JP3319642B2 - Photopolymerizable composition, color filter using the same, and method for producing the same - Google Patents

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 component 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 the formation of a transparent conductive layer provided on a color filter and subsequent processing into a transparent electrode. That is, the liquid crystal display panel is
Usually, a protective layer is formed after forming a multicolor image layer having red, green, blue pixels or optionally further a black or light-blocking black matrix on a transparent substrate made of glass, and then forming a protective layer thereon. A transparent conductive layer is formed by sputtering ITO (indium tin oxide). Then, ST
In the case of an N-type or ferroelectric liquid crystal panel, a transparent electrode is further processed by photolithography to obtain a color filter with an electrode. Then, an alignment film is formed on the color filter with electrodes. A panel is manufactured by injecting a liquid crystal between these two substrates after sealing a transparent electrode and an alignment film on another transparent substrate with a certain gap kept by a spacer.

In the process of forming a color filter for a series of liquid crystal display panels, a protective layer on a multicolor image layer includes:
1) imparts flatness; 2) exhibits sufficient hardness so that a spacer does not enter into the cell gap of the liquid crystal; and 3) various chemicals (photoresist solvents) used in the photolithography process of the transparent conductive layer. , Acid etching solution, alkaline resist stripping solution, solvent for alignment film coating solution, etc.) and 4) transparency in the visible light region, no haze or turbidity, 5) multicolor In addition to the adhesion to the image layer, the adhesive may be directly provided on the substrate on which the multicolor image is not formed, and therefore, it is necessary to have excellent adhesion to the substrate. For this purpose, JP-A-60-21
No. 6307, thermosetting such as polycarboxylic acid or anhydride thereof, nylon resin described in JP-A-60-249332, melamine compound and epoxy resin described in JP-A-63-131103. Resins have been proposed. Certainly, these thermosetting resins can almost achieve the target in the required performance of the above 1) to 4).

However, in order to secure the seal in the non-image portion of the protective layer, there is a demand that the protective layer must be removed on a transparent substrate, and Japanese Patent Application Laid-Open Nos. 57-42009, 1-130103 and As described in JP-A-1-134306, there has been a demand that the protective film on the scribe line must be removed. However, it is difficult to carry out these accurately with the thermosetting resin as described above. Further, such a thermosetting resin is generally a combination of a curing agent and an epoxy resin, and thus has a high reactivity.
When the components are mixed and placed, the reaction proceeds with time and the viscosity of the coating solution increases, so that it is difficult to make the film thickness uniform, the usable time is short, and it is difficult to obtain the accuracy of the film thickness. There are drawbacks.

As an effective means for solving these problems, there has been a demand for a so-called photosensitive resin type which is photosensitive and can develop unexposed portions. Examples of known photosensitive materials which are provided on a color filter layer by coating or the like and which are cured by light and used as a protective layer are described in JP-A-57-42009 and JP-A-57-2009. 60-24
No. 4932, UV-curable resin disclosed in JP-A-59-7
No. 317, a vinylcarbonyl group-containing polymer described in JP-A-59-184325, a photosensitive resin comprising PVA and a photosensitive agent, a rubber-based resin described in JP-A-60-42704, and a rubber-based resin described in JP-A-2-191901. A photosensitive resin obtained by removing a pigment from a pigment-dispersed photosensitive resin composition used as a coloring layer is known.

Further, a protective layer which is cured by light and which can be developed with an aqueous alkali solution which is advantageous in terms of hygiene and pollution control in the unexposed area, and after which heating gives the cured film greater alkali resistance, is most preferred. The method described in JP-A-3-126950 is disclosed in JP-A-3-126950.
It is known that this can be achieved by using the composition described in No. 132091 and the composition described in JP-B-4-20923.

However, these compositions for forming a photosensitive protective layer still have poor developability when formed into a photosensitive coating film, stickiness (tack) on the surface, and curing of the coating film or image after development. It was insufficient in terms of alkali resistance, solvent resistance, transparency, and adhesion to a substrate. There is also a method of forming a photopolymerizable composition layer composed of such a composition on a temporary support and transferring the same. However, the transferability in such a case is insufficient. When a transparent conductive layer is formed on the protective layer, the above-mentioned various chemicals (solvents for photoresist,
Even if the transparent conductive layer 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.

