JP2013231878A - Method for forming cured layer or cured pattern, method for manufacturing color filter, and color filter, solid-state imaging device and liquid crystal display device manufactured by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a cured layer or a cured pattern, by which the obtained layer itself has excellent strength and extremely suppresses generation of a residue when the layer is used as a base layer for a colored film formed of a colored radiation-sensitive composition, a method for manufacturing a color filter having excellent spectral characteristics, and a color filter, a solid-state imaging device and a liquid crystal display device manufactured by using these methods, and to provide a method for forming a cured layer or a cured pattern, by which a heating temperature in a heating and curing process can be reduced, a method for manufacturing a color filter having excellent spectral characteristics, and a color filter, a solid-state imaging device and a liquid crystal display device manufactured by using these methods.SOLUTION: The method for forming a cured layer or a cured pattern includes a step of heating a coating layer that is formed by applying a polymerizable composition containing a compound having a thermally polymerizable group on a substrate, or a pattern formed of the coating layer, in an environment with an oxygen concentration of 100 ppm or less. The method for manufacturing a color filter also includes the above step. The color filter, a solid-state imaging device and a liquid crystal display device are manufactured by the above methods.

Description

  The present invention relates to a method for forming a cured layer or a cured pattern, a method for producing a color filter, and a color filter, a solid-state imaging device, and a liquid crystal display device that are produced using these methods.

For example, a transparent film used in a solid-state imaging device is generally obtained by applying a transparent polymerizable composition on a substrate and then performing a post-bake treatment on the obtained coating layer.
Further, a color filter used in a solid-state imaging device is generally a pattern in which a colored film obtained from a colored radiation-sensitive composition is irradiated with ultraviolet rays through a predetermined mask pattern and then developed with an alkaline solution. It is obtained by forming an image and then post-baking. Thereby, a color filter in which organic pixels of a plurality of colors such as red pixels, green pixels, and blue pixels are two-dimensionally arranged on a support such as a semiconductor substrate is provided.
Furthermore, a solid-state imaging device is usually formed by forming a transparent film on a color filter and forming a microlens.

  By the way, in recent years, the increase in the number of pixels in a solid-state imaging device has been remarkable, and the reduction in the pixel size is remarkable when compared with a solid-state imaging device having the same inch size as a conventional one. Also, as the pixel size decreases, the performance requirements for color separation become stricter. To maintain device characteristics such as color shading characteristics and color mixing prevention, the performance required for color filters is reduced to thinner, rectangular, and between each colored pixel. Therefore, there is a demand for performance such as eliminating an overlap region where colors overlap each other.

As a method for manufacturing such a color filter, a photolithographic method has been widely used. In the photolithography method, a colored radiation-sensitive composition is applied to a support and dried to form a colored layer, and then the colored layer is subjected to pattern exposure / development to form a first color (for example, green) colored pixel. This is a method of forming and then forming the remaining colored pixels in the same manner.
For example, Patent Document 1 discloses that, when the pixel size is 3.5 μm or more and 3.0 μm or less, variations in pixel size and shape of the color filter are significantly suppressed, and the influence on image quality and color unevenness is reduced. In order to provide a solid-state imaging device in which the occurrence of residue is greatly suppressed and the influence on color unevenness is reduced, the reflectance at a wavelength of 365 nm of the planarization layer as the underlayer of the colored pixel is 2% or less. Techniques to do this are disclosed.

JP 2009-65178 A

  However, along with the miniaturization of pixels of solid-state imaging devices, it is difficult for the conventional photolithographic pattern formation to achieve both the spectral characteristics of the color filter and the pattern formability in response to the demand for finer and thinner color filters. It has become to.

  In particular, in a color filter for a solid-state imaging device, the thickness of the organic pattern constituting the color filter is, for example, 1 μm or less and the pixel size is 2 μm or less (for example, 0.5 to 2.0 μm). There is a tendency to achieve such a small size. As the color filter is miniaturized in this way, the residue generated in the process of the photolithography method has a greater effect on image quality and color unevenness. Therefore, a technique capable of extremely suppressing the generation of the residue is required. .

The present invention has been made in view of the above problems, and its purpose is to improve the strength of the layer itself, and when used as an underlayer of a colored film with a colored radiation-sensitive composition. , A method of forming a cured layer or a cured pattern that can extremely suppress the generation of residue, a method of manufacturing a color filter having excellent spectral characteristics, a color filter manufactured using these, a solid-state imaging device, and A liquid crystal display device is provided.
Another object of the present invention is a method for forming a cured layer or a cured pattern capable of lowering the heating temperature in heat curing, a method for producing a color filter having excellent spectral characteristics, and the production using these. A color filter, a solid-state imaging device, and a liquid crystal display device.

  In the production of the color filter, the arrangement order of the pixels constituting the color filter can be arbitrarily set. However, when the color filter array having n-color pixels is formed using the above-described photolithography method, n times A color filter array in which integrated values of n defective rates generated in a series of steps of coating, exposure, development, and post-baking are finally obtained by performing coating, exposure, development, and post-baking. Will contribute to the yield.

In view of the above, the present inventor, as a result of intensive studies, in particular, the “development residue” generated in the process of forming a coating layer using a colored radiation-sensitive composition and developing and exposing it is finally It has been found that it contributes most to the defective rate of the manufactured color filter.
In particular, on the transparent film formed in the lower layer of the color filter, for example, a colored film is formed using a colored radiation-sensitive composition of the nth color, and when this colored film is exposed and developed, this unexposed portion (this unexposed portion) The exposure part is an area where the colored film of the nth color is to be removed by the developer, and forms other colored pixels such as the (n + 1) th color, the (n + 2) th color,. The coloring residue derived from the colored radiation-sensitive composition of the n-th color affects the transmission spectral characteristics of the other colored pixels and increases the device defect rate. Become.

  In order to efficiently remove development residues in the unexposed areas, efforts have been made to optimize development and rinsing process conditions, but drastic improvements are rarely expected.

  Further, in order to suppress the generation of residues, it is conceivable to suppress the content of the photosensitive component and the component that develops development characteristics in the colored radiation-sensitive composition, but in this case, it is required in the photolithography method. In particular, the problem that the pixel having a reduced thickness and size is difficult to form in a desired shape (that is, the patterning performance is inferior) is likely to occur.

In view of the above circumstances, the present inventor has recently considered that the “development residue”, which is often considered to be mainly caused by the degree of alkali solubility of the layer formed from the photosensitive composition, depends on the photosensitive composition. The investigation was conducted by paying attention to the degree of curing (degree of polymerization) in the underlying layer of the layer to be formed. As a result, in the case of using a method in which the underlayer is formed of a photocurable composition and exposed with high exposure energy, the diffusion of exposure energy in the direction along the film surface also increases, and the pixel finally obtained When it is difficult to control the size of the base layer, the base layer is formed from a thermosetting composition, and the base layer is heated and cured in a state where the oxygen concentration is in a specific low range. In this case, a coating layer is formed on the underlayer using a photosensitive composition, and even if the coating layer is exposed and developed, the generation of development residue is drastically maintained in a state where the pixel size is controlled. It was found that it can be suppressed.
In addition, the present inventors heated the coating layer formed using the thermosetting composition in a state where the oxygen concentration was in a specific low range as described above, and thereby the degree of cure (polymerization in the cured layer). It was also found that the strength of the cured layer itself can be improved.
Furthermore, the present inventors specify the oxygen concentration of the coating layer formed using the thermosetting composition in the situation where the degree of curing (degree of polymerization) in the cured layer does not have to be increased so much. It is possible to lower the heating temperature than the conventional level by heating in a low range, and it is very effective especially when using a substrate having low heat resistance as the underlayer. The title and the present invention have been completed.

That is, the present invention is as follows.
[1]
A coating layer formed by coating a polymerizable composition containing a compound having a thermally polymerizable group on a substrate or a pattern formed by the coating layer is heated in an environment where the oxygen concentration is 100 ppm or less. A method for forming a cured layer or a cured pattern, comprising the step of:
[2]
The method for forming a cured layer or a cured pattern according to [1], wherein the coating layer or pattern is heated in the presence of an inert gas in a sealed heating tank.
[3]
The method for forming a cured layer or a cured pattern according to [1] or [2], wherein the polymerizable composition is a transparent polymerizable composition.
[4]
Any of [1] to [3], wherein the polymerizable composition further comprises (i) colorless transparent particles, or (ii) any one or more of a color pigment and a dye. A method for forming a cured layer or a cured pattern according to claim 1.
[5]
The method for forming a cured layer or a cured pattern according to any one of [1] to [4], wherein the thermally polymerizable group is a radically polymerizable group.
[6]
The manufacturing method of a color filter containing the formation method of the hardened layer or hardened pattern of any one of [1]-[5].
[7]
The color filter obtained by the manufacturing method of the color filter as described in [6].
[8]
[7] A solid-state imaging device having the color filter according to [7].
[9]
[7] A liquid crystal display device having the color filter according to [7].

  The present invention preferably further has the following configuration.

