JPH07110577A - Photopolymerizable composition, color filter using the composition and its production method - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable composition excellent in alkali developability and especially a binder to constitute the composition by incorporat ing a photopolymerization initiator, an addition-polymerizable monomer and a specified resin. CONSTITUTION:A photopolymerization initiator or a photopolymerization base, an addition-polymerizable monomer having an ethylenic unsaturated double bond, a resin having repeating units shown by formulas I and II and having 500-30,000 number average mol.wt. and a resin obtained by the reaction of 1.0 to 0.1 equivalent of a primary amine shown by formula III with one equivalent of an anhydride group are incorporated. In the formulas I to III, Ar<1> is phenyl (the phenyl can be replaced by 1-4C alkyls, 1-4C alkoxyls, 6-10C aryls, 8-12C aralkyls, halogen atom or the combination of the >=2 kinds), (x) and (y) are the molar fraction of the repeating unit in the resin, x=0.85 to 0.55, y=0.15 to 0.45, R is 1-6C alkylenes, and Ar<2> is aryls.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable composition which is excellent in chemical resistance of a cured product after photopolymerization and heat treatment and can be developed with an aqueous alkali solution. The photopolymerizable composition according to the present invention is particularly useful for forming a protective layer of a color filter.

[0002]

2. Description of the Related Art A color filter is an important part of a liquid crystal display panel and has various required performance items.
When used as a TN or FLC liquid crystal display panel, heat resistance and chemical resistance are particularly important in forming a transparent conductive layer provided on a color filter and subsequently processing the transparent electrode. That is, the liquid crystal display panel is
A multicolor image layer is usually provided on a transparent substrate made of glass. This multicolor image layer is usually a matrix of alternating red, green and blue pixels. The size of this pixel varies depending on the purpose of use, but one side is 10 to 100 μm × 5
It has a size of about 0 to 400 μm, and its shape is not necessarily a rectangle of the above size, and it may have a shape processed into a desired shape according to the purpose of use. Further, in some cases, those having a black matrix or a light blocking black matrix between the above-mentioned red, green and blue pixels and in the peripheral portion are also used. Further, a color filter is obtained by forming a protective layer on such a multicolor image layer. A transparent conductive layer is usually formed on this by sputtering of ITO. Then, in the case of an STN type or a ferroelectric liquid crystal type panel, it is further processed into a transparent electrode by photolithography to obtain a color filter with an electrode. Then, an alignment film is formed on the color filter with electrodes. Further, a transparent electrode and an alignment film on another transparent substrate are sealed with a spacer with a constant gap therebetween, and then a liquid crystal is injected between the two substrates to manufacture a panel.

In the process of forming a color filter for a series of liquid crystal display panels, the protective layer on the multicolor image layer is
1) provides flatness, 2) exhibits sufficient hardness so that the spacer does not go into the liquid crystal cell gap, and 3) various chemicals used in the photolithography process of the transparent conductive layer (solvent of photoresist) , Acid etching solution, alkaline resist stripping solution, solvent for alignment film coating solution, etc.), and 4) transparency in the visible light range without clouding or turbidity 5) multicolor In addition to the close contact with the image layer, it may be directly provided on the substrate on which the multicolor image is not formed, so that it is necessary to have excellent adhesion to the substrate. For this purpose, JP-A-60-21
6307 epoxy compound and polyvalent carboxylic acid or anhydride thereof, nylon resin described in JP-A-60-244932, melamine compound described in JP-A-63-131103 and thermal curing such as epoxy resin Resins have been proposed. Certainly, these thermosetting resins have almost reached the target in terms of the required performance of the above 1) to 4).

However, in order to secure the seal at the non-image portion of the protective layer, it is necessary to remove the protective layer on the transparent substrate, and JP-A-57-42009, JP-A-1-130103 and the like. There has been a demand that the protective film on the scribe line must be removed as described in JP-A-1-134306. However, it is difficult to accurately carry out these with the thermosetting resin as described above. In addition, such thermosetting resins are generally a combination of a curing agent and an epoxy resin, and thus are
When the components are mixed and placed, the reaction progresses over time and the viscosity of the coating liquid increases, making it difficult to make the film thickness uniform, the usable time is short, and the accuracy of the film thickness is difficult to obtain. There are drawbacks.

