JPS6240445A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive composition suitable for the formation of a resin relief similar in thermal behavior to a smooth org. polymer film by adding an org. polymer having <=100 deg.C glass transition point in the form of fine particles to a hydrophilic high molecular compound having photosensitivity by 1-25wt% of the amount of the high molecular compound. CONSTITUTION:An org. polymer having <=100 deg.C, preferably <=30 deg.C glass transition point in the form of fine particles is added to a hydrophilic hgih molecular compound having photosensitivity by 1-25wt%, preferably 15-25wt% of the high molecular compound. The hydrophilic high molecular compound having photosensiticity is preferably prepd. by introducing ammonium dichromate into gelatin, casein or polyvinyl alcohol so as to provide photosensitivity. Polyethyl acrylate, polybutyl acrylate or styrene-butadiene rubber may be used as the org. polymer having <=100 deg.C glass transition point.

Description

[Detailed description of the invention] [Field of invention] The present invention relates to a photosensitive composition.

More specifically, the present invention relates to a photosensitive composition suitable for forming a resin relief such as a gelatin relief formed in the manufacturing process of a micro color filter for a color imaging device.

[Background of the Invention] In VTR cameras and the like, the micro color filter provided on the light-receiving surface of the imaging device 5 in order to extract color signals corresponding to color images is composed of multiple layers of colored resin films. The resin film is made by coating a photosensitive hydrophilic polymer compound on the light-receiving surface of the imaging device and developing it into a desired pattern to form a resin relief (cured resin 11!I formed as a pattern). It is prepared by coloring it with dye. For example, when using the additive color method, blue, green, and red dyes are used, and when using the subtractive color method, the three colors cyan, yellow, and magenta are used.

In recent years, solid-state image sensors have been developed as imaging devices, and since they are very advantageous in reducing the size of the entire imaging device, their use has been studied, and some have already been put into practical use. Solid-state image sensing devices are usually formed and used on wafers, but they have the disadvantage that their functionality tends to deteriorate, especially due to contamination with impurities such as alkali ions. Therefore, the surface (light-receiving surface) of the solid-state image sensor is usually covered and protected with phosphosilicate glass or the like. On the other hand, the micro color filter attached to the light-receiving surface of the solid-state image sensor is used to accurately color separate the received image and reproduce it with high precision, so the thickness of the colored resin film that makes up the filter, High precision is required for surface smoothness. However, the surface of a coating layer such as phosphosilicate glass on a solid-state image sensor often does not have sufficient smoothness. For this reason, when forming a colored resin film on the protective layer of the light-receiving surface of a solid-state image sensor, usually a smooth layer made of an organic polymer such as a lipophilic resist is first provided on the protective layer. There is.

The present inventor has conducted various experiments regarding the production of micro color filters, but has found that the colored resin film formed on the smooth layer of the polymer deforms or moves, or that the resin It has been found that there is a tendency for cracks to occur in the film.

For this reason, the present inventor conducted research to investigate the cause and found that the above-mentioned deformation, movement, and cranking of the colored resin film are caused mainly by the organic polymer forming the smooth layer and the colored resin film. It was found that this is due to the difference in behavior due to heat from the formed polymer compound.

That is, colored resin films are produced by forming a resin pattern (relief) from a photosensitive resin in which a photosensitive group is attached to a hydrophilic polymer compound such as gelatin, casein, or polyvinyl alcohol, and then dyeing this. This manufacturing process includes heat treatment for the purpose of drying, resist dyeing, etc.The smooth layer and the colored resin film, which have different thermal behaviors (for example, thermal expansion properties), are mutually separated in this heat treatment process. It was found that this was the main cause of deformation, movement, and cracking of the colored resin film.

[Object of the Invention] An object of the present invention is to provide a photosensitive composition suitable for producing a colored resin film of a micro color filter.

The present invention aims to provide a photosensitive composition suitable for forming a resin relief whose thermal behavior is similar to that of a smooth layer made of an organic polymer, especially when used in the production of a colored resin film for a micro color filter. purpose.

[Summary of the Invention] The present invention provides a photosensitive hydrophilic polymer compound and 1 to 25% by weight (preferably,
15 to 25% by weight) of a particulate organic polymer having a glass transition point of 100°C or lower (preferably 30°C or lower).

The photosensitive hydrophilic polymer compound is preferably one of gelatin, casein, and polyvinyl alcohol.