[10]
The coating layer is a transparent coating layer formed by coating a transparent polymerizable composition containing a compound having a thermally polymerizable group on a substrate, and the transparent coating layer has an oxygen concentration of 100 ppm or less. The method for producing a color filter according to [6], wherein a transparent cured layer is formed by heating under,
Forming a first colored radiation-sensitive layer by applying a first colored radiation-sensitive composition on the transparent cured layer; and
A method for producing a color filter, comprising: a step of forming a first colored pattern by exposing and developing the first colored radiation-sensitive composition.
[11]
The first colored pattern is a pattern in which a through-hole group having a first through-hole part group and a second through-hole part group is formed in the first colored radiation-sensitive layer,
The second colored radiation-sensitive composition is embedded in each through-hole in the first through-hole portion group and the second through-hole portion group so that a plurality of second colored pixels are formed. Laminating a second colored radiation-sensitive layer with the second colored radiation-sensitive composition on one colored pattern;
By exposing and developing the position corresponding to the first through-hole portion group of the first colored radiation-sensitive layer of the second colored radiation-sensitive layer, the second colored radiation-sensitive layer, Removing a plurality of second colored pixels formed inside each through hole of the second through hole portion group provided in the first colored layer;
On the first colored pattern, the third colored radiation-sensitive composition is embedded in each through-hole in the second through-hole portion group, and a plurality of third colored pixels are formed on the first colored pattern. Laminating a third colored radiation-sensitive layer with a three-colored radiation-sensitive composition; and
The third colored radiation-sensitive layer is removed by exposing and developing a position corresponding to the second through-hole portion group of the first colored radiation-sensitive layer of the third colored radiation-sensitive layer. The method for producing a color filter according to [10], further comprising a step.
[12]
The first colored radiation-sensitive composition is a composition containing a compound having a thermally polymerizable group, and before the step of laminating the second colored radiation-sensitive layer, the first colored pattern is oxygenated. The method for producing a color filter according to [11], wherein heating is performed in an environment having a concentration of 100 ppm or less.
[13]
A pattern formed by the coating layer is formed by exposing and developing a first colored radiation-sensitive layer formed by coating a first colored radiation-sensitive composition on the substrate. The method for producing a color filter according to [6], wherein the first colored pattern is heated in an environment having an oxygen concentration of 100 ppm or less to form a cured pattern,
The first colored pattern is a pattern in which a through-hole group having a first through-hole part group and a second through-hole part group is formed in the first colored radiation-sensitive layer,
The curing is performed so that a plurality of second colored pixels are formed by embedding a second colored radiation-sensitive composition inside each through-hole in the first through-hole portion group and the second through-hole portion group. Laminating a second colored radiation-sensitive layer with the second colored radiation-sensitive composition on the pattern;
By exposing and developing the position corresponding to the first through-hole portion group of the first colored radiation-sensitive layer of the second colored radiation-sensitive layer, the second colored radiation-sensitive layer, Removing a plurality of second colored pixels formed inside each through hole of the second through hole portion group provided in the first colored layer;
On the first colored pattern, the third colored radiation-sensitive composition is embedded in each through-hole in the second through-hole portion group, and a plurality of third colored pixels are formed on the first colored pattern. Laminating a third colored radiation-sensitive layer with a three-colored radiation-sensitive composition; and
The third colored radiation-sensitive layer is removed by exposing and developing a position corresponding to the second through-hole portion group of the first colored radiation-sensitive layer of the third colored radiation-sensitive layer. The manufacturing method of a color filter which further has a process.
[14]
The second colored radiation-sensitive composition is a composition containing a compound having a thermally polymerizable group, and before the step of laminating the third colored radiation-sensitive layer, the second colored pixel is oxygenated. The method for producing a color filter according to any one of [11] to [13], wherein the heating is performed in an environment having a concentration of 100 ppm or less.

According to the present invention, the strength of the layer itself can be made excellent, and when used as an underlayer of a colored film with a colored radiation-sensitive composition, the generation of a residue can be extremely suppressed, a cured layer or cured A pattern forming method, a color filter manufacturing method having excellent spectral characteristics, a color filter manufactured using the method, a solid-state imaging device, and a liquid crystal display device can be provided.
In addition, according to the present invention, a method for forming a cured layer or a cured pattern, a method for producing a color filter having excellent spectral characteristics, and a color produced using these, which can lower the heating temperature in heat curing. A filter, a solid-state imaging device, and a liquid crystal display device can be provided.

It is a schematic sectional drawing which shows the structural example of a color filter and a solid-state image sensor. It is a schematic sectional drawing which shows the state by which the 1st colored radiation sensitive layer was provided in the transparent cured layer. It is a schematic sectional drawing which shows the state by which the through-hole group was formed in the 1st coloring radiation sensitive layer in FIG. 2, and the 1st coloring pattern was formed. It is a schematic sectional drawing which shows the state in which the 2nd coloring pattern and the 2nd coloring radiation sensitive layer were formed. It is a schematic sectional drawing which shows the state from which the 2nd coloring radiation sensitive layer in FIG. 4 and a part of 2nd coloring pixel which comprises a 2nd coloring pattern were removed. It is a schematic sectional drawing which shows the state in which the 3rd coloring pattern and the 3rd coloring radiation sensitive layer were formed. It is a schematic sectional drawing which shows the state from which the 3rd coloring radiation sensitive layer in FIG. 6 was removed. It is a figure which shows the measurement result by the length measurement scanning electron microscope of the green pattern in Example 1. FIG. It is a figure which shows the measurement result by the length measurement scanning electron microscope of the green pattern in the comparative example 1. FIG. It is a figure which shows the measurement result by the length measurement scanning electron microscope of the blue pattern in Example 2. FIG. In Example 2, the figure which shows the relationship between the wavelength in the red cured layer before forming a blue radiation sensitive layer, and the transmittance | permeability, and the relationship between the wavelength in the red area | region of a laminated body after blue pattern formation, and the transmittance | permeability. It is. It is a figure which shows the measurement result by the length measurement scanning electron microscope of the blue pattern in the comparative example 2. The figure which shows the relationship between the wavelength and transmittance | permeability in the red cured layer before forming a blue radiation sensitive layer in the comparative example 2, and the relationship between the wavelength and transmittance | permeability in the red area | region of a laminated body after blue pattern formation. It is.

In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acrylic and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a mass average molecular weight of less than 2,000. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.
The “radiation” as used in the present invention means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

<Method for forming cured layer or cured pattern>
The method for forming the cured layer or cured pattern of the present invention is as follows.
A coating layer formed by coating a polymerizable composition containing a compound having a thermally polymerizable group on a substrate or a pattern formed by the coating layer is heated in an environment where the oxygen concentration is 100 ppm or less. The process of carrying out.

  According to the method for forming a cured layer or a cured pattern described above, the strength of the layer itself can be improved, and when it is used as an underlayer of a colored film with a colored radiation-sensitive composition, generation of a residue is caused. It can be extremely suppressed. As a result, when a color filter is produced using the above-described cured layer or cured pattern forming method, a color filter having excellent spectral characteristics can be produced. The reason is not clear, but is estimated as follows.

First, in the method for forming a cured layer or a cured pattern of the present invention, the cured layer or the cured pattern is formed by applying a polymerizable composition containing a compound having a thermally polymerizable group onto a substrate. Alternatively, the pattern formed by the coating layer is formed by heat curing in an environment having an oxygen concentration of 100 ppm or less.
In this way, by thermally curing the coating layer or pattern in an environment where the oxygen concentration is extremely low, thermal polymerization in the coating layer or pattern proceeds at a very high efficiency without being inhibited by oxygen. It is thought that it can be made to. In other words, it is considered that the remaining amount of the thermally polymerizable group derived from the compound having a thermally polymerizable group in the cured layer or the cured pattern can be extremely reduced.
In the color filter manufacturing method, the thermally polymerizable group in the coating layer or pattern can react with unreacted components in the colored radiation-sensitive layer formed on the coating layer or pattern. However, if the reaction proceeds for some reason in the region to be removed by development of the colored radiation-sensitive layer, the residue of the colored radiation-sensitive layer remains on the cured layer or cured pattern even after development. It is assumed that it will be easier to remain.
However, according to the present invention, as described above, since the remaining amount of the thermopolymerizable group in the cured layer or the cured pattern can be very small, the above reaction is suppressed, thereby dramatically increasing the generation of residues. Presumed to have been suppressed. And according to this invention, it can be considered that the color filter having excellent spectral characteristics can be manufactured by suppressing the generation of the residue as described above, thereby suppressing the color mixing with other colors.
In addition, as described above, thermal polymerization can proceed at a very high efficiency without being inhibited by oxygen, so that the degree of cure (degree of polymerization) in the cured layer or cured pattern is high, and the cured layer or cured It is considered that the strength of the pattern itself can be improved.

  In addition, according to the present invention, since the thermal polymerization can proceed with very high efficiency as described above, in the situation where it is not necessary to increase the degree of cure (polymerization degree) in the cured layer, the cured layer or cured pattern is formed. The heating temperature at the time of heat curing can be lowered, and this is particularly effective when a substrate having low heat resistance is used as the underlayer.

In particular, for example, a color filter for a solid-state imaging device that is required to have a minute size such that the thickness is 0.7 μm or less and / or the pixel pattern size (one side in a square pattern) is 2 μm or less (for example, 0.5 to 2.0 μm). It is effective to produce.
Therefore, this invention relates also to the manufacturing method of a color filter including the formation method of a cured layer or a cured pattern.