As an effective means for solving these problems, a so-called photosensitive resin type which is photosensitive and capable of developing an unexposed portion has been demanded. Known examples of the photosensitive layer, which is provided on the color filter layer by a method such as coating and is photocured to be used as a protective layer, are disclosed in JP-A-57-42009 and JP-A-57-42009. 60-24
UV-curable resin described in JP-A-4932, JP-A-59-7.
No. 317, a vinyl carbonyl group-containing polymer, JP-A No. 59-184325, a photosensitive resin comprising PVA and a photosensitizer, JP-A No. 60-42704, a rubber resin, and JP-A No. 2-191901. A photosensitive resin obtained by removing a pigment from a photosensitive resin composition in which a pigment is dispersed and used as a coloring layer is known.

Further, a protective layer that is hardened by light and can be developed in an unexposed area with an alkaline aqueous solution which is advantageous in terms of hygiene and pollution control, and after which the cured film is given more alkali resistance by heating is most preferable. For such a method, the composition described in JP-A-3-126950, JP-A-52-
It is known that the composition described in No. 132091 and the composition described in Japanese Patent Publication No. 4-20923 can be used.

However, these photosensitive protective layer forming compositions still have a developability when formed into a photosensitive coating film, a stickiness (tack) on the surface, and a coating film or an image after curing treatment after development. It was insufficient in terms of alkali resistance, solvent resistance, transparency and adhesion to the substrate. There is also a method of forming a photopolymerizable composition layer made of such a composition on a temporary support and transferring this, but the transferability in such a case was insufficient. Further, when forming a transparent conductive layer on the protective layer, the various chemicals described above (solvent of photoresist,
Even if it has resistance to an acidic etching solution, an alkaline resist stripping solution, a solvent for an alignment film coating solution, etc., there is a problem that defects such as cracks occur in the formed transparent conductive layer.

[0008]

Therefore, the object of the present invention is to provide 1) flatness, 2) hardness, 3) chemical resistance, 4) transparency, 5) adhesion to a substrate, and 6) transparent conductivity. It is an object of the present invention to provide a photopolymerizable composition having an excellent alkali developability, particularly a binder for constituting the same, so as to provide a protective layer (OC layer) having each required performance in forming the layer.
A second object of the present invention is to subject the photocured product after development to alkali resistance treatment at a relatively low temperature and for a short treatment time, and a photopolymerizable composition having a small amount of components volatilized during the heat treatment. To provide. A third object of the present invention is to provide a method for producing a color filter particularly useful for a liquid crystal display panel, which comprises using the above photopolymerizable composition and forming a protective layer on the color filter by a coating method or a transfer method. There is a thing.

[0009]

Means for Solving the Problems As a result of diligent efforts, the inventors of the present invention have found that the objects of the present invention are (1) a photopolymerization initiator or a photopolymerization initiator system, and (2) an ethylenically unsaturated double bond. And (3) a resin having a number average molecular weight of 500 to 30,000, which has at least repeating units represented by the following general formulas (I) and (II), and a general formula (III) below. Photopolymerizable composition comprising a resin obtained by reacting a primary amine obtained by reacting with 1 equivalent of an anhydride group in a ratio of 1.0 to 0.1 equivalent, and a photopolymerizable composition using the same. The inventors have found that this can be achieved by a color filter having a protective layer formed, and have completed the present invention.

[0010]

[Chemical 2]

[Wherein Ar ^{1 is a} phenyl group (wherein the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a carbon number of 6)
To 10 aryl groups, C8 to C12 aralkyl groups, halogen atoms or combinations of two or more thereof) x, y: mole fraction of repeating units in the resin, x =
It represents 0.85 to 0.55 and y = 0.15 to 0.45. Ar ² —R—NH ₂ (III) [In the formula, R is an alkylene having 1 to 6 carbon atoms which may have a branch,
Ar ² is an aryl group (the aryl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carbon number 6).
To 10 aryl groups, C8 to C12 aralkyl groups, halogen atoms or a combination of two or more thereof. The present invention will be described in detail below.

The composition of the resin used in the present invention is such that the composition ratio of repeating units is x = 0.85 to 0.55, y = 0.1.
5 to 0.45 is preferable, but x = 0.8 is particularly preferable.
0 to 0.55 and y = 0.20 to 0.45. When the composition ratio of x is less than 0.55, the exposed portion of the photopolymerizable composition has insufficient resistance to an alkali developing solution, and when it exceeds 0.85, the developability of the unexposed portion with the developing solution is poor.

