JPH0371446B2 - - Google Patents

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. In addition, performance such as excellent water resistance and solvent resistance is required. On the other hand, in recent years, various solid-state imaging devices with built-in color separation filters have been announced as photoelectric conversion devices such as charge coupled devices (hereinafter referred to as "CCD"). The color separation filter of this solid-state image sensor is formed, for example, on a CCD element through the following steps. That is, after flattening the surface of the CCD element (substrate) with a transparent coating,
A photosensitive material made by adding a photosensitive substance to polyvinyl alcohol, gris, gelatin, etc., is uniformly applied onto the substrate, and ultraviolet rays are irradiated through a pattern mask to change the hue of the first color. Only the portion to be constructed is photocured, the uncured portion is dissolved and removed, developed, this portion is dyed with a material having predetermined spectral characteristics, and then covered with a transparent anti-stain protection film. Furthermore, the photosensitive material described above is applied onto this resist-dye protective film, and the hue portion of the second color is exposed, developed, dyed, and a resist-dye protective film is formed 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 colored portion, and finally, a surface protective film is formed. This anti-stain protection film and surface protection film have the properties required for the above-mentioned protective coating, namely adhesion, smoothness,
In addition to toughness, heat resistance, light resistance, water resistance, solvent resistance, etc., performance such as transparency and resistance to staining with dyes is also required. Furthermore, in CCDs, etc., in order to selectively remove coatings applied to areas such as bonding pads where anti-dye protection coatings or surface protection coatings are unnecessary, the coatings are imparted with photosensitivity and are partially coated. It is necessary to make the coating film insoluble in a solvent by photo-curing it, and to remove the uncured portion with a solvent, and for this purpose, excellent photosensitivity is required. Furthermore, the materials constituting 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, and it may be suitable for this coating method as well. required. 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 problem) The present invention is based on the general formula () (In the formula, R ¹ is a hydrogen atom, a methyl group, an ethyl group,
Lower alkyl groups such as propyl group and butyl group, R ²
is a hydrogen atom, a lower alkyl group or a methoxy group,
A polymerizable monomer represented by a lower alkoxy group such as an ethoxy group, a propoxy group, or a butoxy group (n means an integer of 2 to 5), and a general formula () (In the formula, R ³ is a hydrogen atom or a lower alkyl group, m
is an integer from 1 to 5). Examples of the polymerizable monomer of general formula () include 1-methacryoloxy-2-(4-methyl)cinnamoyloxyethane, 1-methacryoloxy-2-(4-ethyl)cinnamoyloxyethane, and 1-methacryoloxy-2-(4-ethyl)cinnamoyloxyethane. 2-(4-n-propyl)cinnamoyloxyethane, 1-methacloyloxy-2-(4-isopropyl)cinnamoyloxyethane, 1-methacloyloxy-2-(4-n-butyl)
Cinnamoyloxyethane, 1-methacryloyloxy-2-(4-isobutyl)
Cinnamoyloxyethane, 1-acryloxy-2-(4-methyl)cinnamoyloxyethane, 1-acryloxy-2-(4-isobutyl)cinnamoyloxyethane, 1-methacryloxy-3-(4-methyl)cinnamoy Roxypropane, 1-methacryloxy-4-(4-isopropyl)cinnamoyloxybutane, 1-acryloxy-2-cinnamoyloxyethane, 1-methacryloxy-2-cinnamoyloxyethane, 1-(α-ethyl)acryloxy- 2-cinnamoyloxyethane, 1-(α-propyl)allyloxy-2-cinnamoyloxyethane, 1-acryloxy-2-(4-methoxy)cinnamoyloxyethane, 1-acryloxy-2-(4-ethoxy) Cinnamoyloxyethane, 1-acryloxy-2-(4-propoxy)cinnamoyloxyethane, 1-methacryloxy-2-(4-methoxy)
Cinnamoyloxyethane, 1-metachloroyloxy-2-(4-ethoxy)
Cinnamoyloxyethane, 1-metachloroyloxy-2-(4-propoxy)
Cinnamoyloxyethane, 1-(α-ethyl)acryloxy-2-cinnamoyloxyethane, 1-(α-ethyl)acryloxy-2-(4-methoxy)cinnamoyloxyethane, 1-(α-ethyl)acryloxy -2-(4-ethoxy)cinnamoyloxyethane, 1-acryloxy-3-cinnamoyloxypropane, 1-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)acryloxy-4-(4-propoxy)cinnamoyloxybutane, 1-(α-butyl)acryloxy-4-(4-butoxy)cinnamoyloxybutane, etc. It will be done. Examples of the polymerizable monomer of general formula () include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-
Glycidyl propyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 4,5-epoxypentyl methacrylate, 6,7-epoxy acrylate Examples include -epoxyheptyl, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl methacrylate, and 6,7-epoxyheptyl α-ethyl acrylate. Among these compounds, in the general formula (), R ³ is preferably a hydrogen atom, a methyl group or an ethyl group, and m is preferably 1 or 2. When producing the photosensitive resin of the present invention, the copolymerization ratio of the polymerizable monomer of general formula () and the polymerizable monomer of general formula () is the number of copolymerized moles of ()/(( It is preferable that the number of moles of copolymerization of )+the number of moles of copolymerization of ()×100=2 to 60, particularly preferably 5 to 40. If the copolymerization ratio of the polymerizable monomer of general formula () is small, the photosensitive performance will decrease,