Here, the solid-state imaging device according to the embodiment of the present invention will be briefly described with reference to FIG. 1 as an example.
As shown in FIG. 1, the solid-state imaging device 10 includes a light receiving element (photodiode) 42 provided on a silicon substrate, a color filter 13, a planarizing film 14, a microlens 15, and the like. In the present invention, the planarizing film 14 is not necessarily provided. In FIG. 1, in order to clarify each part, the ratios of the thicknesses and widths are disregarded and some of them are exaggerated.

  The support is not particularly limited as long as it is used for a color filter in addition to a silicon substrate. For example, soda glass, borosilicate glass, quartz glass, and a transparent conductive film attached to these are used for liquid crystal display elements. And a photoelectric conversion element substrate used for a solid-state imaging device, such as an oxide film or silicon nitride. Further, an intermediate layer or the like may be provided between the support and the color filter 13 as long as the present invention is not impaired.

  A P well 41 is provided on the silicon substrate, and a photodiode 42 is provided on a part of the surface of the P well. The photodiode 42 is formed by performing heat treatment after ion-implanting N-type impurities such as P and As into a part of the surface of the P-well. Further, an impurity diffusion layer 43 having an N-type impurity concentration higher than that of the photodiode 42 is provided in a region different from the part of the surface of the P well 41 of the silicon substrate. The impurity diffusion layer 43 is formed by ion implantation of N-type impurities such as P and As and then performing heat treatment, and the role of the floating diffusion layer that transfers charges generated when the photodiode 42 receives incident light. Fulfill. In addition to the well 41 being a P-type impurity layer and the photodiode 42 and the impurity diffusion layer 43 being an N-type impurity layer, the well 41 is an N-type impurity layer, and the photodiode 42 and the impurity diffusion layer 43 being a P-type impurity layer. You can also

An insulating film 47 such as SiO ₂ or SiO ₂ / SiN / SiO ₂ is provided on the P well 41, the photodiode 42, and the impurity diffusion layer 43. On the insulating film 47, poly-Si, tungsten, An electrode 44 made of tungsten silicide, Al, Cu or the like is provided. The electrode 44 serves as the gate of the gate MOS transistor, and can serve as a transfer gate for transferring charges generated in the photodiode 42 to the impurity diffusion layer 43. Further, a wiring layer 45 is formed above the electrode 44. Above the wiring layer 45, a BPSG film 46 and a P-SiN film 48 are provided. The interface between the BPSG film 46 and the P-SiN film 48 is formed so as to curve downward above the photodiode 42, and serves as an in-layer lens for efficiently guiding incident light to the photodiode 42. Fulfill. On the BPSG film 46, a planarizing film layer 49 is formed for the purpose of planarizing the surface of the P-SiN film 48 or the uneven portions other than the pixel region.

  The color filter 13 is formed on the planarizing film layer 49. In the following description, a colored film (so-called solid film) formed on a silicon substrate without dividing the region is referred to as a “colored (colored radiation sensitive) layer”, and is formed by dividing the region into a pattern. A colored film (for example, a film patterned in a stripe shape) is referred to as a “colored pattern”. In addition, among the colored patterns, a colored pattern that is an element constituting the color filter 13 (for example, a colored pattern patterned into a square or a rectangle) is referred to as a “colored (red, green, blue) pixel”.

  The color filter 13 includes a plurality of two-dimensionally arranged green pixels (first color pixels) 20G, red pixels (second color pixels) 20R, and blue pixels (third color pixels) 20B. Each of the colored pixels 20R, 20G, and 20B is formed above the light receiving element 42. The green pixels 20G are formed in a checkered pattern, and the blue pixels 20B and the red pixels 20R are formed between the green pixels 20G. In FIG. 1, in order to explain that the color filter 13 is composed of pixels of three colors, the colored pixels 20R, 20G, and 20B are displayed in a line.

  The planarization film 14 is formed so as to cover the upper surface of the color filter 13 and planarizes the color filter surface.

  The microlens 15 is a condensing lens arranged with the convex surface facing upward, and is provided above the planarizing film 14 (or a color filter when no planarizing film is provided) and above the light receiving element 42. Each microlens 15 efficiently guides light from the subject to each light receiving element 42.

Next, the method for forming a cured layer or a cured pattern according to the present invention will be described in detail, taking a method for producing a color filter as an example.
In the method for producing a color filter according to an embodiment of the present invention, a transparent coating layer is first formed by coating a transparent polymerizable composition containing a compound having a thermopolymerizable group on a substrate.
For example, in the case of producing the solid-state imaging device shown in FIG. A transparent coating layer is formed.
Here, the thickness of the transparent coating layer can be appropriately changed depending on the application. The range of 005 to 1 μm is preferable, the range of 0.01 to 0.8 is more preferable, and the range of 0.05 to 0.7 μm is more preferable.

Next, the transparent coating layer obtained as described above is heated in an environment having an oxygen concentration of 100 ppm or less to form a transparent cured layer.
The environment having an oxygen concentration of 100 ppm or less is preferably an environment having an oxygen concentration of 50 ppm or less. In such an environment where the oxygen concentration is 100 ppm or less, the oxygen concentration is usually 0.01 ppm or more.
The heating method in an environment where the oxygen concentration is 100 ppm or less is not particularly limited as long as this low oxygen concentration can be achieved. For example, a heating element having a transparent polymerizable layer is disposed in the heating tank, and the heating tank is sealed. A method of heating in the presence of an inert gas by introducing an inert gas while exhausting the air in the heating tank is preferable. Thereby, it can suppress that heating temperature fluctuates.
Examples of the inert gas include nitrogen gas, argon gas, and helium gas, and nitrogen gas is preferable.
In addition, the heating method in an environment where the oxygen concentration is 100 ppm or less is to arrange a heating element having a transparent polymerizable layer in the heating tank, and after sealing the heating tank, the heating tank is evacuated with a vacuum pump or the like. Alternatively, a method of heating under vacuum may be used.

As a heating device for performing heating in an environment having an oxygen concentration of 100 ppm or less, a hot plate, an oven, and the like can be given.
When the main purpose is to improve the strength of the layer itself and to suppress the generation of residues, the heating temperature is preferably 120 ° C. to 250 ° C., more preferably 180 ° C. to 230 ° C., 200 It is particularly preferable that the temperature is ˜220 ° C.
Moreover, when the main purpose is to lower the heating temperature during the formation of a cured layer or a cured pattern (during heat curing), the temperature is preferably 120 ° C to 180 ° C, more preferably 120 ° C to 160 ° C. Preferably, it is 120 to 150 degreeC. The heating time varies depending on the heating means, but is usually about 1 to 60 minutes, preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.

In view of the above, the heating device is preferably a hot plate unit capable of obtaining a sealed space in which the oxygen concentration is maintained at 100 ppm or less.
Since such a hot plate unit can be usually incorporated in a semiconductor coater developer, there is an advantage that the manufacturing efficiency of the color filter is hardly impaired.

  As described above, a transparent cured layer is formed by heating the transparent coating layer. For example, in the case of manufacturing the solid-state imaging device shown in FIG. 1, this transparent cured layer constitutes the planarizing film layer 49. .

  In the formation of the transparent cured layer, the transparent coating layer is exposed to g-line, h-line, i-line, etc., preferably i-line, before heating in the environment where the oxygen concentration is 100 ppm or less. An optional pre-curing treatment may be performed.

  Next, as shown in the schematic cross-sectional view of FIG. 2, the transparent cured layer 60 (corresponding to the flattened film layer 49 in the solid-state imaging device 10 shown in FIG. 1) formed on the first is formed. The 1st colored radiation sensitive layer 11 is formed by apply | coating 1 colored radiation sensitive composition.

  The first colored radiation-sensitive layer 11 is formed by coating the first colored radiation-sensitive composition on a support by a coating method such as spin coating, slit coating, spray coating, and the like, and drying to form a colored layer. Can be done.

  As thickness of the 1st coloring radiation sensitive layer 11 here, the range of 0.3-1 micrometer is preferable, The range of 0.35-0.8 is more preferable, The range of 0.35-0.7 micrometer is more preferable.

Next, the position 11A on the first colored radiation-sensitive layer 11 is exposed and developed to remove, for example, an unexposed portion of the first colored radiation-sensitive layer. As a result, the through-hole group 120 is formed in the 1st colored radiation sensitive layer 11, and the 1st colored pattern 12 is formed (refer to the schematic sectional drawing of FIG. 3).
Here, the position 11 </ b> A is determined so that the through-hole group 120 is provided in a checkered pattern when viewed from the upper surface of the first colored radiation-sensitive layer 11. Therefore, the 1st coloring pattern 12 by which the through-hole group 120 is provided in the 1st coloring radiation sensitive layer 11 has a some square 1st coloring pixel in checkered form.
The through-hole group 120 has a first through-hole part group 121 and a second through-hole part group 122.

In the case where the first colored radiation-sensitive composition is a composition containing a compound having a thermally polymerizable group, it is preferable to heat the first colored pattern 12 to form a cured pattern.
This heating is preferably performed in an environment where the oxygen concentration is 100 ppm or less, more preferably in an environment where the oxygen concentration is 100 ppm or less, as in the case of heating the transparent coating layer described above (here, the oxygen concentration). Is usually 0.01 ppm or more). The conditions for the heating temperature, heating time, heating means, and the like are the same as those described for heating the transparent coating layer.
Thereby, it is considered that the thermal polymerization in the first coloring pattern proceeds with very high efficiency without being inhibited by oxygen. In other words, it is considered that the remaining amount of the thermally polymerizable group derived from the compound having the thermally polymerizable group in the first colored pattern is very small.
Therefore, in order to form the second or third colored pixel, as described later, the second or third colored radiation sensitive composition is provided on the first colored pattern by providing the second or third colored radiation sensitive composition. When the layer is formed and then exposed and developed, the thermally polymerizable group remaining in the first colored pattern reacts with the unreacted components in the second or third colored radiation-sensitive composition, resulting in a residue. Therefore, a color filter having more excellent spectral characteristics can be manufactured.