The number average molecular weight of the resin is preferably one having a molecular weight of 500 to 30,000, more preferably 700 to 20,000. It is difficult to produce a copolymer having a number average molecular weight of less than 500, and when it exceeds 30,000, the alkali developability of the photosensitive layer is poor, and
The developer resistance is also poor. That is, since the alkali developability is poor, it is soaked in a developing solution for a long time, and the exposed area is likely to swell, so that a good image cannot be obtained.

The resin used in the present invention can be obtained, for example, by copolymerizing maleic anhydride and one or more of the following monomers in the following group in the presence of a polymerization initiator in a suitable solvent. Examples of monomers include styrene, methylstyrene, ethylstyrene, propylstyrene, isopropylstyrene, butylstyrene, sec-butylstyrene, tert-butylstyrene, dimethylstyrene, diethylstyrene, methoxystyrene, ethoxystyrene, propoxystyrene, Examples thereof include butoxystyrene, vinylbiphenyl, benzylstyrene, chlorostyrene, fluorostyrene, bromostyrene, chloro-methylstyrene and the like.

Further, the resin of the present invention may be further copolymerized with a monomer copolymerizable therewith as long as the performance of the resin is not impaired.

Of these, a particularly preferred example is a styrene / maleic anhydride copolymer.

Specific examples of the primary amine of the present invention include benzylamine, phenethylamine and 3-phenyl-1-.
Propylamine, 4-phenyl-1-butylamine, 5
-Phenyl-1-pentylamine, 6-phenyl-1-
Hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2-chlorobenzylamine, 3
-Chlorobenzylamine, 4-chlorobenzylamine,
2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2
-(3-chlorophenyl) ethylamine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4
-Fluoro-α, α-dimethylphenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine,
4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine and the like can be mentioned. Examples of particularly preferred primary amines are benzylamine and phenethylamine.

In the present invention, the reaction ratio of the copolymer and the primary amine is 0. 1 with respect to 1 equivalent of the maleic anhydride group.
1 to 1.0 equivalent is preferable, but 0.2 is particularly preferable.
To 1.0 equivalent. If it is less than 0.1 equivalent, the resistance of the photopolymerizable composition after exposure to alkali developer is poor. Further, the intended reaction can be efficiently progressed by making the charged amount of the amine excess over the maleic anhydride equivalent, but in that case, the excess amine is removed by a method such as reprecipitation of the copolymer, It is desirable to purify. The total amount of the resin in the photopolymerizable composition is 20% by weight to 90% by weight, and particularly preferably 30% by weight, based on the solid content in the composition.
To 70% by weight. If it is less than 20% by weight, the tackiness of the photosensitive layer is increased and the handling property is poor, and if it exceeds 90% by weight, the resistance of the exposed portion of the composition to the alkaline developer is poor.

The addition-polymerizable monomer having an ethylenically unsaturated double bond can be used alone or in combination with other monomers, and specifically, t-butyl (meth) acrylate, ethylene glycol. Di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxyethylated trimethylolpropane tri (meth) Acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate,
1,4-diisopropenylbenzene, 1,4-dihydroxybenzene di (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitic acid, lauryl (meth) acrylate, (meth) Includes acrylamide or xylylene bis (meth) acrylamide. Again 2
-A reaction product of a compound having a hydroxyl group such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate with a diisocyanate such as hexamethylene diisocyanate, toluene diisocyanate, and xylene diisocyanate. Can also be used. Of these, particularly preferred are pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate,
Tris (2-acryloyloxyethyl) isocyanurate.

The total amount of the monomers in the photopolymerizable composition is 10% by weight to 80% by weight, particularly preferably 30% by weight to 70% by weight, based on the total solid content of the composition. If it is less than 10% by weight, the exposed portion of the composition is poor in resistance to an alkali developing solution, and if it exceeds 80% by weight, tackiness of the photosensitive layer is increased, resulting in poor handleability.

The photoinitiator or photoinitiator system included in the photopolymerizable composition of the present invention can be virtually any known initiator or initiator system. Examples include p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenyl. There are acridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethylketal, thioxanthone / amine and the like. Particularly preferred is 2-
(P-Butoxystyryl) -5-trichloromethyl-
It is a compound containing a trihalomethyl group such as 1,3,4-oxadiazole. The addition amount of the photopolymerization initiator is from 0.1% by weight to 20% by weight of the total solid content, particularly preferably 0.5.
% To 5% by weight. If it is less than 0.1% by weight, the photocuring efficiency of the composition is low, and thus it takes a long time to expose the composition
If it exceeds 0% by weight, the light transmittance from the ultraviolet region to the visible region is deteriorated, which is not suitable for the protective layer of the color filter. Further, known additives such as plasticizers, fillers, stabilizers, etc. can be contained, and pigments, dyes, etc. can be added for uses other than the protective layer of the color filter.

