JPS6185421A - Production of photosensitive resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin suitable as photosensitive coating film- forming material, by copolymerization between each specific two sorts of polymerizable monomers. CONSTITUTION:The objective resin can be obtained by copolymerization between (A) a polymerizable monomer of formula I (R<1> is H or lower alkyl; R<2> is H, lower alkyl or lower alkoxy; n is 2-5) [e.g., 1-methacryloxy-2-(4-methyl) cinnamoyloxyethane] and (B) another polymerizable monomer of formula II (R<3> is H or lower alkyl; m is 1-5) (e.g., glycidhyl acrylate). USE:The coating film from this photosensitive resin is suitable as protective film for the base surface of various articles, antifouling protective layer for color-separation filter, surface-protective layer, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a photosensitive resin, and more particularly to a method for producing a photosensitive resin suitable as a material for forming a photosensitive coating film.

(Prior Art) Conventionally, in order to prevent deterioration and damage to the substrate surface of various articles, it has been widely practiced to form a protective coating on the surface of the substrate. This type of protective coating film must have high adhesion to the substrate, be smooth and strong, and have high heat and light resistance (so that it will not change in quality such as discoloration over a long period of time). Performance such as excellent water resistance and solvent resistance is required.

On the other hand, in recent years, charge coupled devices (rC
Various solid-state image sensors with built-in color separation filters have been announced as photoelectric conversion elements such as CDJs.

The color separation filter of this solid-state image sensor is, for example, a CCD.
It is formed on the element through the following steps. That is,
After the surface of the CCD element (substrate) is flattened with a transparent coating film, a photosensitive material made by adding a photosensitive substance to polyvinyl alcohol, grue, gelatin, etc. to impart photosensitivity is uniformly applied onto the substrate. , irradiate ultraviolet rays through a pattern mask to photocure only the portion that should constitute the hue portion of the first color, melt and remove the uncured portion and develop, and dye this portion with a dye having predetermined spectral characteristics. Dyeing and then covering with a transparent resist protection film. Furthermore, the above-mentioned photosensitive material is coated on this dye resist protective film, and the hue portion of the second color is exposed, developed, dyed and formed with the resist dye WLm* by the same process, and then the third color is coated with the photosensitive material. Similar steps are used to expose, develop, and dye the hue portion, and finally, a surface protective film is formed. In addition to the properties required for the above-mentioned protective coatings, such as adhesion, smoothness, toughness, heat resistance, light resistance, water resistance, and solvent resistance, these anti-dye protection films and surface protection films also have the following properties: Furthermore, performance such as transparency and resistance to staining by dyes are also required.

Furthermore, in CCDs and the like, in order to selectively remove these coatings applied to areas such as bonding pads 7) where anti-dye protection coatings or surface protection are unnecessary, the coatings are imparted with photosensitivity; It is necessary to partially photocure the coating film to make it insoluble in a solvent and remove the uncured portion with a solvent, and for this purpose, excellent photosensitivity is required. Furthermore, the materials that make up these coatings are applied as a solution, but in order to form a uniform coating,
A spin coating method using a spin coater may be used.
It is also required to be suitable for this coating method.

Until now, no photosensitive coating film-forming material has been found that satisfies all of these required performances.

(Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing an excellent photosensitive resin that has all of the above-mentioned performances required as a material for forming a photosensitive coating film.

(Means for Solving the Problems) The present invention is based on the general formula (1) (wherein R1 is a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and R2 is a hydrogen atom or a lower Alkyl group or lower alkoxy group such as methoxy group, etho, propoxy group, butoxy group, n is 2 to 5
(means an integer of 1 to 5) and a polymerizable monomer represented by the general formula (■) 4 (wherein R3 is a hydrogen atom or a lower alkyl group, and m means an integer of 1 to 5) The present invention provides a method for producing a photosensitive resin characterized by copolymerizing the photosensitive resin with a monomer.