Therefore, as a method for solving such a problem, we have already found a method described in, for example, Japanese Patent Application Nos. 5-202272 and 4-60668. However, even in these methods, there is a problem that tackiness is slightly increased since a large amount of a photopolymerizable monomer component is required in order to secure developability and formability of a transparent conductive layer.

In order to reduce the amount of the photopolymerizable monomer component, for example, it is conceivable to introduce a polymerizable group into a polymer binder. Such compounds are known per se, and for example, JP-B-51-37316 discloses examples of polymer compounds containing a carboxyl group and an ethylenically unsaturated double bond. Also, Japanese Patent Application Laid-Open No. H5-2570
No. 09 also describes an example in which a polymer compound containing a carboxyl group and an ethylenically unsaturated double bond is used for a protective film of a color filter. However, even in these methods, there is a problem in alkali resistance after curing, especially in chemical resistance at the time of forming the transparent conductive layer, because a carboxyl group remains in the cured resin.

[0010]

The object of the present invention is to achieve 1) flatness, 2) hardness, 3) chemical resistance, 4) transparency,
5) a photopolymerizable composition having excellent alkali developability and having no tack, which provides a protective layer (OC layer) having each required performance in the form of a transparent conductive layer; In particular, it is to provide a binder for constituting the same. A second object of the present invention is to provide a photopolymerizable composition, in which the alkali-resistant treatment of the photocured product after development can be performed at a relatively low temperature and a short treatment time, and the components volatilized during the heat treatment are small. Is to provide. A third object of the present invention is to use the photopolymerizable composition and form a protective layer on a color filter by a coating method or a transfer method,
An object of the present invention is to provide a method of manufacturing a color filter particularly useful for a liquid crystal display panel.

[0011]

The present inventors have made intensive efforts and as a result, the object of the present invention is to provide (1) a photopolymerization initiator or a photopolymerization initiator system, and (2) an ethylenically unsaturated double bond. And (3) a resin having at least a repeating unit represented by the following general formulas (I) and (II) and a number average molecular weight of 500 to 30,000, and a resin represented by the following general formula (III) The primary amine is used in an amount of 0.9 to 0.1 equivalent to 1 equivalent of the anhydride group, and a compound having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule is added to 1 equivalent of the anhydride group. A photopolymerizable composition comprising a resin obtained by reacting at a ratio of 0.05 to 0.9 equivalents, and a color filter having a protective layer formed using the same, has been found to be achieved. ,
The present invention has been accomplished.

[0012]

Embedded image

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, an aryl group having 6 to 10 carbon atoms,
To 12 aralkyl groups, halogen atoms or a combination of two or more thereof.) X, y: the molar fraction of the repeating unit in the resin, and x =
0.85 to 0.50, y = 0.15 to 0.50. R-NH ₂ (III) wherein R is an alkyl group having 1 to 12 carbon atoms and 7 carbon atoms
To 16 aralkyl groups, and aryl groups having 6 to 18 carbon atoms. (The alkyl group, aralkyl group, and aryl group may each have a branch, and further have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom having 6 carbon atoms.
To an aryl group, an aralkyl group having 7 to 12 carbon atoms, a halogen atom, or a combination of two or more thereof. Hereinafter, the present invention will be described in detail.

The composition of the resin having at least the repeating units represented by the aforementioned general formulas (I) and (II) used in the present invention has a composition ratio of the repeating units of x = 0.85.
０．５0.50, y = 0.15５〜0.50, preferably x = 0.80０．５0.55, y = 0.20０〜
0.45. When the composition ratio of x is less than 0.50, the resistance of the exposed portion of the photopolymerizable composition to the alkali developing solution is insufficient, 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 from 500 to 30,000, more preferably from 700 to 20,000. It is difficult to produce a copolymer having a number average molecular weight of less than 500,
When the ratio exceeds the above range, the alkali developability of the photosensitive layer is inferior and the developer resistance is also inferior. That is, since the alkali developability is inferior, the developer is immersed in the developer for a long time, and the exposed portion is easily swelled, so that a high quality image cannot be obtained.