The photopolymerizable composition of the present invention is suitable as a material for forming a protective layer of a color filter. That is, after the photopolymerizable composition of the present invention is provided in layers on the color filter having the pixels, a protective layer is formed through steps such as exposure, development and heating. In order to provide a layered form, for example, a method of applying the solution by a known means such as spraying and immersing in a liquid, or a method of forming a photopolymerizable composition layer on a temporary support and transferring it, is there. The thickness of the protective layer is usually 0.1 μm to 50 μm, particularly preferably 1 μm to 5 μm.

As the support for the color filter, a metal support, a metal-bonded support, glass, ceramics, a synthetic resin film or the like can be used. Particularly preferred are glass and synthetic resin film which are transparent and have good dimensional stability.

The photopolymerizable composition of the present invention is also used as a layer transfer material. That is, the photopolymerizable composition is directly provided on a temporary support, preferably a polyethylene terephthalate film, or is provided in a layered form on an oxygen barrier layer, a release layer, or a polyethylene terephthalate film provided with a release layer and an oxygen barrier layer, usually Laminate a removable synthetic resin cover sheet on top for handling protection. Alternatively, a layer structure (described in JP-A-5-173320) in which an alkali-soluble thermoplastic resin layer and an intermediate layer are provided on a temporary support, and a photopolymerizable composition layer is further provided can be applied. At the time of use, the cover sheet is removed, and the photopolymerizable composition layer is laminated on the permanent support, for example, the surface of the support having color filter pixels. Next, when there are oxygen barrier layers, release layers, etc., between those layers and the temporary support, and when there are release layers and oxygen barrier layers, between the release layers and oxygen barrier layers, the release layers are also oxygen barrier layers. If not, the temporary support and the photopolymerizable composition layer are peeled off to remove the temporary support, thereby laminating the composition layer on the color filter layer. Then, exposure is performed. When forming a transparent electrode on the color filter layer via a protective layer as in the case of STN, the protective layer is patterned by exposing through a mask and developing.
Development is accomplished by washing away the unpolymerized areas with a suitable alkaline developer. On the other hand, when a transparent conductive layer is provided on the entire surface as in the case of TFT, no mask is required.

As a developing solution for the photopolymerizable composition of the present invention, a dilute aqueous solution of an alkaline substance is used, and a solution containing a small amount of an organic solvent miscible with water is also included.
Suitable alkaline substances are alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium hydrogen carbonate, potassium hydrogen carbonate), Alkali metal silicates (sodium silicate, potassium silicate) Alkali metal metasilicates (sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg, Tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.01% by weight to 30% by weight, and the pH is preferably 8 to 14.

Suitable water-miscible organic solvents are methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether. , Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-
Butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate,
They are methyl lactate, ε-caprolactam and N-methylpyrrolidone. The concentration of water-miscible organic solvent is 0.1% by weight
~ 30% by weight. Further, a known surfactant can be added. The concentration of the surfactant is 0.01% by weight to
10% by weight is preferred.

The developing solution can be used as a bath solution or a spray solution. In order to remove the uncured portion of the photopolymerizable composition layer, a method of rubbing with a rotating brush or rubbing with a wet sponge in a developing solution can be combined. Usually, the liquid temperature of the developing solution is preferably around room temperature to 40 ° C. It is also possible to include a water washing step after the development processing.

After the developing step, heat treatment is performed. That is, a support having a layer photopolymerized by exposure (hereinafter referred to as a photocurable layer) is heated in an electric furnace, a dryer, or the like, or the photocurable layer is irradiated with an infrared lamp. The heating temperature and time depend on the composition of the polymerizable composition used and the thickness of the formed layer. Generally, it is preferable to heat at about 120 ° C. to about 250 ° C. for about 10 minutes to about 60 minutes in order to obtain sufficient solvent resistance and alkali resistance.

Next, I is formed on the protective layer thus formed.
A TO (indium tin oxide) layer is formed by a sputtering method. When processing the ITO layer as a transparent electrode, a photoresist layer is formed on the ITO layer, an electrode pattern is baked, the photoresist layer is developed, the ITO layer is etched, and the photoresist is peeled off. Furthermore, N-methylpyrrolidone or γ is generally used for forming the alignment film.
A coating liquid for forming an alignment film such as polyimide containing a polar organic solvent such as butyrolactone as a solvent is applied, dried, and subjected to an alignment treatment. The photopolymerizable composition of the present invention is protected against color filters prepared by any of various known methods such as a transfer method, a colored resist method, a dyeing method, a printing method, and an electrodeposition method. It is useful as a layer forming material.