Examples of the polymerizable monomer of general formula (I) include l-methacryoloxy-2-(4-methyl)cinnamoyloxyethane, 1-methacryoloxy-2-(4-ethyl)cinnamoyloxyethane, l-methacryoloxy -2(4-n-propyl)cinnamoyloxyethane, 1-metachloroyloxy-2-(4-isopropyl)cinnamoyloxyethane, 1-metachloroyloxy-2-(4-n-butyl)cinnamoyloxyethane, ■- Methachloroyloxy 2-(4-isobutyl)cinnamoyloxyethane, ■-Acryloxy 2-(4-methyl)cinnamoyloxyethane, 1-Methachloroyloxy-3-(4-methyl)cinnamoyloxypropane, 1- Methachloroyloxy-4-(4-isopropyl)cinnamoyloxybutane, 1-acryloxy-2-cinnamoyloxyethane, ■-Methachloroyloxy-2-cinnamoyloxyethane, 1-(α-ethyl)acryloxy-2-cinnamoy Roxyethane, 1-(α-propyl)acryloxy-2-cinnamoyloxyethane, 1-acryloxy-2-(4-methoxy)cinnamoyloxyethane, 1-acryloxy-2-(4-ethoxy)cinnamoyloxyethane , l-acryloxy-2-(4-propoxy)cinnamoyloxyethane, 1-methacryloxy-2-(4-methoxy)cinnamoyloxyethane, 1-methacryloxy-2-(4-ethoxy)cinnamoyloxyethane, 1 -Metachlorooxy-2-(4-propoxy)cinnamoyloxyethane, 1-(α-ethyl)acryloxy-2-cinnamoyloxyethane, 1-(α-ethyl)acryloxy-2-(4-methoxy)cinnamoyloxy Ethane, 1-(α-ethyl)acryloxy-2-(4-ethoxy)cinnamoyloxyethane, l-acryloxy-3-cinnamoyloxypropane, ■-methacryloxy-3-cinnamoyloxypropane, 1-(α -ethyl)acryloxy-3-cinnamoyloxypropane, 1-(α-propyl)acryloxy-3-cinnamoyloxypropane, 1-acryloxy-3-(4-methoxy)cinnamoyloxypropane, 1-methacryloxy-4- Cinnamoyloxybutane, 1-methacryloxy-4-(4-ethoxy)cinnamoyloxybutane, 1-(α-ethyl)acroxy-4-(4-propoxy)cinnamoyloxybutane, 1-(α-butyl)acryloxy -4-(4-butoxy)cinnamoyloxybutane, and the like.

Examples of the polymerizable monomer of general formula (n) include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, and acrylic acid. -3,4-epoxybutyl, methacrylic acid-3,4
-Epoxybutyl, methacrylic 1% t-4,5-epoxypentyl, 6,7-nipoxyhbutyl acrylate,
Examples thereof include 6,7-epoxyheptyl methacrylate, 6,7-nipoxyheptyl methacrylate, and 6,7-epoxyheptyl α-ethyl acrylate. Among these compounds, in the general formula (n), R3 is a hydrogen atom,
A methyl group or an ethyl group is preferred, and the value of m is preferably 1 or 2.

When producing the photosensitive resin of the present invention, general formula (1)
The copolymerization ratio between the polymerizable monomer of formula (II) and the polymerizable monomer of general formula (II) is the number of copolymerized moles of (I)/(the number of copolymerized moles of (1)) of copolymerizable monomer (II). Polymerization mole number)X100=2~
It is preferably 60, particularly preferably 5-40. If the copolymerization ratio of the polymerizable monomer of general formula (I) is small, the photosensitive performance will decrease, and if the copolymerization ratio of the polymerizable monomer of general formula (II) is small, the smoothness and photocuring of the coating film will decrease. In this case, the adhesion, heat resistance, solvent resistance, dye resistance, and hardness of the coating film decrease.

