JPH08220751A - Photopolymerizable composition, color filter using same and production thereof - Google Patents

Abstract

PURPOSE: To provide a production method of a color filter by which a protective layer (OC layer) having enough performances such as flatness, hardness, chemical resistance, transparency, adhesion property with a substrate and forming property for a transparent conductive layer can be formed. CONSTITUTION: This photopolymerizable compsn. contains (1) a photopolymn. initiator or photopolymn. initiator system, (2) addition-polymerizable monomers having ethylene-type unsatd. double bonds, and (3) a resin obtd. by allowing primary amines expressed by formula III to react with a resin having 500-30000 number average mol.wt. and repeating units expressed by formulae I and II and then further allowing a compd. having isocyanate groups and ethylenic unsatd. double bonds in one molecule to react. A protective layer is formed by using the obtd. photopolymerizable compsn. to obtain a color filter. In formulae I, II, Ar<1> is a phenyl group, x, y are molar ratios of the repeating units in the resin satisfying x=0.85 to 0.50 and y=0.15 to 0.50. In formula III, R is an alkyl group of 1-12 carbon number, aralkyl group of 7-16 carbon number or aryl group of 6-18 carbon number.

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 developability when formed into a photosensitive coating film, surface tackiness, and resistance of the coating film or image after curing after development. It was insufficient in terms of alkalinity, 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 the transparent conductive layer is formed on the protective layer, it is resistant to the above-mentioned various chemicals (photoresist solvent, acidic etching solution, alkaline resist stripping solution, alignment film coating solution solvent, etc.). Even if it does, 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 No. 5-202272 and Japanese Patent Application Laid-Open No. 5-265208. However, even in these methods, a large amount of a photopolymerizable monomer component is required in order to secure the developability and the formability of the transparent conductive layer, so that there is a problem that the tack is slightly increased in some cases.

In order to reduce the amount of the photopolymerizable monomer component used, it is considered to introduce a polymerizable group into the polymer binder, for example. Such compounds are known per se, and examples of polymer compounds containing a carboxyl group and an ethylenically unsaturated double bond are described in, for example, Japanese Patent Publication No. 51-37316. Also, Japanese Patent Laid-Open No. 5-2570
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, since the carboxyl group remains in the resin after curing, there is a problem in alkali resistance after curing, particularly in chemical resistance when forming the transparent conductive layer.

[0011]

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. To provide a photopolymerizable composition which is excellent in alkali developability and has no tack so as to give a protective layer (OC layer) having each required performance in forming the layer, and particularly to a binder for constituting the same. is there. 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.

[0012]

The inventors of the present invention have made diligent efforts, and as a result, the object of the present invention was to (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 having at least repeating units represented by the following general formulas (I) and (II), and (3) represented by the following general formula (III): The primary amine is reacted at a ratio of 1.0 to 0.1 equivalent with respect to 1 equivalent of the anhydride group, and then a compound having an isocyanate group and an ethylenically unsaturated double bond in the same molecule is added. A photopolymerizable composition comprising a resin obtained by reacting the primary amine at a ratio of 0.9 to 0.01 equivalent to 1 equivalent of the primary amine,
The present invention has been accomplished by finding out that it is achieved by a color filter having a protective layer prepared by using the same.

[0013]

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, and a carbon number of 6).
To 10 aryl groups, C7 to C12 aralkyl groups or halogen atoms or a combination of two or more thereof) x, y: x is the mole fraction of the repeating unit in the resin, and x =
It represents 0.85 to 0.50 and y = 0.15 to 0.50. R—NH ₂ (III) [In the formula, R is an alkyl group having 1 to 12 carbon atoms, and 7 to 16 carbon atoms.
Represents an aralkyl group and an aryl group having 6 to 18 carbon atoms. (The alkyl group, aralkyl group and aryl group may each have a branch, and further, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 6 to 1 carbon atoms.
0 aryl group, an aralkyl group having 7 to 12 carbon atoms or a halogen atom or a combination of two or more thereof may be substituted). The present invention will be described in detail below.