The photopolymerizable composition of the present invention can be suitably used for forming a protective layer on a color filter layer, but is not limited to this application. A color resist for forming a color filter pixel, which contains a dye or a pigment and requires a high degree of chemical resistance (for example, disclosed in JP-A-63-298304), a solder resist for a printed circuit board (for example, JP-A-3-223856). Disclosure), a resist for electroless plating (disclosed in the publication), a protective film for an electric element, an interlayer insulating film, an adhesive (disclosed in, for example, JP-A-3-126950). Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, "part" means part by weight and "%" means% by weight.

[0031]

【Example】

Synthesis Example 1 153.2 parts of copolymer (number average molecular weight = 2800) of styrene / maleic anhydride = 68/32 molar ratio was mixed with propylene glycol monomethyl ether acetate / methyl ethyl ketone = 80/20 weight ratio mixed solvent 612.8.
Dissolved in part. 26.8 parts of benzylamine (0.5 equivalent to the acid anhydride) was added to propylene glycol monomethyl ether acetate / methyl ethyl ketone = 80.
A solution dissolved in 107.2 parts of a mixed solvent having a / 20 weight ratio was added dropwise at room temperature over about 1 hour. Further, the mixture was stirred at room temperature for 6 hours to obtain a benzylamine-modified product of a styrene / maleic anhydride copolymer.

Example 1. (For forming liquid protective layer) <Production of coating liquid for forming protective layer> Mix and dissolve with the following composition,
A coating liquid for forming a protective layer was prepared by filtering with a filter having a hole diameter of 0.2 μm. 20 parts by weight solution of copolymer No. 1 produced in Synthesis Example 1 (solvent is a mixture of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether in a 1/1 weight ratio) 68 parts Dipentaerythritol hexaacrylate 3. 4 parts-Tris (acryloyloxyethyl) isocyanurate 10.2 parts 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole 0.65 parts-Hydroquinone monomethyl ether 0.007 Part-Fluorine-based surfactant (F177P manufactured by Dainippon Ink and Chemicals, Inc.) 0.002 part

<Production of Protective Layer> Formed on a 1.1 mm thick glass substrate (size 350 mm × 400 mm),
The protective layer forming coating liquid is applied onto a color filter layer having R (red), G (green) and B (blue) pixels by a spin coater and dried to form a protective layer forming photosensitive film having a thickness of 3 μm. A transparent layer was formed. 200 mj / cm through the mask for baking the protective layer using the aligner of the ultra-high pressure mercury lamp light source
The substrate was irradiated with ultraviolet rays at a light amount of 2, and then developed by spraying a developing solution, which is a 1% sodium carbonate aqueous solution, onto this substrate, and washed with water. Then, for heat treatment, 200 ℃
It was left for 20 minutes in the drier and then cooled.

The protective layer on the color filter layer thus obtained was sputtered with an ITO film to give a thickness of 0.2 μm.
Provided with a thick film, and a positive photoresist (FH HF Electronics, FH
2130), exposed through an electrode pattern mask, developed, etched the ITO layer with hydrochloric acid / iron chloride aqueous solution, and peeled with a resist stripping solution (Fuji Hunt Electronics Technology Co., Ltd., MS2001). The ITO electrode without the obtained was obtained. The electrode was peeled off using an adhesive tape, but it was not peeled off. Further, an alignment film coating liquid (N-methylpyrrolidone / γ-butyrolactone solution of polyimide resin) was applied onto this with a spin coater and dried, but an alignment film layer was obtained without swelling. The pencil hardness of the protective layer was 5H. Table 2 shows the evaluation results of other items.

Example 2. (Film-like protective layer forming material) The protective layer forming coating liquid of Example 1 is applied onto a polyethylene terephthalate film temporary support having a thickness of 75 μm and dried to form a protective layer forming photosensitive layer having a thickness of 3 μm. Formed. A 15 μm-thick polypropylene cover sheet was laminated on this to obtain a film-shaped protective layer forming material. A glass substrate having the color filter layer described in Example 1 was prepared. First, remove the cover sheet from the film-like protective layer forming material,
The photosensitive layer was laminated so as to be in contact with the color filter layer, and laminated using a laminator. Then, when the temporary support was peeled off, a photosensitive layer was formed on the color filter layer. As in the case of Example 1, the photosensitive layer was exposed and developed and heat-treated to form a protective layer. An ITO electrode was formed on this protective layer in the same manner as in Example 1. As a result, an ITO electrode was obtained which was in close contact with the ITO electrode and had no defects. Similarly, an alignment film could be formed without the protective layer swelling. The pencil hardness was 5H. Table 3 shows the evaluation results of other items.