The resin having at least the repeating units represented by the above-mentioned general formulas (I) and (II) used in the present invention can be prepared by, for example, mixing maleic anhydride and one or more of the following groups of monomers according to a conventional method. It is obtained by copolymerizing in a suitable solvent in the presence of a polymerization initiator. Examples of monomers include styrene, methyl styrene, ethyl styrene, propyl styrene, isopropyl styrene, butyl styrene, sec-butyl styrene, tert-butyl styrene, dimethyl styrene, diethyl styrene, methoxy styrene, ethoxy styrene, propoxy styrene, Butoxystyrene, vinylbiphenyl, benzylstyrene,
Chlorostyrene, fluorostyrene, bromostyrene, chloro-methylstyrene and the like can be mentioned.

Further, a monomer copolymerizable therewith may be further copolymerized as long as the performance of the resin of the present invention is not impaired. Of these, a particularly preferred example is a styrene / maleic anhydride copolymer.

Specific examples of the primary amine used in the present invention include alkylamines such as methylamine, ethylamine, propylamine, i-propylamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, and cyclohexyl. Amine, heptylamine, octylamine, 2-ethylhexylamine, laurylamine, adamantylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine and the like, and aralkylamines such as benzylamine, phenethylamine and 3 Phenyl-1-propylamine,
4-phenyl-1-butylamine, 5-phenyl-1-
Pentylamine, 6-phenyl-1-hexylamine,
α-methylbenzylamine, o-methylbenzylamine, m-methylbenzylamine, p-methylbenzylamine, pt-butylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-
Methyl-3-phenylpropylamine, o-chlorobenzylamine, m-chlorobenzylamine, p-chlorobenzylamine, o-fluorobenzylamine, m-fluorobenzylamine, p-fluorobenzylamine, p-bromophenethylamine, 2- (O-chlorophenyl) ethylamine, 2- (m-chlorophenyl) ethylamine,
2- (p-chlorophenyl) ethylamine, 2- (o-
(Fluorophenyl) ethylamine, 2- (m-fluorophenyl) ethylamine, 2- (p-fluorophenyl) ethylamine, p-fluoro-α, α-dimethylphenethylamine, o-methoxybenzylamine, m-methoxybenzylamine, p- Methoxybenzylamine, o-ethoxybenzylamine, o-methoxyphenethylamine, m
-Methoxyphenethylamine, p-methoxyphenethylamine and the like, and arylamines such as aniline, octylaniline, anisidine, 4-chloroaniline,
-Naphthylamine and the like. Among these, preferred examples of the primary amine include 2-methoxyethylamine, 3-methoxypropylamine, cyclohexylamine and butylamine, and more preferred are aralkylamines, and among them, benzylamine and phenethylamine are particularly preferred.

In the present invention, the reaction ratio between the copolymer and the primary amine is 0.1 to 1 equivalent of maleic anhydride group.
1 to 0.9 equivalent is preferred, particularly preferably 0.2 to 0.9 equivalent.
To 0.9 equivalent. When the amount is less than 0.1 equivalent, the developability of the photopolymerizable composition and the alkali developer resistance after exposure are poor.

Specific examples of the compound having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule used in the present invention include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Propyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, diethylene glycol mono (meth) )
Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate,
Examples include glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol tri (meth) acrylate. Of these,
A particularly preferred specific example is 2-hydroxyethyl (meth) acrylate.

In the present invention, the reaction ratio of the compound having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule is one equivalent of the anhydride (based on the amount of the anhydride before the reaction of the primary amine). The equivalent is preferably 0.9 to 0.05 equivalent, and particularly preferably 0.7 to 0.05 equivalent.
If it exceeds 0.9 equivalent, the alkali resistance of the photopolymerizable composition after curing is poor, and if it is less than 0.05 equivalent, the formability of the transparent conductive layer is poor.

The resin of the present invention is obtained by reacting at least the resin having repeating units represented by the following general formulas (I) and (II) with the primary amine to convert a part of the unit (II) to maleic acid monoamide. Which is obtained by reacting a part of the unit (II) with a compound having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule,
It is a resin having maleic acid monoamide and an ethylenically unsaturated double bond in the molecule. The reaction order of the primary amine and the compound having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule may be either first or simultaneous. However, from the viewpoint of preventing a side reaction between the primary amine and the ethylenically unsaturated double bond, a compound having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule after reacting the primary amine. Is desirable.
In this case, the target reaction can be efficiently advanced by using the charged amount of these compounds, particularly the compound having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule, in the above-mentioned equivalent amount or more. . In such a case, an excess of these compounds may be allowed to remain as long as there is no problem in performance, but may be purified and removed by a method such as reprecipitation.