The composition of the resin having at least the repeating units represented by the general formulas (I) and (II) used in the present invention has a composition ratio of repeating units of x = 0.85-.
0.50 and y = 0.15 to 0.50 are preferable, and x = 0.80 to 0.55 and y = 0.20 are particularly preferable.
It is 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 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,
When it exceeds 0, the alkali developability of the photosensitive layer is poor and the developing solution 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 having at least the repeating units represented by the general formulas (I) and (II) used in the present invention is, for example, maleic anhydride and one or more of the monomers of the following groups, which are suitable according to a conventional method. It can be obtained by copolymerizing in a different solvent in the presence of a polymerization initiator. Examples of monomers include styrene, methylstyrene, ethylstyrene, propylstyrene, isopropylstyrene, butylstyrene, sec-butylstyrene, tert-butylstyrene, dimethylstyrene, diethylstyrene, methoxystyrene, ethoxystyrene, propoxystyrene, Butoxystyrene, vinylbiphenyl, benzylstyrene,
Examples thereof include chlorostyrene, fluorostyrene, bromostyrene, chloro-methylstyrene and the like.

Further, the resin of the present invention may be further copolymerized with a monomer copolymerizable therewith so 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 alkylamines such as methylamine, ethylamine, propylamine, i-propylamine, butylamine and t-amine.
Butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, 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 as aralkylamines, benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6-phenyl-1-. Hexylamine, α-methylbenzylamine, o-methylbenzylamine, m-
Methylbenzylamine, p-methylbenzylamine, p
-T-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, 1-
Naphthylamine etc. can be mentioned. Among these, preferred examples of primary amines are 2-methoxyethylamine, 3-methoxypropylamine, cyclohexylamine and butylamine, more preferred are aralkylamines, and among them, benzylamine and phenethylamine are particularly preferred.

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. This equivalent amount of maleic anhydride groups is converted into maleic acid monoamide. If the amount is less than 0.1 equivalent, the developability of the photopolymerizable composition and the alkali developer resistance after exposure are poor. Further, the intended reaction can be efficiently progressed by making the charged amount of amine excess over the maleic anhydride equivalent, but in that case, excess amine is removed by a method such as reprecipitation of the copolymer, It is desirable to purify.

Specific examples of the compound having an isocyanate group and an ethylenically unsaturated double bond which can be used in the present invention include isocyanatoethyl (meth) acrylate, (meth) acryloyl isocyanate and 3 -Isopropenyl-α, α-dimethylbenzyl isocyanate, isocyanatomethylstyrene and the like can be mentioned. Further, a 1: 1 addition reaction product of a diisocyanate compound and a (meth) acrylate having a hydroxyl group can also be used. Examples of the diisocyanate compound include toluylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and isophorone diisocyanate. Examples of (meth) acrylates having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and hydroxystyrene. Among these, isocyanatoethyl (meth) is particularly preferable.
An acrylate is mentioned.

In the present invention, the reaction ratio of the compound having an isocyanate group and an ethylenically unsaturated double bond in the same molecule is 1 equivalent of the primary amine (that is, the reaction between maleic anhydride and the primary amine). It is preferably 0.9 to 0.01 equivalents, and particularly preferably 0.7 to 0.03 equivalents, relative to 1 equivalent of the carboxyl group generated in Step 1.). This equivalent amount of carboxyl groups is reduced, and instead the ethylenically unsaturated double bond is chemically bonded to the side chain of the polymer. Therefore, if this reaction ratio exceeds 0.9 equivalent, the alkali developing solution property of the photopolymerizable composition is poor, and if it is less than 0.01 equivalent, the formability of the transparent conductive layer is poor. At this time, the target reaction can be efficiently progressed by using the charged amount of the compound having an isocyanate group and an ethylenically unsaturated double bond in the same molecule in the above equivalent amount or more. In that case, an excess compound having an isocyanate group and an ethylenically unsaturated double bond in the same molecule may be left as it is as long as there is no problem in performance, but it is purified by a method such as reprecipitation. May be removed.