When producing the photosensitive resin of the present invention, a third monomer component may be copolymerized in addition to the polymerizable monomers of general formulas (I) and (■), as long as the photosensitivity is not impaired. Good too.

Examples of the third monomer component include methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate,
41 Acryloyloxychalcone 4 Esters of acrylic acid or methacrylic acid such as v-methacryloyloxychalcone, 41-acryloyloxy-(4-methoxychalcone), 4'-methacryloyloxy-(4-methoxychalcone), styrene, α-methyl Vinyl aromatic compounds such as styrene, p-methylstyrene, and vinylnaphthalene are used. The amount of these third monomer components is usually about 0.2 mol or less per 1 mol of the total amount of the polymerizable monomers of general formulas (I) and (II).

The form of copolymerization of the polymerizable monomer of general formula (1) and the polymerizable monomer of general formula (II) is not particularly limited, and may be random copolymerization by addition polymerization, block copolymerization, etc. The copolymerization method may be either a solution polymerization method or an emulsion polymerization method.

Next, regarding the method for producing the photosensitive resin of the present invention, a case where a solution polymerization method is used will be described in detail.

The solvent used in the solution polymerization is not particularly limited as long as it dissolves the R-mer and the polymerization initiator, dissolves the photosensitive resin to be produced, and does not itself react; for example, Acetone, methyl ethyl ketone, methyl-
n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n
- Ketone solvents such as propyl ketone, diisobutyl ketone, cyclohexanone, and holon; ethers such as ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, and tetrahydrofuran; System solvent, ethyl formate, propyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, M-n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Examples include ester solvents such as ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate. These solvents may be used alone or in combination of two or more.

Further, the polymerization catalyst used in the solution polymerization method is not particularly limited, and for example, a radical polymerization initiator can be used. As a radical polymerization initiator, 2.2
'-7zobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2゜2' -Dimethyl azobisisobutyrate, 1.11-
Azobis(cyclohexane-1-carbonitrile), 2
．． Azo compounds such as 2'-azobis(2-amidinopropane) dihydrochloride, benzoyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 1.1-
Examples include peroxy compounds such as bis(t-butylperoxy)3.3.5-trimethylcyclohexane and 2°2-bis(t-butylperoxy)octane. When using these radical polymerization initiators, the amount used is usually 1/1000 to 1/200 mol, preferably 1/800 to 1/200 mol, per 1 mol of the total amount of monomers used for polymerization. It is 300 moles.

If the amount used is too small, the polymerization yield will decrease, and if the amount used is too large, the molecular weight photosensitivity (the molecular weight of the resin will tend to decrease).

Note that the polymerization temperature in these cases is not particularly limited, but is usually in the range of 20 to 120°C.

The amount of solvent used in the solution polymerization method is generally 0.5 to 4 times (by weight), preferably 1 to 3.5 times (by weight) based on the amount of the premonomer.

If the amount of the solvent used is less than 0.65 times the amount, the viscosity of the polymerization system will be high (not only will the stirring efficiency deteriorate, but the photosensitive resin to be formed will be more likely to gel.
If the amount exceeds twice the amount, the molecular weight of the photosensitive resin tends to decrease.

The photosensitive resin obtained by the present invention mainly consists of a structural unit represented by the general formula (and general formula (IV) (wherein R1, R2, R3, n and m have the above-mentioned meanings).

The molecular weight of the photosensitive resin obtained by the present invention is 50,000 to 600.000 in terms of polystyrene equivalent number average molecular weight.
It is preferable that it is, especially 10o, ooo~400,
000, this number average molecular weight is preferably 50
If the molecular weight is less than ,000, when the UV irradiated area is photocrosslinked as a photosensitive coating and the unirradiated area is dissolved in a solvent for patterning, the molecular weight is small, so it is difficult to photocrosslink and make it insolubilized in the solvent. It is necessary to irradiate a larger amount of ultraviolet rays, and as a result, the sensitivity as a photosensitive performance deteriorates. Furthermore, in this case, since a large amount of ultraviolet rays are irradiated, patterning characteristics are also deteriorated due to halation. On the other hand, when the number average molecular weight exceeds 600,000, the storage stability of the photosensitive resin deteriorates and gelation tends to occur.