If the copolymerization ratio of the polymerizable monomer of general formula () is small, the smoothness of the coating film and the adhesion, heat resistance, solvent resistance, dyeing resistance, and hardness of the coating film when photocured will decrease. become. 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 () and (), as long as the photosensitive performance is not impaired. . 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, 4'acryloyloxychalcone, 4'-methacryloyloxychalcone, 4'-acryloyloxy-
Acrylic acid or methacrylic acid esters such as (4-methoxychalcone) and 4'-methacryloxy-(4-methoxychalcone), vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, and vinylnaphthalene. 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 () and (). Polymerizable monomer of general formula () and general formula ()
The form of copolymerization with the polymerizable monomer is not particularly limited, and may be random copolymerization by addition polymerization, block copolymerization, etc., and the copolymerization method may be any of solution polymerization method, emulsion polymerization method, etc. good. 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 for solution polymerization is not particularly limited as long as it dissolves the monomer and polymerization initiator, dissolves the photosensitive resin to be produced, and does not react itself; for example, acetone, Methyl ethyl ketone, methyl-n-propyl ketone,
Methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-
Ketone solvents such as amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, holon, ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, Ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, tetrahydrofuran, ethyl formate, propyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetate Ester solvents such as -butyl, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate can be mentioned. 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 the radical polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4- dimethylvaleronitrile), 2,2' dimethyl azobisisobutyrate, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-
Azo compounds such as azobis(2-amidinopropane) dihydrochloride, benzoyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 1,1-bis(t-butylperoxy) 3,
Examples include peroxy compounds such as 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 mol, based on 1 mol of the total amount of monomers used for polymerization.
~1/300 mole. If the amount used is too small, the polymerization yield will decrease, and if the amount used is too large, the molecular weight will be photosensitive (the molecular weight of the resin will tend to decrease).The polymerization temperature in these cases is not particularly limited, but it is usually The temperature is 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 the amount (weight) of the premonomer, preferably 1 to 3.5 times the amount (weight). weight).
If the amount of solvent used is less than 0.5 times the amount, not only will the viscosity of the polymerization system become high and the stirring efficiency will deteriorate;
The resulting photosensitive resin becomes more likely to gel. Furthermore, if the amount of solvent used exceeds 4 times the amount, the molecular weight of the photosensitive resin tends to decrease. The photosensitive resin obtained by the present invention has the general formula () and general expression () It mainly consists of a structural unit represented by (in the formula, R ¹ , R ² , R ³ , n and m have the above-mentioned meanings). The molecular weight of the photosensitive resin obtained by the present invention is
Polystyrene equivalent number average molecular weight: 50,000 to 600,000
It is preferable that it is, and it is especially preferable that it is 100000-400000. If this number average molecular weight is less than 50,000, when forming a photosensitive coating film by photocrosslinking the ultraviolet irradiated areas and dissolving the unirradiated areas in a solvent for patterning, the molecular weight is small, so photocrosslinking and solvent removal are required. It is necessary to irradiate a larger amount of ultraviolet rays in order to make it insolubilized, 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, the number average molecular weight
When it exceeds 600,000, the storage stability of the photosensitive resin deteriorates and gelation tends to occur. The degree of molecular weight dispersion of the photosensitive resin obtained by the present invention is not particularly limited, but from the viewpoint of pattern resolution, which is one of the photosensitive properties, the polystyrene equivalent weight average molecular weight/polystyrene equivalent number average molecular weight is 5 or less. It is preferable that 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 to dissolve the photosensitive resin,
It is not particularly limited as long as it does not react with this. 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- Ketone solvents such as n-propyl ketone, diisobutyl ketone, cyclohexanone, and holon, ethyl ether,
Ether solvents such as isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, tetrahydrofuran, ethyl formate, propyl formate, n-butyl formate, ethyl acetate, acetic acid −
Ester solvents such as n-propyl, 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 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% by weight. Examples of the method for applying the photosensitive resin solution onto the substrate surface include a spray method, a roll coating method, and a spin coating method. The coating film obtained by applying these methods is usually heat treated at 50 to 100°C for about 10 minutes to 1 hour (prebaking) to remove the solvent.