In the resin of the present invention, all or part of the unit (II) is maleated by reacting the resin having at least the repeating units represented by the following general formulas (I) and (II) with the primary amine. Maleic acid in the molecule obtained by converting into acid monoamide and further reacting a part of the carboxyl group of the maleic acid monoamide thus produced with a compound having an isocyanate group and an ethylenically unsaturated double bond in the same molecule. It is a resin having an acid monoamide and an ethylenically unsaturated double bond. A specific synthesizing method can be performed as follows, for example. A resin having at least the repeating units represented by the 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, but examples thereof include methyl ethyl ketone, propylene glycol monomethyl ether acetate and a mixture thereof, and the reaction temperature is preferably around room temperature. Then, a compound having an isocyanate 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 an appropriate catalyst. At this time, a suitable thermal polymerization inhibitor may be added. Examples of the catalyst include tertiary amines such as triethylamine and tin catalysts such as dibutyltin diacetate, and the reaction temperature is 50 ° C to 1 ° C.
00 ° C is preferred. These resins may be subjected to a purification treatment in each reaction step, if necessary.

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 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. Also 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 20% 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. Acridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethylketal, thioxanthone / amine, represented by the following general formula (V) described in Japanese Patent Application No. 6-212794. Bis (halogen-substituted methyl oxadiazole),

[0027]

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In the general formula (V), R¹Is -CO-R⁶CO
-, -C_nH_2n-Or-C_nH_2n-R⁷-C_nH_2n-Show
However, n represents the integer of 1-10. R²And R³Is that
Which may be the same or different, and each of which has a hydrogen atom or a carbon atom number of 1 to
10 alkyl groups, alkoxy having 1 to 10 carbon atoms
Group, acyloxy group having 2 to 10 carbon atoms or halogen
Atom, R^FourAnd R^FiveMay be the same or different
A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or carbon
Phenyl optionally substituted with 6 to 12 elementary atoms
Groups, X, Y, and Z may be the same or different.
Represents a hydrogen atom or a halogen atom. However, X, Y,
And Z do not represent a hydrogen atom at the same time. R⁶Is -C_mH_2m−
Or-OC_mH_2mRepresents O-, and m represents an integer of 2 to 20.
You R⁷Is -O-, -S-, -N (R⁸)-,-SO
₂-, -OCO-R⁹COO-, -SO₂-R⁹SO₂-,
-CO-R⁹CO- or -OR⁹Represents O-. R⁸Is charcoal
Alkyl group having 1 to 10 elementary atoms or 6 to 12 carbon atoms
Represents a phenyl group which may have a substituent. R⁹Is
-C_lH_2l-, -C_lH_2lOR^TenOC_lH_2l-, -NH
C_lH _2lNH-, -NHCH₂-C₆H_Four-CH₂NH-,
-OC_lH_2lO- or -C₆H_FourRepresents −, and 1 is 2 to 20
Represents the integer. R^TenIs -C₆H_Four-C_pH_2p-C₆H_Four-,
-C₆H_Four-SC₆H_Four-, -C₆H_Four-SO₂-C₆H
_Four-, -C₆H_Four-, -C₆H_Four-OC₆H_Four-, -C₆H_Four
-C (CF₃)₂-C₆H_Four-Or-C₆H_Four-C₆H_Four-Show
And p represents an integer of 2 to 10.

Trihalomethyl-s-triazine represented by the following general formula (VI) described in Japanese Patent Application No. 6-253756:

[0030]

[Chemical 4]

In the general formula (VI), X represents a chlorine atom or a bromine atom. Y is an alkyl group, CF ₃ group, CF ₂ Cl
Group, an alkyl group substituted by a halogen atom, Z-C
_{^{O-OR 3, C 6 F}} 5 group, or a group represented by C ₆ H ^₄ -R _4. However, R ³ represents a hydrogen atom or an alkyl group, Z is _{-C 2 H 4 -, - C} 3 H 6 -, - CH = CH-, o
-Represents a phenylene group. R ⁴ is a hydrogen atom, hydroxyl group, alkyl group, substituted alkyl group, aryl group, alkoxy group, substituted alkoxy group, halogen atom, alkoxycarbonyl group, cyano group, acyl group, nitro group, formyl group, mercapto group, alkylthio group. Represents a group or a dialkylamino group. R ¹ and R ² are each a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, a substituted alkoxy group, an acyloxy group, a halogen atom, an alkoxycarbonyl group, a cyano group, a nitro group, a carboxyl group or the general formula (VII) or It represents a group represented by the general formula (VIII). General formula (VII)