The molecular weight dispersion of the photosensitive resin obtained by the present invention includes:
Although there is no particular limitation, it is preferable that the weight average molecular weight in terms of polystyrene/number average molecular weight in terms of polystyrene is 5 or less from the viewpoint of pattern resolution, which is one of the photosensitive properties.

The photosensitive resin obtained by the present invention can be made into a photosensitive resin solution for forming a photosensitive coating film by dissolving it in a suitable solvent. The solvent used at this time is not particularly limited as long as it dissolves the photosensitive resin and does not react with it. For example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n
- Ketone solvents such as butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, holon, etc., ethyl ether, isopropyl ether, n-butyl ether, isoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol , dioxane, ether solvents such as tetrahydrofuran, ethyl formate, propyl formate, formic acid-n
-Butyl, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Ester solvents such as the following are used. The concentration of the photosensitive resin solution is not particularly limited and can be appropriately selected depending on the purpose of use, but is usually 5 to 50 ffifft%.

As a method of applying a photosensitive resin solution to the substrate surface,
Examples include a spray method, a roll coating method, a spin coating method, and the like.

The coating film obtained by applying these methods usually has a thickness of 50 to
After heat treatment is performed at 100° C. for about 10 minutes to 1 hour (brebake) to remove the solvent, ultraviolet rays of, for example, 250 to 400 nm are irradiated through a photomask. For example, the amount of UV irradiation is usually 10
~500 mJ/cnl. The solvent used to dissolve and remove the unirradiated areas of the coating film for development may be any solvent as long as the unirradiated areas are eluted, and is usually a good solvent for photosensitive resins such as methyl ethyl ketone and isopropyl alcohol. A mixture of a poor solvent and a suitable proportion is used. Further, since the coating film developed in this manner is usually swollen, it is shrunk by rinsing if necessary. A poor solvent such as methyl isobutyl ketone is used as the rinsing liquid.

Next, the coating film obtained in this way is
By heat-treating (post-baking) at ℃ for 30 minutes to 2 hours, a photocured coating film with a desired shape can be obtained.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Note that the polystyrene equivalent number average molecular weight and polystyrene equivalent weight average molecular weight in this example were determined using a gel permeation chromatogram under the following measurement conditions.

Equipment: High-temperature high-speed gel permeation chromatogram (Model 150-CALC/ manufactured by Waters, USA)
GPC) Column: 5HODEX A-8M manufactured by Showa Denko ■.

Length 50cI11 Measurement temperature = 40℃ Flow rate: 1m11 minutes Solvent: Tetrahydrofuran Sample concentration: Photosensitive resin (Ig) / Tetrahydrofuran (100mj2) Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemical Company Example 1 Stirring device, thermometer, for cooling After purging the inside of a 500 m 14 round bottom flask equipped with a condenser and a nitrogen gas inlet with nitrogen gas, 343 g (3.9 mol) of degassed and distilled dioxane was added to the flask, and further glycidyl methacrylate 42. 6g (0°30mol), ■-Methachloroyloxy-2-cinnamoyloxyethane 26.
0 g (0.10 mol) and 0.17 g (0.001 mol) of azobisisobutyronitrile were charged.

Next, the reaction solution was copolymerized by heating at 50° C. for 18 hours while stirring, and then the reaction solution was cooled to room temperature and treated with methanol No. 21 to solidify the produced copolymer. After the coagulated copolymer was filtered off, it was dried under reduced pressure at room temperature to obtain 28 g of a white powdery copolymer. When the composition ratio of this copolymer was determined by ultraviolet absorbance method, the molar ratio of glycidyl units to cinnamoyl units was 77:23. The number average molecular weight of this copolymer in terms of polystyrene was 170,000. The ratio of the weight average molecular weight in terms of polystyrene to the number average molecular weight in terms of polystyrene (MW/MN) was 2.51.