[Effects of the Invention] The colored resin film formed on the surface of the organic polymer smooth layer of a solid-state imaging device using the photosensitive composition of the present invention does not easily deform even when subjected to ordinary heat treatment, and does not cause cracks. There are hardly any. Therefore, the micro color filter manufactured using the photosensitive composition of the present invention exhibits highly accurate color resolution.

Furthermore, the photosensitive composition of the present invention can be particularly advantageously used in the production of micro color filters consisting of fine patterns. Furthermore, since the manufacturing process of a micro color filter using the photosensitive composition of the present invention does not require special consideration in selecting the conditions for heat treatment, the manufacturing process is only eight steps.

In addition, when the photosensitive composition of the present invention forms a layer in contact with a layer made of a lipophilic resin, it exhibits advantageous behavior such as affinity and similarity in thermal behavior. The products are useful in a variety of applications.

[Detailed Description of the Invention] The photosensitive composition of the present invention comprises a photosensitive hydrophilic polymer compound and a particulate organic polymer having a glass transition point of 100° C. or lower.

Preferred examples of the above hydrophilic composition include gelatin,
Mention may be made of casein, and polyvinyl alcohol. Techniques for making these compounds photosensitive are already known. That is, photosensitivity can be introduced using, for example, dichromic acid.

As an example of a particulate organic polymer having a glass transition point (Tg) of 100°C or less, polyethyl acrylate CTg=-
29 to -23°C), polybutyl acrylate (Tg = approximately -70°C), polyvinyl acetate (Tg = +28 to +31°C)
), and styrenic butadiene rubber (Tg = approx. -67
℃) is formed in the form of fine particles. Note that the above glass transition points (Tg) are values for molecules having a molecular weight of approximately 100,000, and may vary slightly due to differences in molecular weight, manufacturing method, etc. Moreover, the 1 g value of styrene and butadiene rubber is shown for a rubber with a styrene content of 22 mol%.

In addition, the glass transition point of the above-mentioned particulate 41 polymer is 3
The temperature is preferably 0°C or lower.

The fine particles of the above-mentioned organic polymer usually have an average particle diameter of 10 mμ.
~Igm, especially with an average particle size of 50-200
Such finely divided organic polymers, preferably m 4 , are advantageously introduced into the composition as a latex.

The fine particulate Ia polymer having a glass transition point of 100°C or lower has a molecular weight of 1 to 2 to 1 to 2% relative to the photosensitive hydrophilic polymer compound.
It is blended in an amount within the range of 5% by weight (preferably 15 to 25% by weight). The above particulate matter Jj! If the amount of the polymer blended is too large, it will be difficult to manufacture resin reliefs with high precision, while if it is too small, the effect of the blend will be difficult to appear.

The photosensitive composition of the present invention may contain any additives as long as they do not impair the desired properties of the composition.

In producing a micro color filter, the photosensitive composition of the present invention can be used in the same manner as conventionally used photosensitive gelatin.

Next, Examples and Comparative Examples of the present invention will be shown. In each example, "part j" means "part by weight." A smooth layer was formed by applying an SVR resist (manufactured by Tokyo Ohka Corporation, vinyl cinnamate polymer resist) to the surface of the sample (on which a coating layer made of phosphosilicate glass was provided).

Due to the formation of this smooth layer, the height difference between the uneven portions on the light-receiving surface of the solid-state image sensor was 0.5 pm.

A photosensitive composition liquid having the following formulation was applied onto the above smooth layer so that the dry thickness was 1.3 parts m.

i11 Nagisada 1j Photocurable dichromate gelatin (average molecular weight: 100,000) 10 parts Polyethyl acrylate latex (average molecular weight: 100,000, Tg = -29 to -23°C 1 solid content near 0% by weight) 2 parts water
100 copies A mask consisting of a stripe pattern (exposure pattern, width 10 ALm) was placed on top of this.
A pattern consisting of alternately parallel shielding parts and @30 m permeable grooves) was placed and exposed to ultraviolet light.Next, the exposed composition layer was washed with hot water to dissolve the uncured parts. It was removed (developed) to leave a cured film (cured pattern) consisting of striped protrusions.

The cured film was dyed with a cyan dye (copper phthalocyanine (tetra)sulfonic acid pyridinium salt) to obtain a cyan colored resin film.

Next, acetic acid tannic acid aqueous solution (tannic acid 0
．． After immersing it in an aqueous solution containing 0.5% by weight of antimonylpotassium tartrate and 0.2% of acetic acid for 1 minute, washing with water for 30 seconds and then dipping it in an aqueous solution of potassium antimonyl tartrate at 40°C (0.125% by weight of potassium antimonyl tartrate and 0.2% by weight of acetic acid). The cyan colored resin film was subjected to resist dyeing treatment by immersing it in an aqueous solution containing % by weight for 1 minute.