For example, ultraviolet rays of 250 to 400 nm are irradiated through a photomask. The amount of UV irradiation is, for example, at a wavelength of 254n.
The amount of ultraviolet rays is usually 10 to 500 mJ/cm ² . 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. Furthermore, since the coating film developed in this manner is usually swollen, it is shrunk by rinsing as 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 200°C 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-C, manufactured by Waters, USA)
ALC/GPC) Column: SHODEX A-8M manufactured by Showa Denko Co., Ltd., length
50cm Measurement temperature: 40℃ Flow rate: 1ml/min Solvent: Tetrahydrofuran Sample concentration: Photosensitive resin (1g) / Tetrahydrofuran (100ml) Standard polystyrene: Standard polystyrene manufactured by Pressure Chemical Co., USA Example 1 Stirring device, thermometer, cooling After purging the inside of a 500 ml 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, followed by 42.6 g (0.30 mol) of glycidyl methacrylate. , 1-
Methachlorooxy-2-cinnamoyloxyethane
26.0 g (0.10 mol) and 0.17 g (0.01 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 (2) 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 and cinnamoyl units was found to be
It was 77:23. Further, the number average molecular weight of this polymer 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 added to
After pressure filtration with a 0.2 μm membrane filter, it was spin-coated onto a silicon wafer at a rotation speed of 2400 rpm using a spin coater. The surface of the resulting coating film was extremely smooth, and no film roughness was observed at all. After heat-treating this at 150℃ for 30 minutes,
The film thickness measured with a stylus-type film thickness meter (Talystep, manufactured by Dank Taylor Hobson) was 1.01 μm. Furthermore, the copolymer solution was spin-coated onto a silicon wafer at a rotational speed of 2400 rpm, heat-treated for 10 minutes in a constant temperature bath at 80°C, and then exposed through a photomask using a Canon Inc. ) manufactured exposure machine (PLA-521F)
UV rays were irradiated using a This was immersed in a mixed solvent of methyl ethyl ketone and isopropyl alcohol (4.5:1 by weight) at room temperature for 1 minute to dissolve the unirradiated areas and develop.
The sample was rinsed by immersion in methyl isobutyl ketone at room temperature for 1 minute to obtain a coating film in the desired shape faithful to the photomask. This was further heat treated in a constant temperature bath at 150°C for 1 hour. In this case, the optimum value of the ultraviolet irradiation time (hereinafter referred to as optimum exposure time) was 4 seconds (30 mJ/cm ² in terms of ultraviolet energy with a wavelength of 254 nm).
The optimal exposure time refers to the UV irradiation time that does not cause the photocured coating film to become rough after development due to an insufficient amount of UV irradiation, and does not cause a decrease in resolution due to an excessive amount of UV irradiation. It is something. 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. The light transmittance was 95% or more in the entire wavelength range of 350 to 800 nm. Next, in order to examine the adhesion of the photocured coating film on this glass plate, a cross-cut test (JIS K-5400) by tape peeling was conducted, but no peeling was observed. Further, this glass plate was placed in boiling water and left 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 in a gear oven at 200°C for 200 hours to examine the heat resistance of the coating film, and no cracks were observed. Further, no change in the absorption spectrum was observed. Furthermore, the glass plate on which the photocured coating film prepared in the same manner as above was irradiated with 10,000 lux light for 1,000 hours using a halogen lamp (JCD100V, 650W/B manufactured by Iwasaki Electric Co., Ltd.) to cure the coating film. When examining light resistance, no change in absorption spectrum was observed.
Krack's invention was also not recognized. Further, the pencil hardness of the photocured coating film prepared in the same manner as above was measured in accordance with JIS K-5400 and was found to be 4B. Next, the glass plate with the photocured coating prepared in the same manner as above was placed in a dyeing bath with the following composition, 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 condition of the paint film and examined its stain resistance, we found no abnormalities such as cracks or roughness of the film, and the light transmittance of the paint film was 95% or more in the wavelength range of 400 to 800 nm. It was hot. (Dyeing bath) Acid dye (Kayanol Milling Red RS-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%) onto a silicon wafer was heat-treated in a constant temperature bath at 150° C. for 1 hour. 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 at all. Example 2 53 g (0.31 mol) of 3,4-epoxybutyl methacrylate instead of glycidyl methacrylate
A copolymer was produced in the same manner as in Example 1 except for the following. The number average molecular weight of this copolymer in terms of polystyrene is 185,000, and the value of MW/MN is
It was 2.45. When the composition ratio of this copolymer was determined by ultraviolet absorbance method, the molar ratio of cinnamoyl units and 3,4-epoxybutyl units was found to be
It was 23:77. Next, using 11 g of this copolymer, a copolymer solution was prepared by processing in the same manner as in Example 1, and a coating film with a thickness of 1.0 μm was formed using this in the same manner as in Example 1. Various properties of the coating film were investigated in the same manner as in Example 1. The results are shown in Table 1. Example 3 Instead of 1-methacryoloxy-2-cinnamoyloxyethane, 1-methacryoloxy-2-
(4-Memethoxy)cinnamoyloxyethane 21g
A copolymer was produced in the same manner as in Example 1 except that 320 g (4.4 mol) of tetrahydrofuran was used in place of dioxane. The number average molecular weight of this copolymer in terms of polystyrene is 182,000, and the value of MW/MN is 2.23.