11 g of the copolymer thus obtained was dissolved in 89.0 g of ethyl cellosolve acetate, and this solution was mixed with a pore size of 0.2 μm.
After pressure filtration with a membrane filter of
The coating was applied by spinning at rpm.

The surface of the resulting coating film was extremely smooth, and no film roughness was observed. After heat-treating this at 150"C for 30 minutes, the film thickness was measured using a stylus-type film thickness meter (manufactured by Dank Taylor Hobson Co., Ltd., Christetsub). The film thickness was 1.01 μm.
Met.

Furthermore, the copolymer solution was placed on a silicon wafer at a rotation speed of 2.4.
After spin-coating at 0 rpm and heat-treating for 10 minutes in a constant temperature bath at 80°C, it was exposed through a photomask using Canon #451 (PLA-521F) using a 500W xenon-mercury lamp as a light source. and irradiated with ultraviolet rays. This was mixed with a mixed solvent of methyl ethyl ketone and isopropyl alcohol (M ratio: 4.5
: After melting and developing the unirradiated area by immersing it in 1) at room temperature for 1 minute, it was immersed in methyl isobutyl ketone for 1 minute at room temperature. fffi and rinsing to obtain a coating film with a desired shape faithful to the photomask. This is further heated to 150℃
Heat treatment was performed for 1 hour in a constant temperature bath.

In this case, the optimum value of the ultraviolet irradiation time (hereinafter referred to as optimum exposure time) was 4 seconds (30 mJ/cot in terms of ultraviolet energy energy with a wavelength of 254 nm). The optimum exposure time refers to an ultraviolet irradiation time that does not cause roughening of the photocured coating film after development due to an insufficient amount of ultraviolet irradiation, and does not cause a decrease in resolution due to an excessive amount of ultraviolet irradiation.

The following tests were conducted on the photocured coating film thus produced. First, the absorption spectrum of a glass plate on which a photocured coating film was formed by the above method was measured using a similar glass plate without a coating film as a control. Wavelength 350~
The light transmittance was 95% or more in the entire 800 nm region.

Next, in order to test the adhesion of the photo-cured coating film on this glass plate for 8 times, a cross-cut test (JIS K
-5400), but no peeling was observed. In addition, this glass plate was placed in boiling water and allowed to stand for 5 hours, and then a similar cross-cut test was performed, but no peeling was observed in this case as well. Further, the glass plate with the above-mentioned coating film was placed in toluene and heated under reflux for 5 hours, and then a cross-cut test was conducted, but no peeling was observed in this case as well.

In addition, a glass plate with a photocured coating film prepared in the same manner as above was heat-treated for 200 hours in an open gear at 200°C, and when the heat resistance of the coating film was examined, no cranking was observed. Moreover, no change in the absorption spectrum was observed.

Furthermore, a halogen lamp (JCD manufactured by Iwasaki Electric ■) was applied to the glass plate on which the photocured coating film prepared in the same manner as above was formed.
When the light resistance of the coating film was examined by irradiating it with 10°,000 lux light for 1,000 hours at 650 W/B), no change in the absorption spectrum was observed, and no cranking was observed.

In addition, the pencil hardness of the photocured coating film created in the same manner as above was measured in accordance with JIS K-5400, and it was found to be 4.
It was B.

Next, the glass plate with the photocured coating produced in the same manner as above was placed in a dyeing bath with the composition shown below, left at 100°C for 30 minutes, and then the glass plate was taken out, thoroughly washed with water, and dried. When we visually inspected the paint film and examined its stain resistance, we found no abnormalities such as cracks or film roughness, and the light transmittance of the paint film was over 95% in the wavelength range of 400 to 800 nm. Met.

(Dyeing bath) Acid dye (Kayanoj! Mtj!j!ingR
ed R3-125) 2g glacial acetic acid 2g distilled water
100g These results are summarized in Table 1.