Next, as shown in the schematic cross-sectional view of FIG. 4, a second colored radiation-sensitive composition is embedded in each through-hole in the first through-hole portion group 121 and the second through-hole portion group 122 to obtain a plurality of The second colored radiation-sensitive composition is formed on the first colored pattern 12 in which the through-hole group 120 is formed in the first colored radiation-sensitive layer 11 so that the second colored pixel is formed. Layer 21 is laminated. Thereby, the 2nd coloring pattern 22 which has a some 2nd coloring pixel in the through-hole group 120 of the 1st coloring radiation sensitive layer 11 is formed. Here, the second colored pixel is a square pixel. The formation of the second colored radiation-sensitive layer 21 can be performed in the same manner as the method for forming the first colored radiation-sensitive layer 11 described above.
As thickness of the 2nd coloring radiation sensitive layer 21 here, the range of 0.3-1 micrometer is preferable, The range of 0.35-0.8 is more preferable, The range of 0.35-0.7 micrometer is more preferable.

  Then, by exposing and developing a position 21A corresponding to the first through-hole portion group 121 provided in the first colored radiation-sensitive layer 11 of the second colored radiation-sensitive layer 21, the second colored radiation-sensitive layer 21 is exposed. The radiation layer 21 and the plurality of second colored pixels 22R provided inside each through hole of the second through hole portion group 122 are removed (see the schematic cross-sectional view of FIG. 5).

When the second colored radiation-sensitive composition is a composition containing a compound having a thermally polymerizable group, the second colored pixel is heated by a heating device such as a hot plate or an oven. It is preferable to cure. The heating temperature is preferably 120 ° C to 250 ° C, and more preferably 160 ° C to 230 ° C. The heating time varies depending on the heating means, but is usually about 3 to 30 minutes when heated on a hot plate, and usually about 30 to 90 minutes when heated in an oven.
This heating is preferably performed in an environment where the oxygen concentration is 100 ppm or less, more preferably in an environment where the oxygen concentration is 100 ppm or less, as in the case of heating the transparent coating layer described above (here, the oxygen concentration). Is usually 0.01 ppm or more). The conditions for the heating temperature, heating time, heating means, and the like are the same as those described for heating the transparent coating layer.
Thereby, it is considered that the thermal polymerization in the second colored pixel proceeds with very high efficiency without being inhibited by oxygen. In other words, it is considered that the remaining amount of the thermally polymerizable group derived from the compound having the thermally polymerizable group in the second colored pixel is very small.
Therefore, in order to form the third colored pixel, as described later, the third colored pixel is formed on the first colored pattern formed by forming the second colored pattern having the second colored pixel in the first through-hole portion group. When a colored radiation-sensitive composition is provided to form a third colored radiation-sensitive layer, and then exposed and developed, the thermally polymerizable group remaining in the second colored pixel and the third colored radiation-sensitive composition Since it is possible to suppress the possibility that a residue is generated due to reaction with the photosensitive component therein, a color filter having more excellent spectral characteristics can be produced.

Next, as shown in the schematic cross-sectional view of FIG. 6, a third colored radiation-sensitive composition is embedded in each through-hole in the second through-hole portion group 122 to form a plurality of third colored pixels. As described above, the third colored radiation-sensitive layer 31 is formed from the third colored radiation-sensitive composition on the first colored pattern 12 in which the second colored pattern 22 is formed in the first through-hole portion group 121. . Thereby, the 3rd coloring pattern 32 which has a some 3rd coloring pixel in the 2nd through-hole part group 122 of the 1st coloring radiation sensitive layer 11 is formed. Here, the third colored pixel is a square pixel. The formation of the third colored radiation-sensitive layer 31 can be performed in the same manner as the method for forming the first colored radiation-sensitive layer 11 described above.
As thickness of the 3rd coloring radiation sensitive layer 31 here, the range of 0.3-1 micrometer is preferable, The range of 0.35-0.8 is more preferable, The range of 0.35-0.7 micrometer is more preferable.

  Then, the third colored radiation-sensitive layer 31 is exposed and developed at a position 31A corresponding to the second through-hole portion group 122 provided in the first colored layer 11 of the third colored radiation-sensitive layer 31. As shown in the schematic cross-sectional view of FIG. 7, the first colored pattern 12, the second colored pattern 22, and the third colored pattern 32 are formed on the transparent cured layer 60. The color filter 100 is manufactured.

  As described above, the method for producing the color filter according to the embodiment of the present invention has been described. In the above embodiment, although the heating of the transparent coating layer is not performed in an environment having an oxygen concentration of 100 ppm or less, the first colored radiation-sensitive property. The composition is a composition containing a compound having a thermally polymerizable group, and the first colored pattern formed from the first colored radiation-sensitive composition is heated in an environment having an oxygen concentration of 100 ppm or less. A form in which a cured pattern is formed and a second colored radiation-sensitive layer made of the second colored radiation-sensitive composition is laminated on the cured pattern is also suitable as a method for producing a color filter according to an embodiment of the present invention. is there.

Further, on a base layer (such as a silicon substrate) that does not correspond to a cured layer formed using a polymerizable compound (for example, the transparent cured layer formed by heating the transparent coating layer described in the above embodiment). The first colored radiation-sensitive composition is used to form the first colored pattern as described above, and the first colored pattern is heated in an environment having an oxygen concentration of 100 ppm or less to form a cured pattern. Also in the form of laminating the second colored radiation-sensitive layer made of the second colored radiation-sensitive composition on the cured pattern, generation of a development residue can be suppressed.
The reason for this is that, by first heating the first colored pattern under the above oxygen concentration conditions, thermal polymerization can proceed with very high efficiency in the first colored pattern. The residual amount of the thermally polymerizable group is very small, and the reaction between the surface portion of the first colored pattern and the unreacted component in the second colored radiation-sensitive composition can be suppressed. As a result, it is considered that when the second colored radiation-sensitive layer is exposed and developed, the unexposed portion of the second colored radiation-sensitive layer is surely removed by the developer.
Furthermore, when the first colored pattern is formed (that is, when the first colored radiation-sensitive layer is developed), the region where the first colored pattern is not formed (that is, the region where the surface of the underlayer is exposed). Above, unreacted substances (mostly transparent resins) derived from the first colored radiation-sensitive layer may remain without being removed by the developer. However, according to the present invention, not only the first colored pattern, but also this unreacted material is formed through “heating in an environment where the oxygen concentration is 100 ppm or less”, so that the thermal polymerization proceeds in the unreacted material. The degree is high, and the remaining amount of the thermally polymerizable group is small. Therefore, even if the second colored radiation-sensitive layer is formed on the first colored pattern using the second colored radiation-sensitive composition, for example, the unreacted material in the second colored radiation-sensitive composition and This is considered to be because the reaction with the “unreacted material remaining on the region where the first colored pattern is not formed” can be suppressed, and the development residue in the region where the first colored pattern is not formed can be suppressed.

(Polymerizable composition)
In the method for forming a cured layer or a cured pattern of the present invention, a polymerizable layer for obtaining a coating layer that is subjected to a heating step under an environment having an oxygen concentration of 100 ppm or less, or a pattern formed from the coating layer, Contains a compound having a thermally polymerizable group.
When the pattern formed from the coating layer or the coating layer is a transparent coating layer or a transparent pattern, the polymerizable composition is usually a transparent polymerizable composition.
When the coating layer or the pattern formed from the coating layer is a colored coating layer or a colored pattern, the polymerizable composition is usually a colored radiation-sensitive composition.

  The polymerizable composition is preferably a composition containing (i) colorless transparent particles, or (ii) any one or more of a color pigment and a dye, and the polymerizable composition is the transparent composition described above. In the case of a polymerizable composition, (i) a form containing colorless transparent particles is preferable, and in the case where the polymerizable composition is the colored radiation-sensitive composition, (ii) any one of a colored pigment and a dye. It is preferable that it is a form containing two or more.

  In the polymerizable composition, the compound having a thermopolymerizable group, the details of other components, the preferred content range of each component, and the like are the same as those described in the transparent polymerizable composition below. .

(Transparent polymerizable composition)
Hereinafter, the above-described transparent polymerizable composition will be described in detail.

-Polymerizable compound having a thermally polymerizable group-
The transparent polymerizable composition of the present invention contains a polymerizable compound having a thermally polymerizable group.

The thermopolymerizable group is preferably a radically polymerizable group, and preferable examples of the radically polymerizable group include an ethylenically unsaturated bond group.
Specifically, the polymerizable compound is preferably selected from compounds having at least one ethylenically unsaturated bond group, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as annulate, glycerin and trimethylolethane; Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Further, as other preferable polymerizable compounds, there are fluorene rings described in JP 2010-160418 A, JP 2010-129825 A, Japanese Patent No. 4364216, etc., and 2 ethylenically polymerizable groups. It is also possible to use a compound having a functionality or higher, a cardo resin.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or represents an _{-OC (= O) C (CH} 3) = groups represented by CH _2.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used as a polymerizable compound.