[0032]

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General formula (VIII)

[0034]

[Chemical 6]

In the general formula (VII), R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and in the general formula (VIII), R ⁷ and R ⁸ are each a hydrogen atom. Represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an acyl group. R ⁵ and R ⁶ , and R ⁷ and R ⁸ may combine with each other to form a ring.

Bis (trihalomethyl-s-triazine) represented by the following general formula (IX) described in Japanese Patent Application No. 6-268953,

[0037]

[Chemical 7]

In the general formula (IX), X is a chlorine atom or odor.
Represents an elementary atom. Y is an alkyl group, CF₃Group, CF₂Cl
Group, C₂F_FiveGroup, C₃F₇Substituted with groups other than halogen atoms
Alkyl group, Z-CO-OR², C₆F_FiveGroup or C₆
H_Four-R³Represents a group represented by. Where R²Is a hydrogen atom
Or an alkyl group, Z is -C₂H_Four-, -C₃H₆-,
-CH = CH- or represents an o-phenylene group. R³
Is a hydrogen atom, hydroxyl group, alkyl group, substituted alkyl group,
Reel group, alkoxy group, substituted alkoxy group, halogen
Atom, alkoxycarbonyl group, cyano group, acyl group,
Nitro group, formyl group, mercapto group, alkylthio group
Alternatively, it represents a dialkylamino group. L is -OR^Four−
O-, -O-CO-R^Four-CO-O-, -O-CO-N
HR ^Four-NH-CO-O-, -OC_nH_2n-R^Five-C_n
H_2n-O-, -O-CO-C_nH_2n-R^Five-C_nH_2n-C
OO-, -NH-R^Four-NH-, -NH-CO-R^Four−
CO-NH-, -NH-C_nH_2n-R^Five-C_nH_2n-NH
-, -CO-R^Four-CO-, -CO-OR^Four-O-CO
-, -CO-OC_nH_2n-R^Five-C_nH_2n-O-CO-
Or -CO-NH-R^FourRepresents -NH-CO-, n
Represents an integer of 1 to 10. R^FourIs -C_mH_2m-, -CH₂
-C₆H_Four-CH₂-, -C₆H_Four-, -C₆H_Four-C_lH_2l−
C₆H_Four-, -C₆H_Four-SC₆H_Four-, -C₆H_Four-SO₂
-C₆H_Four-, -C₆H_Four-OC₆H_Four-, -C₆H_Four-C
(CF₃)₂-C₆H_Four-Or-C₆H_Four-C₆H_Four-Show
, M represents an integer of 2 to 20, and l represents an integer of 2 to 10.
Represent R^FiveIs -O-, -S-, -OR⁶-O-, -O-
CO-R⁶-CO-O-, -CO-OR⁶-O-CO
-, -CO-NH-R⁶-NH-CO-, -NH-CO
-R⁶-CO-NH- or -O-CO-NH-R⁶−
Represents NH-CO-O-. R⁶Is -C_pH_2p-, -C₆H_Four
-, -CH₂-C₆H_Four-CH₂-, -C₆H_Four-C_lH_2l−
C₆H_Four-, -C₆H_Four-SC₆H_Four-, -C₆H_Four-SO₂
-C₆H_Four-, -C₆H_Four-OC₆H_Four-, -C₆H_Four-C
(CF₃)₂-C₆H_Four-, -C₆H_Four-C₆H_Four-Or-
C_qH_2q-OR⁷-OC_qH_2qRepresents −, and p is 2 to 2
0 represents an integer, and q represents an integer of 1 to 8. R⁷Is -C₆
H_Four-, -C₆H_Four-C_lH_2l-C₆H_Four-, -C ₆H_Four-S-
C₆H_Four-, -C₆H_Four-SO₂-C₆H_Four-, -C₆H_Four-O
-C₆H_Four-, -C₆H_Four-C (CF₃)₂-C₆H_Four−
Is -C₆H_Four-C₆H_FourRepresents-. R¹Is a hydrogen atom, Archi
Group, aryl group, alkoxy group, substituted alkoxy group,
Acyloxy group, halogen atom, alkoxycarbonyl
Group, cyano group, nitro group or carboxyl group
You