Next, a yellow colored resin film was formed by aligning with the upper layer of the resist-dyed cyan colored resin film by a conventional method. Formation of yellow colored resin film.

The same method as the above-mentioned method for manufacturing the colored resin film was used except that the viridi and nium salt of Color Index (CI) Acid Yellow 141 was used.

On top of the single layer of micro color filter formed by the above steps, a surface coating layer (layer thickness: 1
μm) was formed and subjected to a heat treatment at 200'C (post-bake for 30 minutes) to complete the production of a micro color filter.

The surface of the above micro color filter was inspected using a microscope, but no cracks, deformation or movement of the colored resin film, etc. were observed.

Comparative Example 1 A micro color filter was produced on the surface of a smooth layer on a solid-state image sensor in the same manner as in Example 1 except that a photosensitive composition liquid containing no copolyethyl acrylate latex was used.

When the surface of the above micro color filter was observed using a microscope, cracks were observed in the yellow colored resin film, and the cyan colored resin film was observed to have shrunk and shifted from its designated position. .

[Example 2] Instead of polyethyl acrylate latex, the same amount of polybutyl acrylate latex (average molecular weight: 100,000,
A micro color filter was manufactured on the surface of a smooth layer on a solid-state image sensor in the same manner as in Example 1, except that a photosensitive composition liquid containing Tg = -66°C was used.

When the surface of the above micro color filter was observed using a microscope, no cracks were observed, and no deformation or movement of the colored resin film was observed.

[Example 3J Instead of polyethyl acrylate latex, the same amount of polyvinyl acetate latex (monouniform molecular weight: 10,000, Tg = 2
A micro color filter was manufactured on the surface of a smooth layer on a solid-state image sensor in the same manner as in Example 1, except that a photosensitive composition liquid containing 8-30''0) was used.

The surface of the above micro color filter was observed using a microscope, but no cracks were observed.No deformation or movement of the colored resin film was observed.

[Example 4] Instead of polyethyl acrylate latex, the same amount of styrene φ butadiene rubber latex (average molecular weight: lO
10,000, styrene content: '22 mol%, Tg = -67°C
) A micro color filter was manufactured on the surface of a smooth layer on a solid-state imaging device in the same manner as in Example 1, except that a photosensitive composition liquid containing the following was used.

The surface of the above micro color filter was observed using a microscope, but no cracks, deformation or movement of the colored resin film, etc. were observed.

[Example 5] A micro color filter was manufactured on the surface of a smooth layer on a solid-state image sensor in the same manner as in Example 1 except that an acrylate copolymer resist was used instead of SVR as a resist for forming a smooth layer.

When the surface of the above micro color filter was observed using a microscope, no cracks were observed, and no deformation or movement of the colored resin film was observed.

Patent Applicant Fuji Photo Film Co., Ltd. Representative Patent Attorney Yasushi Yanagawa Procedural Amendment September 25, 1985 Appointed by the Commissioner of the Patent Office Mr. Michibe ~ Shi...:
1j 1. Indication of the case 1985 Patent Application No. 180874 2. Name of the invention Photosensitive composition 3. Relationship with the person making the amendment Patent applicant name (520') Fuji Photo Film Co., Ltd. 4.
agent

Claims (1)

[Scope of Claims] 1. A photosensitive hydrophilic polymer compound and a glass transition point of 1 to 25% by weight based on the above polymer compound.
A photosensitive composition comprising a particulate organic polymer having a temperature of 0°C or less. 2. The photosensitive composition according to claim 1, wherein the amount of the particulate organic polymer is 15 to 25% by weight based on the hydrophilic polymer compound. 3. The photosensitive composition according to claim 1, wherein the photosensitive hydrophilic polymer compound is a compound selected from the group consisting of gelatin, casein, and polyvinyl alcohol. 4. The photosensitive composition according to claim 1 or 2, wherein the particulate organic polymer has a glass transition point of 35° C. or lower. 5. Claim 1 or 2, wherein the particulate organic polymer is a compound selected from the group consisting of polyethyl acrylate, polybutyl acrylate, polyvinyl acetate, and styrene and butadiene rubber. The photosensitive composition described in . 6. The photosensitive composition according to claim 1 or 2, wherein the particulate organic polymer is made of organic polymer latex.