Among them, as the polymerizable compound, RP1040 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd. Dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product) As KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues. These oligomer types can also be used.
As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is essential.
Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferable.

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)
Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAADDPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3), Number of groups represented by formula (2) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3, Compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compound in which R ¹ is all hydrogen atoms), DPCA-120 (In the formula, m = 2, the number of groups represented by formula (2) = 6, and compounds in which R ¹ is all hydrogen atoms). In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  Moreover, it is also preferable that it is at least 1 sort (s) selected from the group of the compound represented by the following general formula (i) or (ii) as a polyfunctional monomer in this invention.

In the general formula (i) and (ii), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - a represents , Y each independently represents an integer of 0 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said general formula (i), the sum total of acryloyl group and methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group.
In said general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, n represents the integer of 0-10 each independently, and the sum total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen atom side ends Is preferred in which X is bonded to X.

  The compounds represented by the general formula (i) or (ii) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the specific monomer of the compound represented by general formula (i) or (ii), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compound represented by the general formula (i) or (ii) is a ring-opening skeleton by a ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available products of the specific monomers represented by the general formulas (i) and (ii) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and pliers manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six lenoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, JP-B 56-17654, JP-B 62-39417, and JP-B 62-39418. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are exemplified. By using it, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
As the polymerizable compound, ethylenically unsaturated compounds having an acid group are also suitable. The ethylenically unsaturated compounds having an acid group can be obtained by, for example, converting (meth) acrylate a part of the hydroxy group of the polyfunctional alcohol and adding an acid anhydride to the remaining hydroxy group to form a carboxy group. can get. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
A polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule is also suitable as the polymerizable compound. Particularly preferred are those represented by the following general formula (I).

(In the formula, R ¹ is an alkyl group, R ² is an n-valent aliphatic group that may contain atoms other than carbon, R ⁰ is an alkyl group that is not H, and n is 2 to 4.)

If the polyfunctional thiol compound represented by the general formula (I) is specifically exemplified, 1,4-bis (3-mercaptobutyryloxy) butane [formula (II)] having the following structural formula: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H, 5H) -trione [formula (III)] and pentaerythritol tetrakis (3-mercaptobutyrate) [formula (IV)] and the like. These polyfunctional thiols can be used alone or in combination.

  About the compounding quantity of the polyfunctional thiol in a transparent polymerizable composition, it is 0.3-8.9 weight% with respect to the total solid except a solvent, More preferably, it is the range of 0.8-6.4 weight%. It is desirable to add in. By adding a polyfunctional thiol, the stability, odor, sensitivity, resolution, developability, adhesion, etc. of the transparent polymerizable composition can be improved.

  About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a transparent polymerizable composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the transparent cured film, those having 3 or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. Further, it is preferable to use a trifunctional or higher-functional polymerizable compound having a different ethylene oxide chain length in that the developability of the transparent polymerizable composition can be adjusted and an excellent pattern forming ability can be obtained. . In addition, selection and use of polymerizable compounds for compatibility and dispersibility with other components (eg, photopolymerization initiator, colorless transparent particles, binder polymer, etc.) contained in the transparent polymerizable composition Is an important factor. For example, compatibility may be improved by the use of a low-purity compound or a combination of two or more. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

  The content of the polymerizable compound having a thermally polymerizable group in the transparent polymerizable composition of the present invention is preferably 0.1% by mass to 100% by mass with respect to the solid content in the transparent polymerizable composition, 1.0 mass%-80 mass% are further more preferable, and 2.0 mass%-70 mass% are especially preferable.

  In addition, when the transparent polymerizable composition of the present invention contains colorless transparent particles described in detail later, the content mass ratio between the colorless transparent particles and the polymerizable compound having a thermally polymerizable group (represented by the general formula (1)). The compound: polymerizable compound having a thermally polymerizable group) is preferably 1: 2 to 20: 1, more preferably 1: 1 to 10: 1, from the viewpoint of thinning.

~ Thermal crosslinking agent ~
The transparent polymerizable compound of the present invention may contain a compound having a thermally crosslinkable group (hereinafter also referred to as a thermal crosslinking agent). As the thermal crosslinking agent, for example, those having at least one group selected from an epoxy group, a methylol group, an alkoxymethyl group and an acyloxymethyl group are preferable.

  More preferable thermal crosslinking agents include (a) an epoxy compound, (b) a melamine compound, a guanamine compound, and a glycoluril compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Or a urea compound, (c) a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Among them, a polyfunctional epoxy compound is particularly preferable as the thermal crosslinking agent.

  The total content of the thermal crosslinking agent in the transparent polymerizable composition is preferably 0.1 to 50% by mass with respect to the total solid content (mass) of the transparent polymerizable composition, although it varies depending on the material. 2 to 40% by mass is more preferable, and 1 to 35% by mass is particularly preferable.

-Various additives-
In the transparent polymerizable composition in the present invention, various additives such as a binder, a curing agent, a curing catalyst, a solvent, a filler, and a polymer other than those described above are included in the range not impairing the effects of the present invention. A compound, a polymerization initiator, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a dispersant, and the like can be blended.

~binder~
The binder may or may not have alkali solubility as long as it is soluble in an organic solvent and maintains dispersion stability and curability.

  The binder is preferably a linear organic polymer that is soluble in an organic solvent. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.

  As the acrylic resin, a copolymer comprising monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, for example, benzyl methacrylate / methacrylic acid, Copolymers such as benzyl methacrylate / benzyl methacrylate, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), ACA230AA (Daicel Chemical Industries, Ltd.) Etc.) are preferable.

~ Curing agent ~
In the present invention, for example, when an epoxy compound is used as the thermal crosslinking agent, it is preferable to add a curing agent. There are many types of epoxy compound curing agents, and the properties, the pot life in the mixture of epoxy compound and curing agent, viscosity, curing temperature, curing time, heat generation, etc. vary greatly depending on the type of curing agent used, An appropriate curing agent must be selected according to the purpose of use, usage conditions, working conditions, and the like of the curing agent. The curing agent is described in detail in Chapter 5 of Hiroshi Kakiuchi “Epoxy resin (Shojodo)”. Examples of the curing agent are as follows.
Those that act catalytically include tertiary amines, boron trifluoride-amine complexes, those that react stoichiometrically with functional groups of epoxy resins, polyamines, acid anhydrides, etc .; Examples include diethylenetriamine, polyamide resin, and medium temperature curing examples such as diethylaminopropylamine and tris (dimethylaminomethyl) phenol; examples of high temperature curing include phthalic anhydride and metaphenylenediamine. In terms of chemical structure, in the case of amines, diethylenetriamine as an aliphatic polyamine; metaphenylenediamine as an aromatic polyamine; tris (dimethylaminomethyl) phenol as a tertiary amine; phthalic anhydride as an acid anhydride; polyamide resin Polysulfide resin, boron trifluoride-monoethylamine complex; Synthetic resin initial condensate includes phenol resin, dicyandiamide and the like.

  These curing agents react with a heat crosslinkable group (for example, an epoxy group in an epoxy compound) in a thermal crosslinker by heating and polymerize to increase the crosslink density and cure. For thinning, both the binder and the curing agent are preferably as small as possible. In particular, the curing agent is 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less with respect to the thermal crosslinking agent. It is preferable to do.

~ Curing catalyst ~
In order to achieve a high organic solvent concentration in the present invention, curing by reaction between epoxy groups is effective in addition to curing by reaction with the curing agent. For this reason, a curing catalyst can be used without using a curing agent. The amount of the curing catalyst added is about 1/10 to 1/1000, preferably about 1/20 to 1/500, more preferably about 1/30, based on the mass of the epoxy compound having an epoxy equivalent of about 150 to 200. It can be cured with a slight amount of about 1/250.

~solvent~
The transparent polymerizable composition in the present invention can be used as a solution dissolved in various solvents. Each solvent used in the transparent polymerizable composition in the present invention is basically not particularly limited as long as the solubility of each component and the coating property of the transparent polymerizable composition are satisfied.

~ Colorless transparent particles ~
The transparent polymerizable composition of the present invention may contain colorless transparent particles.
The colorless transparent particles are not particularly limited, but are preferably inorganic fine particles, and the refractive index with respect to light having a wavelength of 633 nm of the finally obtained transparent cured film or transparent cured pattern is desired to be within a range of 1.60 to 1.90. In some cases, the inorganic fine particles are preferably one or more oxides selected from the group consisting of Si, Ti, Zr, Al and Sn, and one or more oxides selected from Ti, Al and Sn. Two or more oxides are more preferable, and one or two oxides selected from Ti and Al are more preferable.
Specific examples of the oxide include TiO ₂ , Al ₂ O ₃ , SiO ₂ , SnO, SnO _{2 and the} like.

  The method for producing inorganic fine particles is described in, for example, JP-A Nos. 10-81517 and 2001-26423.

The colorless transparent particles preferably have an average particle diameter of 1 to 200 nm, more preferably 10 to 100 nm.
The average particle diameter of the colorless transparent particles can be obtained from the photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom to obtain the average particle size (usually, 300 or more particles are measured in order to obtain the average particle size).

  The refractive index of the colorless transparent particles is preferably 1.6 to 2.8, more preferably 1.7 to 2.7, and most preferably 1.8 to 2.7.

