JP2000298339A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To control the content of a radical polymerizable group such as an alkali-soluble group or a (meth) acryloyloxy group, and to provide excellent curability and coating properties. Another object of the present invention is to provide a photosensitive resin composition having improved sensitivity. SOLUTION: The photosensitive resin composition of the present invention has a constitutional unit represented by the following general formulas (1) and (2), each of which has a carboxyl group or a hydroxyl group and a (meth) acryloyloxyalkyl isocyanate compound. A specific copolymer resin having a product of which part has reacted as a constitutional unit, a bifunctional or higher polyfunctional photopolymerizable acrylate monomer, at least one resin selected from an epoxy resin and an amino resin, and a radical polymerization initiator. An initiator comprising a photoacid generator, which is useful for forming a protective film,
Further, by further containing a pigment and a dispersant,
It can be useful for forming a colored layer. (Wherein, R is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ₁ represents an alkylene group having 2 to 4 carbon atoms. a and b represent an integer corresponding to each mol%. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the formation of thin film patterns in the field of semiconductors, color liquid crystal displays,
Regarding a photosensitive resin composition used for forming a color filter used for a CD image sensor and the like,
U in color filters for color liquid crystal displays
The present invention relates to a V-curable transparent protective film and a negative resist suitable for forming a color matrix.

[0002]

2. Description of the Related Art In a display driven by a liquid crystal, a color filter in a liquid crystal cell occupies a particularly important position for displaying a color. Although the configuration is slightly different depending on each type such as a so-called TFT type, STN type, and TN type, usually, 1) a black portion for light shielding, 2) a red, green, Blue color matrix,
It has four member layers: 3) a transparent film (protective film) for protecting and flattening the color matrix, and 4) a transparent electrode film for driving the liquid crystal.

[0003] Various production methods have heretofore been proposed for forming these layers. Regarding the color matrix, at present, there are four forming methods: a dyeing method, a pigment dispersion method, a printing method, and an electrodeposition method. The method has been put to practical use. The protective film is mainly classified into two types, a thermosetting type and a UV curing type. Further, technologies specific to quality performance and cost reduction in each system are continuously studied.

[0004] As a method of producing a color matrix classified as a pigment dispersion method, a color filter paint prepared by dispersing a pigment in an acrylic resin with a dispersant or the like is applied, dried, and then coated on the paint film. After applying and drying a photosensitive resist material and exposing using a mask,
Develop to form a resist pattern. Thereafter, the portion of the color filter coating film having no resist pattern was removed by etching to obtain a colored pattern. There has also been proposed a method in which a photopolymerization initiator and a photopolymerizable monomer or a photosensitizer are added to a coloring composition for photosensitization, and a coating, drying, exposure, and development are performed on a substrate to obtain a coloring pattern. Photosensitizers used in this method include bisazide compounds, diazo compounds, and the like.
As the photopolymerization initiator, acetophenone, benzyldimethyl ketal, or the like is used, and the sensitivity is improved by the type and combination of the initiator.

When the color filter is made of a colored layer, the protective film plays a role of protecting the color filter and flattening the color filter. Generally, in a color liquid crystal display device, gap unevenness due to undulation of a transparent substrate surface of a color filter, gap unevenness between R, G, and B pixels, or gap unevenness within each of R, G, and B pixels exists. And the flatness of the transparent electrode is impaired.
Color unevenness and contrast unevenness occur, resulting in lower image quality. In particular, in the color liquid crystal display device of the STN mode, since the flatness has a great influence on the image quality, the function of flattening the protective film is extremely demanded.

The protective film is important for the adhesion between the color filter and the counter electrode substrate. However, when the display quality test is performed after the color filter and the counter electrode substrate are bonded, it is determined that the color filter is defective. Considering the suitability for re-use, it is preferable to form it only in a specific region covering the colored layer on the transparent substrate. For this reason, the formation of the protective film is performed using a photocurable resin in which a portion to be cured is easily limited by a mask.

However, conventional resin compositions for forming a colored layer and for forming a protective film use an organic solvent in development after exposure, and are complicated in handling and waste liquid treatment. Therefore, a photocurable resin has been developed which introduces an acidic group into the photocurable resin and enables development after exposure to be alkali development.