A specific synthesizing method can be performed, for example, as follows. At least the aforementioned general formulas (I) and (II)
Is dissolved in a suitable solvent, and the primary amine or a solution thereof is added dropwise thereto. The solvent is not particularly limited as long as it can dissolve the resin without reacting with the anhydride. Examples of the solvent include methyl ethyl ketone, propylene glycol monomethyl ether acetate and a mixture thereof. The reaction temperature is preferably around room temperature. Next, a compound having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule or a solution thereof is added to the obtained resin solution. This is heated and added together with a suitable catalyst. At this time, a suitable thermal polymerization inhibitor may be added. Examples of the catalyst include an acid catalyst such as sulfuric acid and the like and a base catalyst such as pyridine and dimethylaminopyridine. The reaction temperature is preferably 40 ° C to 100 ° C. These resins may be subjected to a purification treatment for each reaction step as needed.

The addition-polymerizable monomer having an ethylenically unsaturated double bond can be used alone or in combination with another monomer. 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 trimellitate, lauryl (meth) acrylate, (meth) Acrylamide or xylylenebis (meth) acrylamide is included. Also 2
Reaction product of a compound having a hydroxyl group such as -hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and the like 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 from 10 to 80% by weight, particularly preferably from 20 to 70% by weight, based on the total solids of the composition. If the amount is less than 10% by weight, the resistance of the exposed portion of the composition to the alkali developing solution is poor. If the amount exceeds 80% by weight, the tackiness of the photosensitive layer increases and the handleability is poor.

As the photopolymerization initiator or the photopolymerization initiator system to be contained in the photopolymerizable composition of the present invention, substantially all known initiators or initiator systems can be used. Examples include p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenyl Acridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, 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 solids, particularly preferably 0.5% by weight.
% By weight to 5% by weight. If the amount is less than 0.1% by weight, the photocuring efficiency of the composition is low, so that it takes a long time for exposure,
If it exceeds 0% by weight, the light transmittance in the range from the ultraviolet region to the visible region is deteriorated, so that it is not suitable for a protective layer of a color filter. Further, known additives such as plasticizers, fillers, stabilizers and the like can be contained, and pigments, dyes and the like 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 a layer 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 the solution in the liquid, or a method of forming a photopolymerizable composition layer on a temporary support and transferring the same. is there. The thickness of the protective layer is usually from 0.1 μm to 50 μm, particularly preferably from 1 μm to 5 μm.

As a support for the color filter, a metal support, a metal-bonded support, glass, ceramic, a synthetic resin film and the like can be used. Particularly preferred are glass and synthetic resin films 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 provided on a temporary support, preferably directly on a polyethylene terephthalate film, or 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. A synthetic resin cover sheet that can be removed for protection in handling is laminated thereon. Alternatively, a layer structure 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 (described in JP-A-5-80503) can be applied. When used, the cover sheet is removed, and the photopolymerizable composition layer is laminated on a permanent support, for example, on the surface of the support having color filter pixels. Then, if there is an oxygen barrier layer, a release layer, etc., between those layers and the temporary support, if there is a release layer and an oxygen barrier layer, between the release layer and the oxygen barrier layer, the release layer is also an oxygen barrier layer. If not, the temporary support is peeled off from the photopolymerizable composition layer, and the temporary support is removed, whereby the composition layer is laminated on the color filter layer. Next, exposure is performed. When a transparent electrode is formed on a color filter layer via a protective layer as in the case of STN, exposure is performed through a mask and developed to pattern the protective layer. The development is carried out by washing away the unpolymerized areas with a suitable alkali developing solution. On the other hand, when a transparent conductive layer is provided on the entire surface as in the case of a TFT, a mask is not required.