The primary particle diameter of these colorless and transparent particles is preferably 1 to 100 nm, and more preferably 1 to 60 nm.
The colorless and transparent particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as they satisfy a predetermined particle size. The shape is most preferably a spherical shape, but may be a bead shape, a shape having a major axis / minor axis ratio of 1 or more, or an indefinite shape.

The specific surface area of the colorless transparent particles is preferably 10~2000m ² / g, more preferably from 20~1800m ² / g, and most preferably 40~1500m ² / g.

As the colorless transparent particles, commercially available particles can be preferably used.
For example, Ishihara Sangyo TTO series (TTO-51 (A), TTO-51 (C), etc.), TTO-S, V series (TTO-S-1, TTO-S-2, TTO-V-3) Etc.), MT series (MT-01, MT-05, etc.) manufactured by Teika Co., Ltd. can be used.

  When colorless transparent particles are added to a transparent polymerizable composition as a dispersion containing colorless transparent particles and a dispersant (details of the dispersant will be described later), the colorless transparent particles contained in the colorless transparent particle dispersion The amount is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 40% by mass, and further preferably 15% by mass to 30% by mass.

  The content of the colorless transparent particles with respect to the total solid content of the transparent polymerizable composition is preferably 10% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and 30% by mass to 80% by mass. More preferably, it is mass%.

~ Dispersant ~
Moreover, when a transparent polymerizable composition contains the said colorless transparent particle especially, in order to improve the dispersibility of a colorless transparent particle, a transparent polymerizable composition may contain a dispersing agent. As the dispersant, known ones can be appropriately selected and used, and examples thereof include a cationic surfactant, a fluorosurfactant, and a polymer dispersant.
As these dispersants, many kinds of compounds are used. For example, a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Nippon Lubrizol); organosiloxane polymer KP341 (Shin-Etsu) Chemical Industry Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc. Cationic surfactants of: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Steal, Pionine D-6315, D-6112W (Nonionic surfactants such as Takemoto Yushi Co., Ltd.); Anionic surfactants such as W004, W005, W017 (manufactured by Yusho Co., Ltd.); MegaFuck F781 (DIC) BYK-2001 (manufactured by BYK), EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (more Morishita) Industry Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco Co., Ltd.) and the like; Solsperse 3000, 5000, 9000, 12000, 13240 13,940, 17000, 20000, 2400 , 26000, 28000, etc. (manufactured by Nippon Lubrizol); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.) are mentioned.

  The dispersants may be used alone or in combination of two or more. The addition amount of the dispersant in the transparent polymerizable composition in the present invention is usually preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the pigment.

~ Radical polymerization initiator ~
The transparent polymerizable composition of the present invention preferably further contains a radical polymerization initiator from the viewpoint of further improving sensitivity.
The radical polymerization initiator is preferably a radical photopolymerization initiator, thereby imparting photosensitivity to the polymerizable composition to form a photosensitive composition, and transparent pixels (white pixels) in the color filter. Since it can be suitably used for a resist or the like for forming the film, it is preferably contained. As the radical polymerization initiator, those known as photopolymerization initiators described below can be used.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators, for example, visible from the ultraviolet region. Those having photosensitivity to light are preferable, and may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and initiates cationic polymerization according to the type of monomer. It may be an initiator.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime. Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  In addition, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbo Rubis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphite Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) Examples thereof include compounds described in JP-A Nos. 53-133428, 57-1819, 57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As an aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products.

  Further, as oxime ester compounds other than those described above, compounds described in JP-T 2009-519904 in which oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, and dyes A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced, a ketoxime compound described in International Publication No. 2009-131189, a triazine skeleton and an oxime skeleton are contained in the same molecule The compound described in US Pat. No. 7,556,910, the compound described in JP2009-221114A having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.

  Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A. Among the cyclic oxime compounds, the cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A are particularly preferable in terms of high light absorption and high sensitivity. In addition, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can achieve high sensitivity by regenerating an active radical from a polymerization inert radical, and can be suitably used. .

Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime photopolymerization initiator is preferably a compound represented by the following formula (1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

(In formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group. Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

  The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (1), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (2).

(In formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
R, A, and Ar in formula (2) have the same meanings as R, A, and Ar in formula (1), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “” represents the bonding position between Y and an adjacent carbon atom in the formula (2).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  Furthermore, the oxime compound is preferably a compound represented by the following formula (3).

(In formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.)
R, X, A, Ar, and n in Formula (3) have the same meanings as R, X, A, Ar, and n in Formula (2), respectively, and preferred examples are also the same.

  Specific examples (C-4) to (C-13) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

The radical photopolymerization initiator used in the present invention may be used in combination of two or more as required.
The content of the radical photopolymerization initiator in the transparent polymerizable composition (the total content in the case of two or more) is 0.1 to 20% by mass relative to the total solid content of the transparent polymerizable composition. A range is preferable, More preferably, it is the range of 0.5-10 mass%, Most preferably, it is the range of 1-8 mass%. Within this range, good sensitivity and pattern formability can be obtained.

  The transparent polymerizable composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, a sensitizer that sensitizes the above-mentioned photo radical polymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer used in the transparent polymerizable composition include compounds described in paragraph numbers [0101] to [0154] of JP-A-2008-32803.
The content of the sensitizer in the polymerizable composition is preferably 0.1% by mass to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency, 5 mass%-15 mass% are more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

~Organic solvent~
The transparent polymerizable composition of the present invention generally contains an organic solvent. The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the transparent polymerizable composition, but it should be selected in consideration of the solubility, applicability, and safety of the binder. Is preferred. Moreover, when preparing the transparent polymeric composition in this invention, it is preferable that at least 2 type of organic solvent is included.

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

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

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

~ Other additives ~
Various additives can be further added to the non-photosensitive transparent polymerizable composition in the present invention as necessary. Specific examples of the various additives include, for example, various additives described in JP-A-2005-326453. An example is a silane coupling agent, and KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.) is preferably used.

More specifically, in the transparent polymerizable composition, when a cured film having a film thickness of 1 μm is formed from the composition, the light transmittance in the thickness direction of the cured film is 90 over the entire wavelength region of 400 nm to 700 nm. % Of the composition is preferred.
Such physical property (transparency) of light transmittance is suitably achieved by adjusting the type and content of each component that can be contained in the above-described transparent polymerizable composition. Further, when the transparent polymerizable composition contains the above colorless transparent particles, for example, adjusting the particle diameter of the colorless transparent particles, adding a dispersant, and adjusting the type and addition amount thereof. Thus, the physical properties of the light transmittance can be suitably achieved.
Regarding the transparent polymerizable composition, the light transmittance is 90% or more over the entire wavelength region of 400 nm to 700 nm, which means that the transparent cured film or the transparent cured pattern is transparent in the underlayer of the color filter or the color filter. It is suitable for fulfilling a sufficient function as a pixel (white pixel).

  The light transmittance is preferably 95% or more, more preferably 99% or more, and most preferably 100% over the entire wavelength region of 400 nm to 700 nm.

  Moreover, the composition of the present invention does not substantially contain a colorant (the content of the colorant is preferably 0% by mass with respect to the total solid content of the composition).

[Colored radiation-sensitive composition]
Next, the colored radiation-sensitive composition described above will be described in detail.
The colored radiation-sensitive composition (more specifically, each of the first colored radiation-sensitive composition, the second colored radiation-sensitive composition, and the third colored radiation-sensitive composition in the above embodiment) Usually contains a colorant.
The colored radiation-sensitive composition is preferably in a form containing at least one of a color pigment and a dye as a colorant.

The first colored radiation-sensitive layer 11 is preferably a green transmission layer or a black layer for a black matrix, and more preferably a green transmission layer.
The colorant in the first colored radiation-sensitive composition is C.I. I. Pigment Green 7, 10, 36, 37, 58 and C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , Is preferably at least one selected from 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214.

Moreover, it is preferable that one of the second colored pixel and the third colored pixel is a red transmissive portion, and the other is a blue transmissive portion.
The colorant contained in the coloring composition for forming the red transmission part is C.I. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, And C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279 Species It is preferably a coloring agent contained in the coloring composition for forming a blue transmission unit, C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, and C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 It is preferable.

  In each of the first colored radiation-sensitive composition, the second colored radiation-sensitive composition, and the third colored radiation-sensitive composition, the content of the colorant composition with respect to the total solid content is 30% by mass or more. It is preferable that it is 35 mass% or more, and it is still more preferable that it is 40 mass% or more. Moreover, content with respect to the total solid of the composition of a coloring agent is 90 mass% or less normally, and it is preferable that it is 80 mass% or less.

  Moreover, it is preferable that a negative radiation sensitive composition is respectively used for the 1st colored radiation sensitive composition, the 2nd colored radiation sensitive composition, and the 3rd colored radiation sensitive composition. As this negative type radiation sensitive composition, there is a negative type feeling sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays. A radiation composition can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.

Specifically, the negative radiation-sensitive composition is preferably a composition containing a photopolymerization initiator, a polymerization component (polymerizable compound), a binder resin (alkali-soluble resin, etc.) and the like. Examples described in Paragraph Nos. [0017] to [0064] of Kaikai 2005-326453.
Such a negative radiation sensitive composition utilizes the fact that the photopolymerization initiator initiates the polymerization reaction of the polymerizable compound upon irradiation with radiation, and as a result, the alkali soluble state becomes alkali insoluble. To do.