There are, for example, Particularly preferred is 2- (p-
Butoxystyryl) -5-trichloromethyl-1,3,3
4-Oxadiazole, a bishalogen-substituted compound as described above, or a trihalomethyl group-containing compound. The amount of the photopolymerization initiator added is 0.1 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 composition has a low photocuring efficiency, so that it takes a long time for exposure, and if it exceeds 20% by weight, the light transmittance in the ultraviolet region to the visible region is deteriorated. Would be unsuitable for.

Further, known additives such as plasticizers, fillers and stabilizers may be contained, and pigments, dyes and the like may 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. To provide a layer, for example, a method of applying the solution by a roll coater, a bar coater, etc., a method of applying the solution by a known means such as spraying and dipping the solution, or a photopolymerizable composition on a temporary support. There is a method of forming a physical layer and transferring this. The thickness of the protective layer is usually 0.1 μm to 50 μm, particularly preferably 0.5 μm to 5 μm.

As the support of 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 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) is also applicable. 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 preferably 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 same publication), a protective film for an electric element, an interlayer insulating film, an adhesive (disclosed above, for example, in JP-A-3-126950), a spacer material and the like. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, "part" means "part by weight" and "%".
Represents% by weight.

[0050]

【Example】

Synthesis Example 1 122.5 parts of a styrene / maleic anhydride = 68/32 molar ratio copolymer (number average molecular weight = 2800) was dissolved in 490.0 parts of methyl ethyl ketone. A solution of 42.9 parts of benzylamine (1.0 equivalent to the acid anhydride) dissolved in 171.6 parts of methyl ethyl ketone was added dropwise thereto at room temperature over about 1 hour, and the mixture was further stirred at room temperature for 6 hours.
Next, 31.0 parts of isocyanatoethyl methacrylate (0.5 equivalent to the amine), 1 part of methyl ethyl ketone
71.6 parts and 0.03 part of 2,5-di-t-hexylhydroquinone are added. Furthermore, dibutyltin diacetate 0.
After adding 02 parts, a modified product of styrene / maleic anhydride copolymer (a resin having a maleic acid monoamide and an ethylenically unsaturated double bond in the molecule) is obtained by reacting at 60 ° C. for 8 hours. It was

Example 1 (for forming liquid protective layer) <Preparation of coating liquid for forming protective layer> Mixing and dissolving 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% by weight solution of the resin produced in Synthesis Example 1 (solvent is methyl ethyl ketone) 68 parts Dipentaerythritol hexaacrylate 1.4 parts Tris (acryloyloxyethyl) isocyanurate 6.8 parts 2- (4-butoxy) Styryl) -5-trichloromethyl-1,3,4-oxadiazole 0.65 part Hydroquinone monomethyl ether 0.007 part Fluorine-based surfactant (Dainippon Ink and Chemicals F177P) 0.002 part

<Example of producing color filter layer> Thickness 10
A coating solution having the following formulation H1 was applied onto a 0 μm polyethylene terephthalate film temporary support and dried to form a thermoplastic resin layer having a dry film thickness of 20 μm.