As a developer for the photopolymerizable composition of the present invention, a dilute aqueous solution of an alkaline substance is used, and a developer containing a small amount of a water-miscible organic solvent is also included.
Suitable alkaline substances include 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 (for example, 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 organic solvents miscible with water include 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,
Methyl lactate, ε-caprolactam, N-methylpyrrolidone. 0.1% by weight of water-miscible organic solvent
３０30% by weight. Further, known surfactants can be added. The concentration of the surfactant is 0.01% by weight or more.
10% by weight is preferred.

The developing solution can be used as a bath solution or a spray solution. To remove the uncured portion of the photopolymerizable composition layer, a method such as rubbing with a rotating brush or rubbing with a wet sponge in a developer can be combined. The temperature of the developer is usually preferably around room temperature to 40 ° C. A water washing step can be added after the development processing.

After the development step, a 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 drier, 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 to obtain sufficient solvent resistance and alkali resistance.

Next, I was placed on the protective layer thus formed.
A TO layer is formed by a sputtering method. When the ITO layer is processed 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 removed. Further, for forming an alignment film, generally, a coating liquid for forming an alignment film such as polyimide containing a polar organic solvent such as N-methylpyrrolidone or γ-butyrolactone as a solvent is applied, dried, and subjected to an alignment treatment. Will be applied.

The photopolymerizable composition of the present invention can be used for a color filter prepared by any of various known methods, for example, a transfer method, a colored resist method, a dyeing method, a printing method, and an electrodeposition method. Is also useful as a material for forming a protective layer.

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 use. A coloring resist for forming a color filter pixel which requires a high degree of chemical resistance by containing a dye or a pigment (for example, disclosed in JP-A-63-298304), a solder resist for a printed board (for example, disclosed in JP-A-3-223856) It is also useful as a resist for electroless plating (disclosed in the same publication), a protective film for an electric element, an interlayer insulating film, an adhesive (disclosed in, for example, JP-A-3-126950), and an alignment film forming material. Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “parts” represents parts by weight and “%” represents% by weight.

[0037]

【Example】

Synthesis Example 1 A mixed solvent of styrene / maleic anhydride = 68/32 molar ratio (weight average molecular weight = 5000) and 122.5 parts of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50/50 weight ratio 490.
Dissolved in 0 parts. To this, 38.6 parts of benzylamine (0.9 equivalent based on the acid anhydride) was added with propylene glycol monomethyl ether acetate / methyl ethyl ketone = 5.
A solution dissolved in 154.4 parts of a 0/50 weight ratio mixed solvent was added dropwise at room temperature over about 1 hour, and the mixture was further stirred at room temperature for 6 hours. Subsequently, 5.2 parts of 2-hydroxyethyl methacrylate (0.1 equivalent to acid anhydride), 20.8 parts of a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50/50 weight ratio,
-Dimethylaminopyridine 0.24 part, 2,5-di-t
-0.01 parts of hexylhydroquinone was added, and
After reacting for 6 hours, a modified styrene / maleic anhydride copolymer (resin having maleic acid monoamide and ethylenically unsaturated double bond in the molecule. Resin No. 1)
I got

Example 1 (Formation of Liquid Protective Layer) <Preparation of Coating Solution for Protective Layer Formation>
The solution was filtered through a filter having a hole diameter of 0.2 μm to prepare a coating solution for forming a protective layer. 68 parts by weight of a 20% by weight solution of resin No. 1 produced in Synthesis Example 1 (solvent is a 1/1 weight ratio mixture of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether) 68 parts 1.4 parts of dipentaerythritol hexaacrylate Tris (acryloyloxyethyl) isocyanurate 6.8 parts 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole 0.65 part Hydroquinone monomethyl ether 0.007 part Fluorine -Based surfactant (F177P manufactured by Dainippon Ink and Chemicals, Inc.) 0.002 parts

<Manufacture of Protective Layer> A 1.1 mm thick glass substrate (350 mm × 400 mm) was formed on a glass substrate.
The above coating liquid for forming a protective layer is coated on a color filter layer having R (red), G (green), and B (blue) pixels by a spin coater and dried, and a 3 μm-thick photosensitive layer is formed. A conductive layer was formed. Using an aligner of an ultra-high pressure mercury lamp light source, 200 mj / cm through a mask for protecting layer baking
The sample was irradiated with ultraviolet light at a light quantity of ² . Thereafter, the substrate was developed by spraying a developing solution, which is a 1% aqueous solution of sodium carbonate, on the substrate, and washed with water. Then, for heat treatment, 200 ° C
After being left in a dryer for 20 minutes, it was cooled.