The first colored radiation-sensitive layer 11, the second colored radiation-sensitive layer 21, and the third colored radiation-sensitive layer 31 are exposed by g-line, h-line, i-line, etc., preferably i-line. Can be done.
The development performed after exposure is usually performed by developing with a developer.

  As the developer, for example, a combination of various organic solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, and 1,8-diazabicyclo [5.4.0] -7-undecene. In addition, when alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.

  The length of one side of the first colored pixel, the second colored pixel, and the third colored pixel (the length of the short side when the pixel is a rectangle, and the length of one side when the pixel is a square) is From the viewpoint of image resolution, 0.5 to 1.7 μm is preferable, and 0.6 to 1.5 μm is more preferable.

  Further, when the colored coating layer or the colored pattern formed by the colored radiation-sensitive composition is subjected to a heating step in an environment having an oxygen concentration of 100 ppm or less, the colored radiation-sensitive composition is subjected to thermal polymerization. Contains a compound having a functional group. Specific examples, preferred examples of the compound having a thermopolymerizable group, and a preferred range of the content with respect to the total solid content of the colored radiation-sensitive composition are the same as those described in the transparent polymerizable composition. The compound having a thermopolymerizable group may correspond to a photopolymerizable compound as long as it has thermal polymerizability. Paragraph No. [0017] of the above-mentioned JP-A-2005-326453. ] To [0064] Among the compounds described in [0064], those having thermal polymerizability may be used.

  Further, the colored radiation-sensitive composition may contain each component described in the above [transparent polymerizable composition] as long as it contains the colorant, and the content of the component in that case (total composition) The solid content standard) is the same as that described in the above [Transparent polymerizable composition].

  The color filter obtained from the above-described method for producing a color filter of the present invention can be suitably used for a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.). Moreover, it can use suitably also for image display devices, such as electronic paper and an organic electroluminescence display. In particular, the color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD and a CMOS.

The color filter of the present invention is also suitable as a color filter for a liquid crystal display device. In this case, the cured layer or cured pattern obtained from the cured layer or cured pattern forming method of the present invention is an existing member constituting a liquid crystal display device, and contains a compound having a thermopolymerizable group. It is suitably provided as a transparent member that can be formed from a composition, a color filter underlayer, a colored pixel in a color filter, and the like.
Such a liquid crystal display device can display a high-quality image with a good display image color and excellent display characteristics.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is useful for a color TFT type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention can also be used for a bright and fine COA (Color-filter On Array) system.
The colored layer formed by the COA method has a rectangular shape with a side length of about 1 to 15 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a through hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is particularly preferably 5 μm or less, but by using the present invention, It is also possible to form a conduction path of 5 μm or less. These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display element composed of these known members. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, 18-24 pages (Yasuhiro Shima), 25-30 pages (Yukiaki Yagi), etc. Have been described.

  When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. In each step, when processing using a commercially available processing solution was performed, each processing was performed according to the method specified by the manufacturer unless otherwise specified.

Example 1
(Preparation of transparent polymerizable composition)
A transparent polymerizable composition was prepared by mixing the following components.
Compound having a thermally polymerizable group: Cyclomer ACA-230β (CR-1000) (Mw = 7700, solid content acid value 15 mgKOH / g) (manufactured by Daicel Chemical Industries)
12.191 parts by mass-Fluorosurfactant: Megafac F-781 (manufactured by DIC Corporation) 0.834 parts by mass-Solvent: Propylene glycol monomethyl ether acetate (PGMEA)
54.56 parts by mass-solvent: ethyl 3-ethoxypropionate (EEP) 32.415 parts by mass

(Formation of transparent cured layer)
A heating tank having a hot plate was provided as a heating means, and a coater developer (ACT8 manufactured by Tokyo Electron Co., Ltd.) configured to introduce nitrogen into the heating tank and seal it was prepared.
A silicon (Bare-Si) substrate is placed on the hot plate, and the transparent polymerizable composition prepared as described above is coated on the silicon (Bare-Si) substrate with a thickness of 0.1 μm. It applied so that it might become. Then, it dried with the hotplate for 2 minutes at 100 degreeC, and the transparent coating layer was formed by cooling for 1 minute at 23 degreeC on a hotplate as it is.
Next, the heating tank was sealed, and nitrogen was introduced while exhausting the air in the heating tank. The oxygen concentration in the heating tank was 80 ppm.
Subsequently, it heated with the hotplate at 200 degreeC for 5 minute (s), and the transparent cured layer was formed by cooling at 23 degreeC after heating.

(Preparation of green radiation-sensitive composition)
A green radiation sensitive composition was prepared by mixing the following components.
-Pigment dispersion: 51.2 parts by mass of the following Green pigment dispersion G1-Photopolymerization initiator: IRGACURE OXE-01 (manufactured by BASF Corporation)
0.87 parts by mass Polymerizable compound: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) 4.7 parts by mass Binder: ACA230AA (manufactured by Daicel Chemical Industries, Ltd.) 7.4 parts by mass, polymerization inhibitor : 0.002 parts by mass of p-methoxyphenol, additive: Pionein D-6112-W (manufactured by Takemoto Yushi Co., Ltd.) 0.19 parts by mass, silane coupling agent: KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.) 10.8 parts by mass of a cyclohexanone solution in a solvent: 14.3 parts by mass of PGMEA Solvent: 6.4 parts by mass of cyclohexanone Fluorosurfactant: cyclohexanone of F-781 (manufactured by DIC Corporation) 0.2% by mass solution 4.2 parts by mass

(Preparation of Green pigment dispersion G1)
PGMEA solution containing Green pigment (Pigment Green 36 / Pigment Green 7 / Pigment Yellow 139 = mass ratio 80/20/30) and BYK-161 (manufactured by BYK) as a dispersion resin is mixed by a bead mill for 15 hours. -Dispersed to prepare a Green pigment dispersion G1 having a solid concentration of 25.5% by mass and a pigment concentration of 15.3% by mass.

[Formation of green pattern]
The green radiation-sensitive composition prepared as described above was applied onto the transparent cured layer so as to form a coating layer having a thickness of 0.6 μm. Then, it dried with the hotplate for 3 minutes at 100 degreeC, and after drying, the green radiation sensitive layer was formed by cooling on a hotplate as it is for 1 minute at 23 degreeC.
The green radiation sensitive layer thus obtained was subjected to an exposure amount of 350 mJ / cm ² using FPA3000i5 + (an i-line stepper manufactured by Canon Inc., NA / σ = 0.60 / 0.65). The pattern was exposed. Here, the exposure pattern was a checkered pattern in which one side of the square lattice was 1.2 μm.

Next, the layered product after exposure was placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemtronics Co., Ltd.), and CD-2040 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). Was used to perform paddle development at 23 ° C. for 60 seconds.
Thereafter, the laminate is fixed to the horizontal rotary table by a vacuum chuck method, and ultrapure water (DIW) (23 ° C.) is straightened from above the rotation center while rotating the color filter at a rotation speed of 50 rpm by a rotating device. It supplied from the nozzle and rinsed for 60 seconds, and then spray-dried.
Thus, a laminate (corresponding to the state of FIG. 3) in which a checkered green pattern was formed on the transparent cured layer was obtained.

  The upper surface of the obtained checkered green pattern was observed using a length-measuring scanning electron microscope (S-9260 manufactured by Hitachi High-Technologies Corporation, Mag: x 30.0 k, HV / IP: 600 v / 8.0 pA). As a result, as shown in FIG. 8, almost no residue was confirmed in the through hole group of the green pattern.

(Comparative Example 1)
In the above [Formation of transparent cured layer], a green pattern was formed in the same manner as in Example 1 except that a post-baking treatment was performed in the air on a hot plate having no nitrogen substitution function.
The upper surface of the obtained checkered green pattern was observed using a length-measuring scanning electron microscope (S-9260 manufactured by Hitachi High-Technologies Corporation, Mag: x 30.0 k, HV / IP: 600 v / 8.0 pA). As a result, as shown in FIG. 9, many residues were confirmed in the through hole group of the green pattern.

(Example 2)
(Preparation of red radiation-sensitive composition)
A red radiation sensitive composition was prepared by mixing the following components.
Pigment dispersion: 51.2 parts by weight of the following Red pigment dispersion R1 Photopolymerization initiator: IRGACURE OXE-01 (manufactured by BASF Corporation)
0.87 parts by mass of a compound having a thermopolymerizable group: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.)
4.7 parts by mass / binder: ACA230AA (manufactured by Daicel Chemical Industries, Ltd.) 7.4 parts by mass / polymerization inhibitor: p-methoxyphenol 0.002 parts by mass / additive: Pionine D-6112-W (Takemoto Yushi 0.19 parts by mass, silane coupling agent: KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.), cyclohexanone 0.9 mass% 10.8 parts by mass, solvent: PGMEA 14.3 parts by mass, Solvent: 6.4 parts by mass of cyclohexanone. Fluorosurfactant: 0.2% by mass of cyclohexanone 0.2% by mass solution of F-781 (manufactured by DIC Corporation).

(Preparation of Red pigment dispersion R1)
Pigment Red254 8.3 parts and Pigment Yellow 139 3.7 parts by weight as a pigment, BYK-161 (manufactured by BYK) 4.8 parts by weight, and PGMEA 83.2 parts by weight as a pigment dispersant Then, the mixture was dispersed and dispersed by a bead mill for 15 hours to prepare a Red pigment dispersion R1.