On the other hand, a coating film obtained by spin-coating a commercially available aqueous gelatin solution (solid content: 20%) on a silicon wafer was
Heat treatment was performed for 1 hour in a constant temperature bath at ℃.

The gelatin film thickness at this time was 1.52 μm. Further, using the same copolymer solution as above, spin coating, heat treatment, exposure, development, rinsing, and heat treatment were performed in the same manner as above to form a two-layered coating film. When this coating film was subjected to a cross-cut test using tape peeling, no peeling was observed.

Example 2 Methacrylic acid-3 instead of glycidyl methacrylate
, 4-epoxybutyl 53g (0.31 mol), and in the same manner as in Example 1 except that a copolymer was produced.

The number average molecular weight of this copolymer in terms of polystyrene is
s, ooo, and the value of MW/MN was 2.45. When the composition ratio of this copolymer was determined by an ultraviolet absorbance method, the molar ratio of cinnamoyl unit to 3,4-epoxybutyl unisotho was 23 near 7.

Next, using 11 g of this copolymer, a copolymer solution was prepared by processing in the same manner as in Example 1, and this was used to prepare a copolymer solution in Example 1.
A coating film having a thickness of 1.0 μm was formed in the same manner as in Example 1, and various properties of this coating film were investigated in the same manner as in Example 1. The results are shown in Table 1.

Example 3 21 g (0,072 mol) of 1-metachlorooxy-2-(4-memethoxy)cinnamoyloxyethane was used instead of 1-metachloroyloxy-2-cinnamoyloxyethane, and 320 g of tetrahydrofuran was used instead of dioxane. A copolymer was produced in the same manner as in Example 1 except for using (4.4 mol). The polystyrene equivalent number average molecular weight of this copolymer was 182,000, and the value of MW/MN was 2.23. When the composition ratio of this copolymer was determined by ultraviolet absorbance method, the molar ratio of glycidyl units and 4-methoxycinnamoyl units was 82:18.

Next, using 10 g of this copolymer, a copolymer solution was prepared by processing in the same manner as in Example 1, and this was used to prepare a copolymer solution in Example 1.
A coating film having a thickness of 1.1 μm was formed in the same manner as in Example 1, and various properties of this coating film were investigated in the same manner as in Example 1. The results are shown in Table 1.

Example 4 500mj equipped with a stirring device, temperature needle, cooling condenser and nitrogen gas inlet! After purging the inside of the round bottom flask with nitrogen gas, 300 g (2.27 mol) of degas-distilled ethyl cellosolve acetate was added to the flask, followed by 45 g (0.32 mol) of glycidyl methacrylate and [-butyl methacrylate]. 10g (0.07 mol)
, 26 g (0.1 mol) of 1-methacryloyloxy-2-cinnamoyloxyethane and 0.17 g (0.001 mol) of azobisisobutyronitrile were charged. Next, the reaction solution was copolymerized by heating at 60° C. for 20 hours while stirring, and then the reaction solution was cooled to room temperature and treated with 2N methanol to solidify the produced copolymer. After the coagulated copolymer was filtered off, it was dried under reduced pressure at room temperature to obtain 61 g of a white powdery copolymer.

When the composition ratio of this copolymer was determined by nuclear magnetic resonance method and ultraviolet absorbance method, the molar ratio of glycidyl units, t-butyl ester units, and cinnamoyl units was 63:14:23. Further, the converted number average molecular weight of this copolymer is 220,000, and MW/MN
The value was 2.35.

Using 11.5 g of the obtained copolymer, a copolymer solution was prepared by processing in the same manner as in Example 1, and using this, a coating film with a thickness of 0.95 μm was formed in the same manner as in Example 1. Various properties of this coating film were investigated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 Instead of glycidyl methacrylate, 32 g (0.32 mol) of methyl methacrylate was used, and the other conditions were as in Example 1.
A copolymer of methyl methacrylate and 1-methacryloyloxy-2-cinnamoyloxyethane was produced in the same manner as above. The number average molecular weight of this copolymer in terms of polystyrene was 140,000, and the value of MW/MN was 3.0.