On the protective layer on the color filter layer thus obtained, an ITO film having a thickness of 0.2 μm was provided by a sputtering method, and a positive photoresist (FH213 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was further formed on the ITO film.
After forming 0), exposure is performed through an electrode pattern mask, developed, and the ITO layer is etched with hydrochloric acid / iron chloride aqueous solution,
When stripping was performed using a resist stripping solution (MS2001, manufactured by Fuji Hunt Electronics Technology Co., Ltd.), an ITO electrode having no defect was obtained. An attempt was made to peel the electrode using an adhesive tape, but the electrode was not peeled. A coating liquid for an alignment film (N-methylpyrrolidone / γ-butyrolactone solution of a polyimide resin) was applied thereon by a spin coater and dried, but an alignment film layer was obtained without swelling. The pencil hardness of the protective layer was 5H.

Example 2 (Material for Forming a Protective Layer in Film Form) The coating solution for forming a protective layer of Example 1 was applied on a polyethylene terephthalate film temporary support having a thickness of 75 μm and dried to form a protective layer having a thickness of 3 μm. A photosensitive layer was formed. A 15 μm-thick polypropylene cover sheet was laminated thereon to obtain a film-like protective layer forming material. A glass substrate having the color filter layer described in Example 1 was prepared. First, the cover sheet was removed from the material for forming a film-like protective layer, the photosensitive layer was overlapped so as to be in contact with the color filter layer, and laminated using a laminator. Thereafter, when the temporary support was peeled off, a photosensitive layer was formed on the color filter layer. Thereafter, as in the case of Example 1, the photosensitive layer was exposed and developed, and then subjected to a heat treatment to form a protective layer. When an ITO electrode was formed on this protective layer in the same manner as in Example 1, an ITO electrode that adhered and had no defects was obtained. Similarly, an alignment film could be formed without swelling of the protective layer. The pencil hardness was 5H.

Example 3 A protective image forming coating solution of Example 1 was applied on a polyethylene terephthalate film temporary support having a thermoplastic layer and a separation layer as in the example of JP-A-5-72724. A 15 μm thick cover film made of polypropylene was laminated thereon to obtain a film-shaped photosensitive transfer material. Laminating the film-shaped photosensitive transfer material on a glass substrate having a color filter layer in the same manner as in Example 2,
After peeling and removing the temporary support, exposure and development and heat treatment were performed in the same manner as in Example 1. As a result, a protective layer free from defects such as bubbles and pinholes was obtained in the pixel portion of the color filter layer. The pencil hardness was 5H. When an ITO electrode was formed on this protective layer in the same manner as in Example 1, an ITO electrode having no defects such as wrinkles and cracks and satisfactory adhesion was obtained. Similarly, an alignment film could be formed without swelling of the protective layer. Table 2 shows the evaluation results of other items.
Shown in

Synthesis Examples 2 to 16 Using the resins shown in Table 1, primary amines and compounds having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule, styrene / maleic Modified acid anhydride copolymer (resin having maleic acid monoamide and ethylenically unsaturated double bond in the molecule. Resin No. 2
16) was obtained.

Table 1: Synthesized polymer compound ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Synthesis example Raw material Resin Number average amine Hydroxyl group and ethylenically unsaturated No Composition (molar ratio) Molecular weight Compound containing double bond ─────────── ────────── Structure St / MAH equivalent to anhydride Equivalent ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 1 68 / 32 2800 pentylamine 0.9 HEMA 0.1 2 68/32 2800 pentylamine 0.7 HEMA 0.3 3 68/32 2800 pentylamine 0.5 HEMA 0.5 4 68/32 2800 pentylamine 0.3 HEMA 0.7 5 69/31 4000 pentylamine 0.7 HEMA 0.3 6 64 / 36 11 300 Phenylamine 0.7 HEMA 0.3 7 68/32 2800 Phenethylamine 0.7 HEMA 0.3 8 68/32 2800 Phenylamine 0.7 HEM 0.3 9 68/32 2800 pentylamine 0.5 HEA 0.3 10 69/31 4000 pentylamine 0.7 HEA 0.3 11 68/32 2800 Cyclohexylamine 0.7 HEMA 0.3 12 68/32 2800 pentylamine 0.05 HEA 0.8 13 68/32 2800 − − HEMA 0.9 14 68/32 2800 Pensylamine 1.0 − − 15 68/32 2800 Cyclohexylamine 1.0 − − 16 90/10 2800 Pensylamine 0.7 HEMA 0.3 ━━━━━━━━━━━ St: styrene MAH: maleic anhydride HEMA: 2-human peroxyethyl methacrylate
HEA: 2-Heatoxyethyl acrylate