Thermoplastic resin layer formulation H1: -Vinyl chloride / vinyl acetate copolymer (weight ratio: vinyl chloride / vinyl acetate = 75/25, degree of polymerization: about 400, MPR-TSL manufactured by Nissin Chemical Co., Ltd.) 290 0.0 g-Vinyl chloride-vinyl acetate-maleic acid copolymer (weight ratio: vinyl chloride / vinyl acetate / maleic acid = 86/13/1, degree of polymerization: about 400, MPR-TM 76. manufactured by Nissin Chemical Co., Ltd.) 0 g-Dibutyl phthalate 88.5 g-Fluorosurfactant (Dainippon Ink & Co., Inc. F-177P) 5.4 g-MEK 975.0 g

Then, the following formulation B1 was formed on the thermoplastic resin layer.
Applying a coating solution consisting of
An m-thick separation layer was provided. Separation layer formulation B1: ・ Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%) 173.2 g ・ Fluorine-based surfactant 8 g ・ Distilled water 2800 g

4 having the above-mentioned thermoplastic resin layer and separation layer
On each of the temporary supports, black (for Bl layer), red (for R layer), blue (for B layer), and green (G) having the formulations shown in Table 1 were prepared.
(For layers) were applied and dried to form a colored photosensitive resin layer having a dry film thickness of 2 μm.

Table 1: Composition of coating liquid for colored photosensitive layer Red Blue Green Black (g) (g) (g) (g) ────────────────────── ────────────── ・ Benzyl methacrylate / 60.0 60.0 60.0 60.0 Methacrylic acid copolymer (molar ratio = 73/27 viscosity = 0.12) ・ Pentaerythritol 43.2 43.2 43.2 43.2 Tetraacrylate ・ Michler's ketone 2.4 2.4 2.4 2.4 ・ 2- (o-chlorophenyl-4,5-2.5 2.5 2.5 2.5 diphenylimidazole dimer ・ Irgacin red BPT (red) 5.4 --- --- --- ・ Sudan blue (blue)- -5.2 --- --- ・ Copper phthalocyanine (green) --- --- 5.6 --- ・ Carbon black (black) --- --- --- 5.6 ・ Methyl cellosolve acetate 560 560 560 560 ・ Methyl ethyl ketone 280 280 280 280 ───────────────────────────────── ─

Further, a polypropylene (12 μm thick) covering sheet was pressure-bonded onto the photosensitive resin layer to prepare red, blue, green and black photosensitive transfer materials. Using this photosensitive transfer material, a color filter was prepared by the following method. The cover sheet of red photosensitive transfer material is peeled off, and the surface of the photosensitive resin layer is transparent glass substrate (thickness 1.1 m
m, size 350 mm × 400 mm) using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.) to apply pressure (0.8 kg / cm ² ) and heat (130 ° C.) to bond them together, and then to form a separation layer. The temporary support and the thermoplastic resin layer were simultaneously removed by peeling at the interface with the thermoplastic resin layer. Next, it is exposed through a predetermined photomask, immersed in a developer having the following formulation at 35 ° C. for 80 seconds to remove unnecessary portions, washed with water and dried to form a red pixel pattern on the glass substrate. did.

Formulation of developer-Sodium carbonate 15g-Butyl cellosolve 1g-Water 1kg

Then, on the glass substrate on which the red pixel pattern was formed, the green photosensitive transfer material was laminated in the same manner as above, peeled, exposed and developed to form a green pixel pattern. A similar process was repeated using blue and black photosensitive transfer materials to form a color filter on a transparent glass substrate.

<Preparation of protective layer> R (red), G above
The above-mentioned coating liquid for forming a protective layer was applied onto a color filter layer having (green) and B (blue) pixels by a spin coater and dried to form a photosensitive layer for forming a protective layer having a thickness of 3 μm. . Using an aligner of an ultra-high pressure mercury lamp light source, ultraviolet rays were irradiated at a light amount of 200 mj / cm ² through a protective layer baking mask. Then, a 1% aqueous sodium carbonate solution was sprayed onto the substrate for development, and the substrate was washed with water. Then, for heat treatment, it was left in a dryer at 200 ° C. for 20 minutes 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. Table 3 shows the evaluation results of other items.

Example 2 (Material for forming protective film 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. To form a photosensitive layer. 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, the cover sheet was removed from the film-shaped 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. Table 3 shows the evaluation results of other items.