When the composition ratio of this copolymer was determined by ultraviolet absorbance method, the composition ratio of methoxycarbonyl units to cinnamoyl units was 78:22.

Next, using this copolymer Log, a copolymer solution was prepared by processing in the same manner as in Example 1, and using this, Example 1
A coating film having a thickness of 0.85 μm was formed in the same manner as in Example 1, and various properties of this coating film were investigated in the same manner as in Example 1. The results are shown in Table 1.

Example 5 Instead of t-butyl methacrylate in Example 4, 4
'-Methachlorooxychalcone 17g (0.06 mol)
67 g of a white powdery copolymer was obtained in the same manner as in Example 4 except that . When the composition ratio of this copolymer was determined by nuclear magnetic resonance method and ultraviolet absorbance method, the molar ratio of glycidyl unit, chalcone unit, and cinnamoyl unit was 64:12:24. The number average molecular weight of this copolymer in terms of polystyrene is 250°00.
0, and the MW/MN value was 2.3. 10 g of this copolymer was dissolved in 90 g of cyclohexanone to prepare 1 liter of a coating solution in the same manner as in Example 1, and various properties of this coating film were investigated. The results are shown in Table 1.

Example 6 Instead of dioxane in Example 1, 340 g of ethylene glycol monoethyl ether heptanoacetate (2,
26 g of a copolymer was obtained in the same manner as in Example 1 except that 58 mol) was used. The composition ratio of this copolymer was determined in the same manner as in Example 1. What was the molar ratio of glycidyl units to cinnamoyl units? It was 7:23. In addition, the number average molecular weight of this copolymer in terms of polystyrene is 18
0,000, and the MW/MN ratio was 2.40. A coating solution was prepared using this copolymer in the same manner as in Example 1, and various properties of this coating film were investigated.

The results are summarized in Table 1.

Example 7 22 g of a white powdery copolymer was prepared in the same manner as in Example 1, except that 0.24 g (0°001 mol) of benzoyl peroxide was used in place of azobisisobutyronitrile in Example 1. I got it. When the composition ratio of this copolymer was determined in the same manner as in Example 1, the molar ratio of glycidyl units to cinnamoyl units was 77:23. Further, the polystyrene PA arithmetic average molecular weight of this copolymer was 180.000, and the MW/MN ratio was 2.50. A coating solution was prepared using this copolymer in the same manner as in Example 1, and various properties of this coating film were investigated. The results are summarized in Table 1.

The following is a margin. (Effects of the invention) The photosensitive resin coating film obtained by the present invention has excellent photosensitivity, and the photocured coating film has high sensitivity in a wide wavelength range from ultraviolet to visible regions. In addition to having excellent light transmittance and transparency, it also exhibits excellent adhesion to substrates made of various materials such as glass, metal, and plastic. In addition, this coating is smooth, tough, and has excellent light and heat resistance, and does not change in quality such as discoloration even after long-term use.It also has excellent water resistance, solvent resistance, and stain resistance. It has a high hardness. Therefore, the coating film formed using the photosensitive resin obtained by the present invention is not only useful as a protective coating film on the substrate surface of various articles, but also as an anti-dyeing protective layer of color separation filters, a surface protective layer, etc. It is extremely suitable as a color separation filter, and a highly reliable color separation filter with excellent color clarity and brightness can be obtained.

Claims (1)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 is a hydrogen atom or lower alkyl group, R^2
is a hydrogen atom, a lower alkyl group or a lower alkoxy group,
(n means an integer from 2 to 5) and the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^3 is a hydrogen atom or a lower Alkyl group, m is 1
A method for producing a photosensitive resin, which comprises copolymerizing a polymerizable monomer represented by (meaning an integer of 5 to 5).