It was hot. When the composition ratio of this copolymer was quantified using ultraviolet absorbance method, it was found that glycidyl units and 4-
The molar ratio with methoxycinnamoyl unit is 82:
I was 18. Next, using 10 g of this copolymer, a copolymer solution was prepared by processing in the same manner as in Example 1, and a coating film with a thickness of 1.1 μm was formed using this in the same manner as in Example 1. Various properties of the coating film were investigated in the same manner as in Example 1. The results are shown in Table 1. Example 4 After purging the inside of a 500 ml round bottom flask equipped with a stirrer, a thermometer, a cooling condenser, and a nitrogen gas inlet with nitrogen gas, 300 g (2.27 mol) of degas-distilled ethyl cellosolve acetate was added to the flask. In addition, 45g of glycidyl methacrylate
(0.32 mol), t-butyl methacrylate 10g (0.07
26 g (0.1 mol) of 1-methacryloyloxy-2-cinnamoyloxyethane and 0.17 g (0.001 mol) of azobisisobutyronitrile were charged. The reaction solution was then copolymerized by heating at 60°C for 20 hours while stirring, and then the reaction solution was cooled to room temperature and treated with methanol in 2.
The resulting copolymer was coagulated. 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. In addition, the converted number average molecular weight of this copolymer is 220000, which is MW/
The value of MN 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 a coating film with a thickness of 0.95 μm was formed using this 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 Methyl methacrylate and 1-methyl methacrylate were used in the same manner as in Example 1 except that 32 g (0.32 mol) of methyl methacrylate was used instead of glycidyl methacrylate.
A copolymer with methachlorooxy-2-cinnamoyloxyethane was produced. The number average molecular weight of this copolymer in terms of polystyrene is 140,000,
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 10 g of this copolymer, a copolymer solution was prepared by processing in the same manner as in Example 1, and a coating film with a thickness of 0.85 μm was formed using this in the same manner as in Example 1. Various properties of the coating film were investigated in the same manner as in Example 1. The results are shown in Table 1. Example 5 In place of t-butyl methacrylate in Example 4, 17 g of 4'-methacryloxychalcone (0.06
Same as Example 4 except that mol) was used,
67 g of a white powdery copolymer was obtained. 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 found to be
It was 64:12:24. In addition, the number average molecular weight of this copolymer in terms of polystyrene is 250,000, and MW/
The MN value was 2.3. A coating solution was prepared by dissolving 10 g of this copolymer in 90 g of cyclohexanone 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 Ethylene glycol monoethyl ether monoacetate was used instead of dioxane in Example 1.
26 g of a copolymer was obtained in the same manner as in Example 1 except that 340 g (2.58 mol) was used. The composition ratio of this copolymer was determined in the same manner as in Example 1, and the molar ratio of glycidyl units to cinnamoyl units was 77:23. In addition, the number average molecular weight of this copolymer in terms of polystyrene is 180,000, which is MW/
The 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 Instead of azobisisobutyronitrile in Example 1, 0.24 g of benzoyl peroxide
22 g of a white powdery copolymer was obtained in the same manner as in Example 1, except that (0.001 mol) was used. 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 number average molecular weight of this copolymer in terms of polystyrene 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.

【table】

[Table] (Note) 〓○〓 in the table indicates that no peeling occurred in the cross-section test.
(Effects of the Invention) The photosensitive resin coating film obtained by the present invention has excellent photosensitivity, and the photocured coating film has high light transmittance in a wide wavelength range from ultraviolet to visible regions. In addition to having excellent transparency, it also exhibits excellent adhesion to substrates made of various materials such as glass, metal, and plastic. In addition, this coating film 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 has excellent solvent resistance and dye resistance, and is highly hard. 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 () (In the formula, R ¹ is a hydrogen atom or a lower alkyl group, R ²
is a hydrogen atom, a lower alkyl group or a lower alkoxy group, n is an integer of 2 to 5), and a polymerizable monomer represented by the general formula () (In the formula, R ³ is a hydrogen atom or a lower alkyl group, m
means an integer of 1 to 5).