Synthesis Example 17 (Resin No. 17) Addition product of methyl methacrylate / styrene / maleic acid and glycidyl methacrylate described in Example 3 of JP-A-5-25709 (carboxyl group and ethylenically unsaturated Resin having a double bond).

Synthesis Example 18 (Resin No. 18) The isobutylene / maleic anhydride copolymer (number average molecular weight of 8) described in Production Example 1 of JP-A No. 52-13209.
0000, 50 mol% maleic anhydride units, 0.8 equivalents of butylamine).

Synthesis Example 19 (Resin No. 19) Styrene / methyl methacrylate / maleic anhydride copolymer of Example 1 described in JP-A-2-97502 (number average molecular weight: 30,000, maleic anhydride unit: 16 Mol%, 1.1 equivalents of propylamine).

Examples 4 to 13 and Comparative Examples 1 to 8 Resin Nos. Using 2 to 11 (Examples) and 12 to 19 (Comparative Examples), coating liquids for forming a protective layer were prepared and evaluated in the same manner.

Comparative Example 9 Resin No. was prepared in the same manner as in Example 3 except that 1.4 parts of dipentaerythritol hexaacrylate in Example 3 was changed to 6.8 parts. Using No. 14, a coating liquid for forming a protective layer was prepared and evaluated in the same manner. The method for evaluating the performance of each sample is described below.

1. Developability The photosensitive layer applied to a glass substrate with a spin coater to a thickness of 3 μm was immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute to evaluate whether or not it was dissolved.

2. Developing solution resistance A photosensitive layer applied by a spin coater so as to have a thickness of 3 μm on a glass substrate is passed through a mask capable of obtaining a rectangular image of 80 μm × 300 μm by 200 mj / cm ^2.
The substrate was exposed to light and immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute to evaluate 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
m), a photosensitive layer is formed to a thickness of 3 μm, exposed (200 mj / cm ² ), developed, and post-heated (20 mj / cm ² ).
(0 ° C., 60 minutes), the unevenness of the surface of the protective layer obtained was measured and evaluated using a film thickness gauge.

4. Hardness A photosensitive layer having a thickness of 3 μm is formed on a glass substrate and exposed (2
00 mj / cm ² ), development, post-heating (200 ° C., 60
), And evaluated according to the pencil hardness test of JIS K5400.

5. Alkali resistance A photosensitive layer having a thickness of 3 μm is formed on a glass substrate and exposed to light (2
00 mj / cm ² ), development, post-heating (200 ° C., 60
After immersion in a 5% aqueous solution of KOH at 50 ° C. for 30 minutes, the surface was evaluated for wrinkles and turbidity.

6. Light-transmitting A photosensitive layer for forming a protective layer having a thickness of 3 μm is formed on a glass substrate, the entire surface is exposed (200 mj / cm ² ), development, post-heating (200 ° C., 60 minutes), and the surface is clear. Was judged to be good in transparency, and what caused cloudiness was judged to be poor in transparency.

7. Substrate adhesion A photosensitive layer for forming a protective layer having a thickness of 3 μm was formed on a glass substrate, and the entire surface was exposed (200 mj / cm ² ), cross-cut after development, and after post-heating (200 ° C., 60 minutes). Then, it was peeled off with a Mylar tape to evaluate the adhesion. 10
A sample having no peeling at zero cross-cut portions was determined to have good adhesion, and a sample having peeled even at one location was determined to have poor adhesion.