As such an alkali-soluble photocurable resin, for example, o-cresol novolak epoxy acrylate having a weight average molecular weight of about 2,000 is known.
Since the resin has an acryloyloxy group that defines curability as a monomer unit, the ratio of the carboxylic acid group and the acryloyloxy group in the resin is constant.

Therefore, in order to improve the density of radical polymerizable groups in the photosensitive resin composition, an acryloyloxy-modified substance of a low molecular weight polyfunctional alcohol, for example, dipentaerythritol hexaacrylate (DP) which is a hexafunctional alcohol
Although it is conceivable to introduce a large number of HA) and the like, there is a problem that the viscosity is too low and the coating suitability is impaired. Also, when a color filter is used, cracks occur in the coating film due to remarkable curing shrinkage. However, there is a problem that poor adhesion is caused.

In general, as a method for introducing a radical reactive group such as a (meth) acryloyloxy group, for example, as a method for preparing urethane acrylate, a diol is reacted with diisocyanate to make the diisocyanate group excessive. A method is known in which an isocyanate group is left at the terminal of a reaction product, and the isocyanate group is reacted with 2-hydroxyethyl methacrylate to introduce a radical polymerizable group such as a methacryloyloxy group at the terminal. An oxy group is in principle only introduced at both ends. Furthermore, a method of partially polymerizing a compound having two or more (meth) acryloyloxy groups for radical polymerization is also conceivable, but the content of the radical-reactive group cannot be controlled, and gelation or the like is not possible. There are also problems.

As described above, it is difficult to control an alkali-soluble group such as a carboxyl group and a radical polymerizable group such as a (meth) acryloyloxy group in a photocurable resin in consideration of the curability, alkali solubility and the like. In addition, no photosensitive resin composition having excellent curability and alkali solubility and excellent coating properties has not been obtained.

[0012]

DISCLOSURE OF THE INVENTION The present invention can control the content of a radical polymerizable group such as an alkali-soluble group or a (meth) acryloyloxy group, and has excellent curability and coating properties.
Another object of the present invention is to provide a photosensitive resin composition having improved sensitivity.

[0013]

In the photosensitive resin composition of the present invention, the structural units represented by the following general formulas (1) and (2) are prepared by converting (meth)
A product obtained by partially reacting with the acryloyloxyalkyl isocyanate compound is used as a constituent unit, and a constituent unit derived from the following general formula (1) is 5 mol% to 55 mol%,
5 mol% to 95 of the structural unit derived from the following general formula (2)
Mol%, containing 5 mol% to 95 mol% of the (meth) acryloyl group-introduced structural unit, and having an acid value of 5 mgKOH / g or less.
A copolymer resin having a weight average molecular weight in terms of polystyrene of 400 mgKOH / g and a polystyrene equivalent of 10,000 to 1,000,000, a bifunctional or higher polyfunctional photopolymerizable acrylate monomer, an epoxy resin and an amino resin. It is characterized by comprising at least one kind of resin, a radical polymerization initiator and an initiator comprising a photoacid generator.

[0014]

Embedded image (Wherein, R is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ₁ represents an alkylene group having 2 to 4 carbon atoms. a and b represent an integer corresponding to each mol%. In addition, in the photosensitive resin composition of the present invention, the structural units represented by the general formulas (1) and (2) each partially form a (meth) acryloyloxyalkyl isocyanate compound via a carboxyl group or a hydroxyl group. Is a structural unit, containing 5 mol% to 55 mol% of the structural unit derived from the general formula (1) and 5 mol% to 95 mol% of the structural unit derived from the general formula (2). Containing 5 to 95 mol% of a (meth) acryloyl group-introduced structural unit and having an acid value of 5 mgKOH / g to 400 mgKOH /
g and a polystyrene equivalent weight average molecular weight of 1
A copolymer resin having a molecular weight of 0.001 to 1,000,000,
A bifunctional or higher polyfunctional photopolymerizable acrylate monomer,
It is characterized by comprising at least one resin selected from an epoxy resin and an amino resin, an initiator comprising a radical polymerization initiator and a photoacid generator, a pigment, and a dispersant.

Further, the copolymer resin in the above-mentioned photosensitive resin composition may further comprise, as a copolymer component, 0 mol% to 75 mol% of a structural unit represented by the following general formula (3); ) Is contained in an amount of 0 mol% to 75 mol%.