Example 3 A 100 μm thick polyethylene terephthalate film temporary support was coated with a coating solution having the formulation H1 described in Example 1 and dried to form a thermoplastic resin layer having a dry film thickness of 20 μm. It was Next, a coating liquid having the formulation B1 described in Example 1 was applied onto the thermoplastic resin layer and dried to form a separation layer having a dry film thickness of 1.6 μm. The protective image-forming coating liquid of Example 1 was applied onto this separating layer, and a polypropylene cover film having a thickness of 15 μm was laminated thereon to obtain a film-like photosensitive transfer material. The film-like photosensitive transfer material was laminated on a glass substrate having a color filter layer in the same manner as in Example 2, the temporary support was peeled and removed, and then exposed and developed in the same manner as in Example 1 and subjected to heat treatment. As a result, a protective layer without defects such as bubbles and pinholes was obtained in the pixel portion of the color filter layer. The pencil hardness was 5H. An ITO electrode was formed on this protective layer in the same manner as in Example 1. As a result, an ITO electrode having no defects such as wrinkles and cracks and having good adhesion was obtained. Similarly, the protective layer did not swell and an alignment film could be formed. Table 3 shows the evaluation results of other items.

Synthesis Examples 2 to 10 Using the resins shown in Table 1, primary amines and compounds having an isocyanate group and an ethylenically unsaturated double bond in the same molecule, styrene / Modified maleic anhydride copolymer (resin having maleic acid monoamide and ethylenically unsaturated double bond in molecule) or amine modified styrene / maleic anhydride copolymer (molecule Resin having maleic acid monoamide therein) and the like were obtained.

Table 2: Resin Synthesis Examples ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ amine and isocyanate groups A compound having an amino group as the raw material resin number average Synthesis example Composition (molar ratio) Molecular weight Structure Anhydrous vs. Anhydrous No. St / MAH Equivalent Equivalent Equivalent ──────────────────────────────────── 1 68/32 2800 Bengalamine 1.0 Isocyanatoethyl methacrylate 0.5 2 68/32 2800 Benzylamin 1.0 1.0 Isocyanatoethyl methacrylate 0.3 3 68/32 2800 Benzyamine 1.0 Isocyanatoethyl methacrylate 0.7 4 68/32 2800 Benzyamine 0.8 Isocyanatoethyl methacrylate 0.5 5 68/32 4000 Benzylamin 1.0 Isocyanatoethyl methacrylate 0.5 6 68/32 11300 Benzyamine 1.0 Isocyanatoethyl methacrylate 0.5 7 68/32 2800 Phenethylamine 1.0 Isocyanatoethyl methacrylate 0.5 8 68/32 2800 Benzyamine 1.0 3-Isofluorophenyl-α, α 0.5-Dimethylbenzyl isocyanate 9 68/32 2800 Benzylamin 1.0--10 68/32 2800 Cyclohexylamine 0.7--11 90/10 2800 Benzyamine 1.0 Isocyanatoethylmethacrylate 0.5 ━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━ St: Styrene MAH: Maleic anhydride

Synthesis Example 12 122.5 parts of a 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 = 50/50 by weight mixed solvent. 490.0
Dissolved in part. To this, 46.4 parts of 2-hydroxyethyl acrylate (1.0 equivalent to the acid anhydride) and propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50/50 weight ratio mixed solvent 185.6.
Parts, 2.4 parts of 4-dimethylaminopyridine, 0.05 parts of 2,5-di-t-hexylhydroquinone were added, and the temperature was 60 ° C.
A modified styrene / maleic anhydride copolymer (a resin having a carboxyl group and an ethylenically unsaturated double bond in the molecule) was obtained by reacting for 12 hours.

Synthesis Example 13 Addition reaction product of methyl methacrylate / styrene / maleic acid and glycidyl methacrylate of Example 3 described in JP-A-5-257090 (carboxyl group and ethylenically unsaturated double bond in molecule) Resin having a).

Synthesis Example 14 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%, propyl Amine 1.1 eq).

Examples 4 to 10 and Comparative Examples 1 to 6 Synthetic Examples 2 to 8 (Examples) and 9 to 9 in the same manner as Example 3.
A coating liquid for forming a protective layer was prepared using the resin of 14 (Comparative Example) and evaluated in the same manner. The evaluation results are shown in Table 3.