Synthetic Examples 2 to 22 Maleic acid monoamide-containing resin (Resin No. 2) was prepared in the same manner as in Synthetic Example 1 using the resins and amines shown in Table 1.
~ 22) were synthesized.

Table 1: Synthesized polymer compounds ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Resin number average amine No. Composition (molar ratio) Molecular weight Equivalent weight to anhydrate ───────────────────────────────────── 1 S / M = 68/32 2800 benzylamine 0.5 2 S / M = 68/32 2800 phenethylamine 0.5 3 S / M = 68/32 2800 benzylamine 0.7 4 S / M = 68/32 2800 phenethylamine 0.7 5 S / M = 68/32 2800 α-methylbenzyl 0.7 amine 6 S / M = 68/32 2800 benzylamine 1.0 7 S / M = 69/31 4000 benzylamine 0.8 8 S / M = 69/31 4000 benzylamine 1.0 9 S / M = 75/25 4000 benzylamine 0.8 10 S / M = 75/25 4000 phenethylamine 0.8 11 S / M = 75 25 4000 Benzylamine 1.0 12 S / M / Vinyl acetate 2800 Benzylamine 0.5 = 54/38/8 13 S / M / Vinyl acetate 2800 Phenethylamine 0.7 = 54/38/8 14 S / M = 68 / 32 2800 aniline 0.5 15 S / M = 68/32 2800 aniline 0.7 16 S / M = 75/25 4000 aniline 0.8 17 S / M = 68/32 2800 butylamine 0.5 18 S / M = 68/32 2800 Butylamine 0.7 19 S / M = 75/25 4000 Butylamine 0.8 20 S / M = 50/50 4900 Benzylamine 0.5 21 S / M = 84/16 2800 Phenethylamine 1.0 22 S / M = 68/32 2800 benzylamine 0.05 ────────────── ───────────────────── where, S: represents a maleic anhydride: styrene M

Synthesis Example 23. (Resin No. 23) Isobutylene / maleic anhydride copolymer of Production Example 1 described in JP-A-52-13209 (number average molecular weight 80,000, maleic anhydride unit: 50 mol%, butylamine: 0.8 equivalent) Use).

Synthesis Example 24. (Resin No. 24) Styrene / methyl methacrylate / maleic anhydride copolymer of Example 1 described in JP-A-2-97502 (number average molecular weight of 30,000, maleic anhydride unit of 16 mol%, propylamine 1 .1 equivalent use).

Synthesis Example 25. (Resin No. 25) Methyl methacrylate / butyl acrylate / itaconic anhydride copolymer of Example 4 described in JP-A-2-97502 (number average molecular weight 36000, itaconic anhydride unit 16 mol%, propylamine 1.1 eq. Used).

Examples 3 to 14 and Comparative Examples 1 to 12 In the same manner as in Example 1, Resin Nos. 2 to 25 were used to prepare coating solutions for forming a protective layer. This was applied on a glass substrate and dried to form a coating film having a thickness of 3 μm, which was exposed, developed (1% sodium carbonate aqueous solution, 30 ° C.) and post-heated. The method of evaluating the performance of each sample is described below.

1. The photosensitive layer coated on a developable glass substrate with a spin coater so as to have a film thickness of 3 μm was immersed in a 1% aqueous sodium carbonate solution at 30 ° C. for 1 minute to evaluate whether or not the layer was dissolved.

2. Resistant to liquid developer A photosensitive layer coated with a spin coater so as to have a thickness of 3 μm on a glass substrate is passed through a mask having a rectangular image of 80 μm × 300 μm to obtain 200 mj / cm 2
It was exposed and immersed in a 1% aqueous sodium carbonate solution at 30 ° C. for 1 minute, and evaluated by whether or not the exposed portion was in close contact with the substrate.

3. Flatness On a 2 μm thick color filter layer on a glass substrate (2 μm
a photosensitive layer having a thickness of 3 .mu.m, exposed (200 mj / cm @ 2), developed and post-heated (20
The surface irregularities of the protective layer obtained by the treatment at 0 ° C. for 60 minutes) were measured using a film thickness meter, and those having irregularities of ± 0.5 μm or less were judged to be good, and those exceeding this were judged to be defective.