[0016]

Embedded image(Wherein, R is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R_TwoIs an aromatic carbocycle, R _ThreeIs an alkyl group or aral
Represents a kill group. c and d correspond to the respective mol%
Represents an integer. )

[0017]

DETAILED DESCRIPTION OF THE INVENTION The photosensitive resin composition of the present invention comprises a specific copolymer resin, a difunctional or higher polyfunctional photopolymerizable acrylate monomer, and at least one resin selected from an epoxy resin and an amino resin. Initiator consisting of a radical polymerization initiator and a photoacid generator, and in forming a colored layer,
Further, it contains a pigment and a dispersant.

The specific copolymer resin basically has a structural unit in which a (meth) acryloyloxy group is introduced into the above-mentioned general formulas (1) and (2), as described later. Accordingly, general formulas (3) and (4) are used as copolymer components. Hereinafter, in the present invention, the (meth) acryloyloxy group means a methacryloyloxy group or an acryloyloxy group, and the (meth) acrylic acid means methacrylic acid or acrylic acid.

In the copolymerization components represented by the general formulas (1) to (4), R is hydrogen or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, and an n group.
-Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-
Examples include a pentyl group.

The copolymer component represented by the general formula (1) is a component that contributes to alkali developability, and the monomers used to introduce this structural unit include acrylic acid,
Examples include methacrylic acid, 2-carboxy-1-butene, 2-carboxy-1-pentene, 2-carboxy-1-hexene, 2-carboxy-1-heptene, and the like. The copolymer component represented by the general formula (1) is a copolymer component contained for the purpose of alkali solubility, and its content is adjusted according to the degree of alkali solubility required for the copolymer resin. The content of the copolymer component represented by the general formula (1) is 5 mol% to 55 mol%, preferably 10 mol%.
Mol% to 25 mol%.

The copolymer component represented by the general formula (2) is basically a component into which a (meth) acryloyl group is introduced, and R ₁ is an ethylene group, a propylene group, a butylene group or the like. . Specific examples of the monomer used to introduce this structural unit include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl. Acrylate, 4-hydroxybutyl methacrylate and the like are exemplified. The copolymer component represented by the general formula (2) is a copolymer component which reacts with a (meth) acryloylalkyl isocyanate compound through its hydroxyl group to introduce a (meth) acryloyl group, and the content thereof is It is adjusted according to the degree of photopolymerizability required for the polymer resin. And the content of the copolymer component represented by the general formula (2) is 5
The mole ratio is from 95% to 95%, preferably from 10% to 50%.

The copolymer resin is characterized by containing the copolymer component represented by the general formula (1) and the copolymer component represented by the general formula (2). Is a copolymer component represented by the general formulas (3) and (4).

The copolymer component represented by the general formula (3) imparts a coating property to the copolymer resin when the copolymer resin of the present invention is used for forming a coating film such as a color filter protective film or a colored layer. R ₂ is exemplified by an aromatic ring such as a phenyl group and a naphthyl group. Examples of the monomer used to introduce this structural unit include styrene and α-
The aromatic ring is a halogen atom such as chlorine and bromine, an alkyl group such as a methyl group and an ethyl group, an amino group such as an amino group and a dialkylamino group, a cyano group, a carboxyl group, and a sulfonic acid group. , A phosphoric acid group or the like. And, the content of the copolymer component represented by the general formula (3) is 0 mol% to 75 mol%, preferably 5 mol% to 50 mol%.

Further, the copolymer component represented by the general formula (4) is a component which suppresses alkali developability when the copolymer resin is used for forming an alkali-developable protective film or a colored layer.
Examples of R ₃ include an aralkyl group such as an alkyl group having 1 to 12 carbon atoms, a benzyl group, and a phenylethyl group.
Examples of the monomer used to introduce this structural unit include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Phenyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth)
Esters of (meth) acrylic acid such as dicyclopentanyl acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobonyl (meth) acrylate, benzyl (meth) acrylate, and phenylethyl (meth) acrylate Is exemplified. The content of the copolymer component represented by the general formula (4) is 0 mol% to 75 mol%, preferably 5 mol% to 50 mol%.