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, and the entire surface is exposed (200 mj / cm ² ), developed, and post-heated (200 ° C., 60 minutes). 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.
Vapor 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 was further performed by tape peeling to evaluate the formability of the transparent conductive layer. A transparent conductive layer having a flat and uniform surface and having no failure such as peeling in an adhesion test has a good formability of the transparent conductive layer, wrinkles and cracks are generated on the surface of the transparent conductive layer,
Alternatively, those in which the transparent conductive layer was peeled off by the adhesion test were judged to be poor in formability.

9. It was applied to a tack glass substrate with a spin coater to a thickness of 3 μm and dried at 80 ° C. for 2 minutes to obtain a protective layer-like photosensitive layer. Evaluate the adhesiveness of the surface by finger touch test,
Compared with the adhesiveness of the surface of the coating film of Color Mosaic K (manufactured by Fuji Hunt Electronics Technology) obtained in the same manner, the film was evaluated as good or better than the coating film of Color Mosaic K. Table 2 shows the evaluation results of the above items.

[0059]

[Table 1]

[0060]

[Table 2]

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

[0062]

The photopolymerizable composition of the present invention has excellent alkali solubility, and the photopolymerized portion has excellent developer resistance, hardness, alkali resistance, light transmittance, substrate adhesion, and transparency. Has conductive layer forming properties and low tack. Particularly useful for forming a protective layer of a color filter, a protective layer having excellent durability and high flatness can be formed.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takayanagi Hill 200, Onakazato, Fujinomiya City, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd. (56) References JP-A-5-265208 (JP, A) JP-A-5-265 27438 (JP, A) JP-A-5-100427 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/038 501 G02B 5/20 101 G03F 7/027 G03F 7 / 033

Claims (6)

(57) [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 number average molecular weight of 500 to 30,000 having a repeating unit represented by formula (II) and a resin represented by the following general formula (I)
Compounds having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule in the same molecule as the primary amine represented by II) are used in an amount of 0.9 to 0.1 equivalent to 1 equivalent of the anhydride group.
A resin obtained by reacting at a ratio of 0.05 to 0.9 equivalent relative to the equivalent. Embedded image [Wherein, Ar ¹ : a phenyl group (the phenyl group has 1 carbon atom)
To 4, an alkyl group, an alkoxy group having 1 to 4 carbon atoms,
May be substituted with an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a halogen atom or a combination of two or more thereof. , X =
0.85 to 0.50, y = 0.15 to 0.50. R-NH ₂ (III) wherein R is an alkyl group having 1 to 12 carbon atoms and 7 carbon atoms
To 16 aralkyl groups, and aryl groups having 6 to 18 carbon atoms. (The alkyl group, aralkyl group, and aryl group may each have a branch, and further have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom having 6 carbon atoms.
To an aryl group, an aralkyl group having 7 to 12 carbon atoms, a halogen atom, or a combination of two or more thereof. ] 2. The photopolymerizable composition according to claim 1, wherein the primary amine is an aralkylamine represented by the following general formula (IV). Ar ² —R′—NH ₂ (IV) [wherein R ′: an alkylene having 1 to 6 carbon atoms which may have a branch, Ar ² : an aryl group (the aryl group has 1 to 4 carbon atoms) Alkyl group, alkoxy group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, 7 to 12 carbon atoms
May be substituted with an aralkyl group, a halogen atom or a combination of two or more of them.) ] 3. The photopolymerizable compound according to claim 1, wherein the compound having a hydroxyl group and an ethylenically unsaturated double bond in the same molecule is 2-hydroxyethyl (meth) acrylate. Composition. 4. The photopolymerizable composition according to claim 1, 2 or 3, 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 comprising a protective layer comprising a cured product of the above. 5. The photopolymerizable composition according to claim 1, wherein at least red, green and blue pixels are arranged in a matrix on a transparent substrate on a multicolor layer. A method for producing a color filter, comprising: forming a layer, exposing, removing an unexposed portion using an alkaline aqueous solution, and then curing the exposed portion by heating. 6. The method according to claim 1, wherein at least red, green and blue pixels are arranged in a matrix on a transparent substrate and on a temporary support on a multicolor layer. A light-sensitive material having a layer of the photopolymerizable composition is brought into close contact, the layer of the photopolymerizable composition is transferred onto the multicolor layer, exposed, an unexposed portion is removed using an alkaline aqueous solution, and then exposed. A method for producing a color filter, comprising curing a portion by heating.