4. Hardness A 3 μm thick photosensitive layer is formed on a glass substrate and exposed (2
00 mj / cm2), development, post-heating (200 ° C, 60
After that, the evaluation was performed according to the pencil hardness test of JIS K5400.

5. A 3 μm thick photosensitive layer is formed on an alkali-resistant glass substrate and exposed (2
00 mj / cm2), development, post-heating (200 ° C, 60
After immersing in a 5% KOH aqueous solution for 30 minutes at 50 ° C., it was evaluated whether or not wrinkles and turbidity were generated on the surface.

6. After forming a 3 μm-thick photosensitive layer for forming a protective layer on a light-transmissive glass substrate, exposing the entire surface (200 mj / cm 2), developing and post-heating (200 ° C., 60 minutes), clear the surface. Those having good transparency and generating haze were judged to have poor transparency.

7. Substrate adhesion A photosensitive layer for forming a protective layer having a thickness of 3 μm was formed on a glass substrate, exposed over the entire surface (200 mj / cm 2), developed, and post-heated (200 ° C., 60 minutes), and then cross-cut. Then, it was peeled off with a Mylar tape and the adhesion was evaluated. 10
If there was no peeling in 0 cross-cut portions, the adhesion was good, and if peeling occurred even in one place, the adhesion was poor.

8. Formability of transparent conductive layer A photosensitive resin layer for forming a protective layer having a thickness of 3 μm is formed on a glass substrate, exposed over the entire surface (200 mj / cm ² ), developed, and post-heated (200 ° C., 60 minutes), and then subjected to a photoelectric conversion. Using a high frequency sputtering device manufactured by Anelva, indium tin oxide (tin oxide content 6% by weight) was applied with a voltage of 800 V, a current of 1.8 A, an output of 270 W, and an argon pressure of 5 × 10 ⁻⁴ To.
Deposition was performed for 10 minutes under the condition of rr. The surface state of the obtained transparent conductive layer was observed with a microscope, and an adhesion test by tape peeling was further performed to evaluate the formability of the transparent conductive layer. The surface of the transparent conductive layer is flat and uniform, and there is no failure such as peeling in the adhesion test, good formability of the transparent conductive layer, and wrinkles or cracks on the surface of the transparent conductive layer.
Alternatively, if the transparent conductive layer was peeled off by the adhesion test, it was determined that the formability was poor. Table 2 shows the evaluation results of the above items.

Table 2: Evaluation results of the composition ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Resin development resistance Development Flatness Hardness Al resistance to light transmission Substrate adhesion Transparent conductivity No liquid Liquid potassium Potency Electrolytic layer After development After heating Formability ──────────────────── ──────────────── Example 1 1 Good Good Good Good 5H Good Good Good Good Good Good Good 3 2 Good Good Good Good 5H Good Good Good Good Good 4 3 Good Good Good 5H Good Good Good Good 5 4 good good good good 5H good good good good good good 6 5 good good good good 5H good good good good good 7 6 good good good 5H good good good 8 7 good good 9 good good 9 good good 9 good 5H Good Good Good Good Good Good good 10 9 good good good good 5H good good good good good good 11 10 good good good good good 5H good good good good good 12 11 good good good 5H good good good 13 good good 13 good good 13 good good 13 good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good Good 5H Good Good Good Good Good Good ──────────────────────────────────── Comparative Example 1 14 Good Good Good 5H good good good good good bad bad 2 15 good good good good 5H good good good good good bad bad 3 16 good good good 5H good good good good bad bad 4 17 good good 5H good good good bad bad 5 18 good good good 5H good good 6 19 Good Good Good Good 5H Good Good Good Good Good Bad 7 20 Good Bad Bad 4H No Good Bad Bad Bad Bad Bad Good Good Good 4H Good Good Good Bad Good Bad 922 Bad Good Good Good 4H Bad Good Bad Bad Bad Bad 10 23 Bad Bad Bad 2H Bad Good Bad Bad Bad 11 Bad Bad Bad 12 Hot Bad Bad Poor Poor Poor HB Poor Good Poor Poor Poor ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Examples 15 to 26 and Comparative Examples 13 to 24 In the same manner as in Example 2, Resin Nos. 2 to 25 were used to obtain film-like protective layer forming materials. Using this, evaluation was performed in the same manner as in the sample preparation method in the above-described evaluation method except that lamination was performed as shown in Example 2 instead of coating with a spin coater. The evaluation results are shown in Table 3.