As the monomers used for introducing the structural units of the general formulas (1) to (4), those exemplified above may be used alone or as a mixture.

As a polymerization solvent used for producing a specific polymer having the structural units of the general formulas (1) to (4), a solvent having no active hydrogen such as a hydroxyl group or an amino group is preferable. Ethers such as, for example, tetrahydrofuran; glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether;
Examples include cellosolve esters such as methyl cellosolve acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate. Aromatic hydrocarbons, ketones, esters, and the like can also be used.

As the polymerization initiator, those generally known as radical polymerization initiators can be used, and specific examples thereof are 2,2'-azobisisobutyronitrile and 2,2 ' Azo compounds such as -azobis- (2,4-dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile);
Benzoyl peroxide, lauroyl peroxide, t
organic peroxides such as tert-butylperoxypivalate, 1,1′-bis- (tert-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used in combination with a reducing agent as a redox polymerization initiator.

In the production of a specific polymer having the structural units of the general formulas (1) to (4), a molecular weight modifier can be used to adjust the weight average molecular weight. , Halogenated hydrocarbons such as carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-
Mercaptans such as dodecyl mercaptan and thioglycolic acid; xanthogens such as dimethyl xanthogen disulfide and diisopropyl xanthogen disulfide;
Terpinolene, α-methylstyrene dimer and the like.

The specific polymer having the structural units of the general formulas (1) to (4) is a random copolymer or a block copolymer of the monomers of the general formulas (1) to (4). May be any of

In the case of a random copolymer, each monomer,
A blended composition comprising a catalyst is placed in a polymerization vessel containing a solvent.
Polymerization can be carried out by dropping the mixture at a temperature of 0 to 110 ° C over 2 to 5 hours and aging.

The specific polymer having the structural units of the general formulas (1) to (4) has a weight average molecular weight in terms of polystyrene (hereinafter, simply referred to as “weight average molecular weight” or “Mw”) of 10,000 to 1,000,000 and an acid value of 5 mgKOH / g to 400 mgKOH.
/ G, hydroxyl value is 5 mgKOH / g to 400 mgKOH
/ G.

The copolymer resin of the present invention is obtained by reacting a (meth) acryloyloxyalkyl isocyanate compound with a specific polymer having the structural units of the above general formulas (1) to (4).

The (meth) acryloyloxyalkyl isocyanate compound is a compound in which a (meth) acryloyloxy group is bonded to an isocyanate group (—NCO) via an alkylene group having 2 to 6 carbon atoms.
Acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate and the like are exemplified.
2-Methacryloyloxyethyl isocyanate is commercially available under the trade name of "Karenz MOI" manufactured by Showa Denko KK.

The reaction between the copolymer having the structural units represented by the general formulas (1) to (4) and the (meth) acryloyloxyalkyl isocyanate compound is carried out in the presence of a small amount of a catalyst. It is performed by dropping into the coalescing solution. Examples of the catalyst include dibutyltin laurate and the like, and a polymerization inhibitor such as p-methoxyphenol, hydroquinone, naphthylamine, tert-butylcatechol, and 2,3-di-tert-butylp-cresol may be used if necessary. used.

The (meth) acryloyloxyalkyl isocyanate compound is added to the structural unit of the general formula (2) in the specific polymer having the structural units of the general formulas (1) to (4) by adding a urethane bond. Combine and
A part of the structural unit of the general formula (1) releases carbon dioxide gas and is bonded by an amide bond.

That is, a reaction product of a copolymer having the structural units represented by the general formulas (1) and (2) and a (meth) acryloyloxyalkyl isocyanate compound is represented by the following general formula (5). It is. ◎

Embedded image .

(Wherein R and R ₁ represent the general formulas (1) to (4)
R ′ is an alkylene group having 2 to 6 carbon atoms, a
₁ + a ₂ is the sum of a in general formula (1) and b ₁ + b
₂ has the same meaning as b in the general formula (2). The (meth) acryloyloxyalkyl isocyanate compound has a reaction rate of about 20 times that of the reaction with the hydroxyl group in the structural unit of the general formula (2) as compared with the reaction with the carboxyl group in the structural unit of the general formula (1). Have. Therefore, the (meth) acryloyloxy group is mainly introduced into the structural unit of the general formula (2), and a (meth) acryloyloxy group is partially introduced into the carboxyl group in the structural unit of the general formula (1). In this case, most of the carboxyl groups remain.

