pixel 10: substrate 20: light receiving section 30: laminated film 40: flattening film 50a: color pixel (1)
50b: color pixel (2)
50c: color pixel (3)
60: protective film

Claims (9)

  In the positive-type colored photosensitive composition containing a dye, a photosensitizer, a curing agent and a solvent, and which may further contain an alkali-soluble resin, the content of the dye is 55.0 to 55.0 parts by mass based on 100 parts by mass of the total solids. 63.0 parts by mass, the content of the photosensitive agent is 10.0 to 30.0 parts by mass, the content of the curing agent is 10.0 to 25.0 parts by mass, and the content of the alkali-soluble resin is 10.0 parts by mass. A positive red-colored photosensitive composition as described below.   In the positive-type colored photosensitive composition containing a dye, a photosensitizer, a curing agent and a solvent, and which may further contain an alkali-soluble resin, the content of the dye is 55.0 to 55.0 parts by mass based on 100 parts by mass of the total solids. 63.0 parts by mass, the content of the photosensitive agent is 10.0 to 30.0 parts by mass, the content of the curing agent is 10.0 to 25.0 parts by mass, and the content of the alkali-soluble resin is 1 part by mass or less. A positive red colored photosensitive composition.   The positive-type red-colored photosensitive composition according to claim 1, which does not contain an alkali-soluble resin. The positive-type red colored photosensitive composition according to any one of claims 1 to 3, further comprising a compound represented by the general formula (IV) or a salt thereof as a dye.

[Wherein, D represents at least one kind of pigment matrix selected from the group consisting of xanthene, azo, anthraquinone, and pyrazolone;
n is an integer of 1 to 4,
R ¹ is an aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclohexyl group, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, or 3 to 24 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms. Represents an aliphatic alkoxyalkyl group, an aliphatic ester group having 3 to 24 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. (The arylalkyl group is an arylalkyl group having 7 to 20 carbon atoms substituted with at least one aryl group selected from the group consisting of an optionally substituted phenyl group and an optionally substituted naphthyl group. Represents a group.)
However, when n is an integer of 2 to 4, R ¹ may be the same or different. ] The positive red-colored photosensitive composition according to any one of claims 1 to 4, comprising a compound represented by formula (I) or a salt thereof as a dye.

[Wherein, R ^{10 to} R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ^{14 to} R ¹⁶ each independently represent a sulfonic acid group or a substituent represented by the general formula (I-1). However, at least one of R ^{14 to} R ¹⁶ represents the general formula (I-1).
—SO ₂ NHR ¹⁷ (I-1)
(Wherein, R ¹⁷ is an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, 2 carbon atoms in the alkyl chain, An alkyl group having 2 to 12 carbon atoms, which is substituted with an alkoxyl group having from 12 to 12, an alkylcarboxylalkyl group represented by the general formula (I-1-1),
L ¹ -CO-OL ^2- (I-1-1)
(Wherein, L ¹ represents an alkyl group having 2 to 12 carbon atoms,
L ² represents an alkylene group having 2 to 12 carbon atoms. )
An alkyloxycarbonylalkyl group represented by the general formula (I-1-2),
^{L 3 -O-CO-L 4} - (I-1-2)
(Wherein L ³ represents an alkyl group having 2 to 12 carbon atoms;
L ⁴ represents an alkylene group having 2 to 12 carbon atoms. )
A phenyl group substituted with an alkyl group having 1 to 20 carbon atoms,
Or an alkyl group having 1 to 20 carbon atoms substituted with a phenyl group. )
Represents a substituent represented by ] The positive red-colored photosensitive composition according to any one of claims 1 to 5, comprising a compound represented by the formula (50) as a dye.

The positive red color according to claim 5 or 6, further comprising, as a dye, at least one dye selected from the group consisting of compounds represented by formulas (II) and (III). Colored photosensitive composition.

[Wherein, R ²¹ and R ²² each independently represent a hydroxyl group or a carboxyl group;
R ²⁰ and R ^{23 to} R ²⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a sulfonic acid group or a nitro group. ]

[Wherein, R ³⁰ represents an alkyl group having 2 to 10 carbon atoms;
R ³¹ , R ³² and R ³⁴ each independently represent a hydrogen atom, a methyl group, a hydroxyl group or a cyano group, and R ³³ represents an alkyl group having 1 to 4 carbon atoms. ]   A color filter including pixels formed by using the positive-type red colored photosensitive composition according to claim 1. A solid-state imaging device using the color filter according to claim 8.

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