Table 3: Evaluation results of the composition ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Resin development resistance Development Flatness Hardness Al resistance to light transmission Substrate adhesion Transparent conductivity No liquid Liquid potassium Potency Electrolytic layer After development After heating Formability ──────────────────── ──────────────── Example 21 Good Good Good Good 5H Good Good Good Good Good Good Good 15 2 Good Good Good 5H Good Good Good Good Good Good 16 3 Good Good Good 5H Good Good Good Good 17 4 Good Good Good Good 5H Good Good Good Good Good Good Good 18 5 Good Good Good Good 5H Good Good Good Good Good Good 19 6 Good Good Good 5H Good Good Good Good 20 7 Good Good Good 8 Good Good 21 Good 5H good Good good good good good good good 22H good good good 5H good good good good good good 23 10 good good good 5H good good good good good 24 11 good good 5H good good good good 25 good good 26 good good 25H good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good good 13 Good Good Good Good 5H Good Good Good Good Good Good ──────────────────────────────────── Comparative Example 13 14 Good Good Good Good 5H Good Good Good Good Good Bad 14 15 Good Good Good Good 5H Good Good Good Good Good Bad Bad 15 16 Good Good Good 5H Good Good Good Good Bad 16 17 Good Good Good 5 Good Good Good 5 H Good 5 Good Good Good Good Good Bad 18 19 Good Good Good 5H Good Good Good Good Bad 1 20 Good Bad Bad Bad 4H Bad Good Bad Bad Bad Bad Bad 20 21 Bad Bad Good Good 4H Good Good Good Bad Bad Bad 21 22 Bad Bad Bad Good 4H Bad Good Bad Bad Bad Bad 22 23 Bad Bad Bad 2H Bad Bad Good Bad Bad 23 24 Bad Good Bad Bad Bad Bad 24 25 Bad Bad Bad Bad 2H Bad Good Bad Bad Bad Bad ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━

From this, it can be seen that the photopolymerizable composition according to the present invention exhibits excellent performances in all the evaluated items.

[0054]

The photopolymerizable composition of the present invention has excellent alkali solubility, and the photopolymerized portion has excellent developer resistance, hardness, alkali resistance, light transmission, substrate adhesion and transparency. It has a conductive layer forming property. It is particularly useful for forming a protective layer of a color filter, and can form a protective layer having excellent durability and high flatness.

Claims (4)

[Claims] 1. A photopolymerization initiator or a photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) at least the following general formula (I):
And a resin having a repeating unit represented by (II) and having a number average molecular weight of 500 to 30,000 and the following general formula (I
A photopolymerizable composition comprising a resin obtained by reacting the primary amine represented by II) in a ratio of 1.0 to 0.1 equivalent to 1 equivalent of an anhydride group. [Chemical 1] [Wherein Ar ^{1 is a} phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 6 carbon atoms).
To 10 aryl groups, C8 to C12 aralkyl groups, halogen atoms or combinations of two or more thereof) x, y: mole fraction of repeating units in the resin, x =
It represents 0.85 to 0.55 and y = 0.15 to 0.45. Ar ² —R—NH ₂ (III) [In the formula, R is an alkylene having 1 to 6 carbon atoms which may have a branch,
Ar ² is an aryl group (the aryl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carbon number 6).
To 10 aryl groups, C8 to C12 aralkyl groups, halogen atoms or a combination of two or more thereof. ] 2. A protective layer comprising a cured product of the photopolymerizable composition according to claim 1 on a multicolor layer in which at least red, green and blue pixels are arranged in a matrix on a transparent substrate. A color filter characterized by having. 3. A layer of the photopolymerizable composition according to claim 1 is formed on a multicolor layer in which at least red, green and blue pixels are arranged in a matrix on a transparent substrate, and the layer is exposed. A method for producing a color filter, which comprises removing an unexposed portion with an alkaline aqueous solution and then curing the exposed portion by heating. 4. A layer of the photopolymerizable composition according to claim 1 on a temporary support on a multicolor layer in which at least red, green and blue pixels are arranged in a matrix on a transparent substrate. The photopolymerizable composition is brought into close contact, the layer of the photopolymerizable composition is transferred onto the multicolor layer, exposed, the unexposed portion is removed using an alkaline aqueous solution, and then the exposed portion is cured by heating. Characteristic color filter manufacturing method.