[Formation of red radiation-sensitive layer]
A heating tank having a hot plate was provided as a heating means, and a coater developer (ACT8 manufactured by Tokyo Electron Co., Ltd.) configured to introduce nitrogen into the heating tank and seal it was prepared.
A silicon (Bare-Si) substrate is placed on the hot plate, and the red radiation-sensitive composition prepared as described above is applied on the silicon (Bare-Si) substrate to a thickness of 0.7 μm. It applied so that it might become a layer. Then, it dried with the hotplate for 2 minutes at 100 degreeC, and formed the red radiation sensitive layer by cooling for 1 minute at 23 degreeC on a hotplate as it is.

The red radiation-sensitive layer thus obtained was subjected to open frame exposure (entire exposure) with an exposure amount of 800 mJ / cm ² using FPA3000i5 + (an i-line stepper manufactured by Canon Inc.).

Next, the layered product after the exposure was placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2060 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). Was used to perform paddle development at 23 ° C. for 60 seconds.
Thereafter, the laminate is fixed to the horizontal rotary table by a vacuum chuck method, and ultrapure water (DIW) (23 ° C.) is straightened from above the rotation center while rotating the laminate at a rotation speed of 50 rpm by a rotating device. It supplied from the nozzle, rinsed for 60 seconds, and then spray-dried.

The obtained laminate was conveyed again into the heating tank of the coater developer.
Next, the heating tank was sealed, and nitrogen was introduced while exhausting the air in the heating tank. The oxygen concentration in the heating tank was 80 ppm.
The inside of the heating tank was heated with a hot plate at 200 ° C. for 5 minutes, and after heating, the red cured layer was formed by cooling at 23 ° C.

(Preparation of blue radiation-sensitive composition)
A blue radiation sensitive composition was prepared by mixing the following components.
・ Pigment dispersion: 51.2 parts by mass of the following Blue pigment dispersion B1 ・ Photopolymerization initiator: IRGACURE OXE-01 (manufactured by BASF Corporation)
0.87 parts by mass Polymerizable compound: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) 4.7 parts by mass Binder: ACA230AA (manufactured by Daicel Chemical Industries, Ltd.) 7.4 parts by mass, polymerization inhibitor : 0.002 parts by mass of p-methoxyphenol, additive: Pionein D-6112-W (manufactured by Takemoto Yushi Co., Ltd.) 0.19 parts by mass, silane coupling agent: KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.) 10.8 parts by mass of a cyclohexanone solution in a solvent: 14.3 parts by mass of PGMEA Solvent: 6.4 parts by mass of cyclohexanone Fluorosurfactant: cyclohexanone of F-781 (manufactured by DIC Corporation) 0.2% by mass solution 4.2 parts by mass

(Preparation of Blue pigment dispersion B1)
Pigment Blue 15: 6 9.5 parts by mass as a pigment, Pigment Violet 23 2.4 parts by mass, BYK-161 (manufactured by BYK) as a pigment dispersant 5.6 parts by mass, and PGMEA 82.5 parts by mass The mixed solution was mixed and dispersed by a bead mill for 15 hours to prepare Blue pigment dispersion B1.

[Formation of blue pattern]
The blue radiation-sensitive composition prepared as described above was applied onto the red cured layer so as to form a coating layer having a thickness of 0.7 μm. Then, it dried on the hotplate for 2 minutes at 100 degreeC, and after drying, the blue radiation sensitive layer was formed by cooling on a hotplate as it is for 1 minute at 23 degreeC.
The blue radiation-sensitive layer thus obtained was subjected to pattern exposure with an exposure amount of 800 mJ / cm ² using FPA3000i5 + (an i-line stepper manufactured by Canon Inc.). Here, the exposure pattern was a pattern in which a plurality of square isolated patterns each having a side of 1.4 μm were arranged in a square pattern (the distance between the centers of the square isolated patterns was 2.8 μm).

Next, the layered product after the exposure was placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2060 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). Was used to perform paddle development at 23 ° C. for 60 seconds.
Thereafter, the laminate is fixed to the horizontal rotary table by a vacuum chuck method, and ultrapure water (DIW) (23 ° C.) is straightened from above the rotation center while rotating the color filter at a rotation speed of 50 rpm by a rotating device. It supplied from the nozzle and rinsed for 60 seconds, and then spray-dried.
As described above, a laminate having a blue pattern formed on the red cured layer was obtained.

  When the upper surface of the obtained blue pattern was observed using a length-measuring scanning electron microscope (S-9260 manufactured by Hitachi High-Technologies Corporation, Mag: x 30.0 k, HV / IP: 600 v / 8.0 pA), As shown in FIG. 10, almost no residue was observed in the region other than the blue pattern (that is, the red region).

Moreover, the relationship between the wavelength and transmittance in the red cured layer before forming the blue radiation-sensitive layer was compared with the relationship between the wavelength and transmittance in the red region of the laminate after forming the blue pattern. The result is shown in FIG.
For the wavelength 450 nm, the wavelength 550 nm, and the “wavelength at which the transmittance shows the minimum value among the wavelengths 650 to 800 nm”, specific numerical values of the transmittance at these wavelengths and “form a blue radiation sensitive layer” The rate of change in transmittance before and after blue pattern formation ”is shown in the table below.

  As can be seen from FIG. 11 and Table 1, in Example 2, the relationship between the wavelength and the transmittance in the red cured layer before forming the blue radiation-sensitive layer, and the red region of the laminate after forming the blue pattern. There was no significant difference between the relationship between the wavelength and the transmittance, and it was confirmed that the spectral characteristics in the red region did not deteriorate even after the blue pattern was formed.

(Comparative Example 2)
In the above [Formation of red radiation-sensitive layer], a blue pattern was formed in the same manner as in Example 2 except that a post-baking treatment was performed in the air on a hot plate having no nitrogen substitution function. .
The upper surface of the obtained blue isolated pattern was observed using a length-measuring scanning electron microscope (S-9260 manufactured by Hitachi High-Technologies Corporation, Mag: x 30.0 k, HV / IP: 600 v / 8.0 pA). However, as shown in FIG. 12, in the region other than the blue isolated pattern (that is, the red region), a residue surrounded by a circle is confirmed.

Moreover, the relationship between the wavelength and transmittance in the red cured layer before forming the blue radiation-sensitive layer was compared with the relationship between the wavelength and transmittance in the red region of the laminate after forming the blue pattern. The result is shown in FIG.
For the wavelength 450 nm, the wavelength 550 nm, and the “wavelength at which the transmittance shows the minimum value among the wavelengths 650 to 800 nm”, specific numerical values of the transmittance at these wavelengths and “form a blue radiation sensitive layer” The rate of change in transmittance before and after blue pattern formation ”is shown in the table below.

  As can be seen from FIG. 13 and Table 2, in Comparative Example 2, the relationship between the wavelength and transmittance of the red cured layer before forming the blue radiation-sensitive layer, and the red region of the laminate after forming the blue pattern. The difference between the relationship between the wavelength and the transmittance was larger than that in Example 2, and it was confirmed that the spectral characteristics in the red region were changed by forming the blue pattern.

  As described above, after forming the transparent coating layer or colored pattern, another colored radiation-sensitive composition is formed thereon by forming a transparent cured layer or colored cured pattern by heating in an environment having an oxygen concentration of 100 ppm or less. It was found that even when the color filter is provided, the spectral characteristics are more difficult to change, and a color filter having excellent spectral characteristics can be manufactured.

DESCRIPTION OF SYMBOLS 10 Solid-state image sensor 11 1st colored radiation sensitive layer 12 1st colored pattern 13,100 Color filter 14 Flattening film 15 Microlens 20G Green pixel (1st color pixel)
20R red pixel (second color pixel)
20B Blue pixel (third color pixel)
21 Second colored radiation-sensitive layer 22 Second colored pattern 31 Third colored radiation-sensitive layer 32 Third colored pattern 41 P well 42 Light-receiving element (photodiode)
43 Impurity diffusion layer 44 Electrode 45 Wiring layer 46 BPSG film 47 Insulating film 48 P-SiN film 49 Flattened film layer 60 Transparent cured layer 120 Through-hole group 121 First through-hole part group 122 Second through-hole part group

Claims (9)

  A coating layer formed by coating a polymerizable composition containing a compound having a thermally polymerizable group on a substrate or a pattern formed by the coating layer is heated in an environment where the oxygen concentration is 100 ppm or less. A method for forming a cured layer or a cured pattern, comprising the step of:   The method for forming a cured layer or a cured pattern according to claim 1, wherein the coating layer or pattern is heated in the presence of an inert gas in a sealed heating tank.   The method for forming a cured layer or a cured pattern according to claim 1 or 2, wherein the polymerizable composition is a transparent polymerizable composition.   The polymerizable composition according to any one of claims 1 to 3, wherein the polymerizable composition further comprises (i) colorless transparent particles or (ii) any one or more of a color pigment and a dye. The method for forming a cured layer or a cured pattern according to Item.   The method for forming a cured layer or a cured pattern according to any one of claims 1 to 4, wherein the thermally polymerizable group is a radically polymerizable group.   The manufacturing method of a color filter containing the formation method of the hardened layer or hardened pattern of any one of Claims 1-5.   A color filter obtained by the method for producing a color filter according to claim 6.   A solid-state imaging device having the color filter according to claim 7.   A liquid crystal display device having the color filter according to claim 7.