Comparative Example 7 A coating solution for forming a protective layer was prepared by using the resin of Synthesis Example 9 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. Was prepared and evaluated in the same manner. The evaluation results are shown in Table 3. 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 film thickness of 3 μm on a glass substrate was passed through a mask capable of obtaining a rectangular image of 80 μm × 300 μm to 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
m), a photosensitive layer is formed to have a thickness of 3 μm, exposure (200 mj / cm ² ), development, and post-heating (20
The unevenness of the surface of the protective layer obtained at 0 ° C. for 60 minutes) was measured and evaluated using a film thickness meter.

4. Hardness A 3 μm thick photosensitive layer is formed on a glass substrate and exposed (2
00 mj / cm ² ), 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 / cm ² ), 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), a clear surface The sample was judged to have good transparency, and the sample with cloudiness was judged to have poor transparency.

7. Adhesion to substrate Cross-cut after forming a 3 μm thick photosensitive layer for forming a protective layer on a glass substrate, exposing the entire surface (200 mj / cm ² ), developing and post-heating (200 ° C., 60 minutes) 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.

9. It was coated on a tack glass substrate with a spin coater so as to have a film thickness of 3 μm, and dried at 80 ° C. for 2 minutes to obtain a protective layer-forming photosensitive layer. Evaluate the adhesiveness of the surface by finger touch test,
The adhesiveness of the surface of the coating film of Color Mosaic K (manufactured by Fuji Hunt Electronics Technology) obtained in the same manner was compared with that of the coating film of Color Mosaic K to be equal to or higher than that of the coating film. Table 3 shows the evaluation results of the above items.

[0080]

[Table 1]

From these results, it can be seen that the photopolymerizable composition of the present invention exhibits excellent performances in all the evaluated items.

[0082]

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, It has a transparent conductive layer forming property and low tack. 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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takayanagi Oka No. 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film Co., Ltd.

Claims (6)

[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 a number average molecular weight of 500 to 30,000 and the following general formula (I
After reacting the primary amine represented by II) in a ratio of 1.0 to 0.1 equivalent to 1 equivalent of the anhydride group, an isocyanate group and an ethylenically unsaturated double bond are further added in the same molecule. A photopolymerizable composition comprising a resin obtained by reacting a compound having the above with a ratio of 0.9 to 0.01 equivalent to 1 equivalent of the primary amine. 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, and 6 carbon atoms).
To 10 aryl groups, C7 to C12 aralkyl groups or halogen atoms or a combination of two or more thereof) x, y: x is the mole fraction of the repeating unit in the resin, and x =
It represents 0.85 to 0.50 and y = 0.15 to 0.50. R—NH ₂ (III) [In the formula, R is an alkyl group having 1 to 12 carbon atoms, and 7 to 16 carbon atoms.
Represents an aralkyl group and an aryl group having 6 to 18 carbon atoms. (The alkyl group, aralkyl group and aryl group may each have a branch, and further, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number of 6 to 1
0 aryl group, an aralkyl group having 7 to 12 carbon atoms or a halogen atom or a combination of two or more thereof may be substituted). ] 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 which may have a branch and has 1 to 6 carbon atoms, Ar ² : an aryl group (wherein the aryl group is an alkyl group having 1 to 4 carbon atoms). Group, alkoxy group having 1 to 6 carbon atoms, 6 carbon atoms
To 10 aryl groups, aralkyl groups having 7 to 12 carbon atoms, halogen atoms, or a combination of two or more thereof. ] 3. The photopolymerizable compound according to claim 1 or 2, wherein the compound having an isocyanate group and an ethylenically unsaturated double bond in the same molecule is isocyanatoethyl (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 having a protective layer formed of the cured product of. 5. 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. Is formed, exposed, the unexposed area is removed using an alkaline aqueous solution, and the exposed area is then cured by heating. 6. The method according to claim 1, 2 or 3 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. A photosensitive 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, and the unexposed portion is removed using an alkaline aqueous solution, and then exposed. A method for producing a color filter, wherein the part is cured by heating.