The structural unit derived from the general formula (2)
Of 5 mol% to 95 mol% of ₁Is 0 mol% to 10
Mol%, b_TwoCan be from 5 mol% to 95 mol%.
5 mol% to 55 mol% of the structural unit derived from the general formula (1)
Of which a₁Is 5 mol% to 55 mol%, a_TwoIs 0 mol%
-10 mol%.

Suitable for forming a protective film or a colored layer of a color filter, and from the viewpoint of alkali solubility and photocurability,
In the copolymer resin of the present invention, the weight average molecular weight is 1
0.00-1,000,000, preferably 20,000
It is preferably in the range of 00 to 100,000. If the weight average molecular weight is less than 10,000, the developability is too good to control the pattern shape at the time of pattern exposure, and when a pattern can be produced, the final film thickness is reduced (film reduction). Yes, and 1,000,000
If it is larger than 00, the viscosity at the time of forming the resist becomes too high, and the coating aptitude deteriorates. In addition, the developability deteriorates and the pattern hardly comes off.

The content of the (meth) acryloyloxy group-introduced constitutional unit is preferably from 5 mol% to 95 mol%, and more preferably from 5 mol% to 50 mol%. And the effect of improving coating film adhesion and resist characteristics is small.

The acid value of the copolymer resin is 5 mg KOH /
g to 400 mg KOH / g, preferably 10 mg KO
H / g to 200 mgKOH / g is preferable. The acid value is related to the alkali developability. If the acid value is too low, there are problems such as poor developability and poor adhesion to the substrate and the color filter resin. Further, if the acid value is too high, there is a problem that the developability is too good to control the pattern shape at the time of pattern exposure. In the copolymer resin, the hydroxyl group in the general formula (2) does not necessarily need to be left, and the hydroxyl value is 0 mgKOH / g to 200 mgKOH / g.
However, if it is left, it is effective for adjusting the solubility in a solvent.

The amount of the methacryloyloxy group-introducing structural unit in the copolymer resin of the present invention can be controlled by changing the reaction amount of 2-hydroxyethyl methacrylate or (meth) acryloyloxyalkyl isocyanate compound or the degree of polymerization. Although it is possible, in the polymer solution obtained by the method for preparing a copolymer resin, the (meth) acryloyloxyalkyl isocyanate compound is dimerized by water in the reaction system to produce a urea-type dimer as a by-product. Was found by ¹ H-NMR analysis of the reaction product. This dimer also has a (meth) acryloyl group.

Further, the lower the molecular weight component in the copolymer resin, the more easily the (meth) acryloyloxy group is introduced, and conversely, the higher the molecular weight component, the lower the introduction ratio. Therefore, a copolymer resin having a desired methacryloyloisyl group-introduced structural unit amount can be obtained by reacting in consideration of the above-mentioned factors affecting the amount of introduction.

In the photosensitive resin composition of the present invention, the copolymer resin is contained in a solid content ratio of 5% by weight to 80% by weight, preferably 10% by weight to 50% by weight. If the amount is more than 80% by weight, the viscosity becomes too high, resulting in a decrease in fluidity and a problem in coating properties. There is a problem that the suitability for exposure and development is impaired.

Next, in the photosensitive resin composition of the present invention,
It contains a polyfunctional acrylate monomer as a photopolymerizable monomer. Multifunctional acrylate monomers are
One of the main components of the photosensitive resin composition of the present invention, for example, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hexane di (meth)
Acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycerin tetra (meth) acrylate, tetratrimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate And the like. These components are used alone or as a mixture.

These polyfunctional acrylate monomers preferably contain at least one kind of trifunctional or higher-functional monomer, and the content thereof preferably accounts for about 30 to 95% by weight of the polyfunctional acrylate monomer.
In addition, these polyfunctional acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and ethylhexyl (meth) as reaction diluents. Monofunctional monomers such as acrylates, styrene, methylstyrene, N-vinylpyrrolidone can be added.

The content of the polyfunctional acrylate monomer as a photopolymerizable monomer is from 3% by weight to 50% by weight, preferably from 5% by weight to 4% by weight in the photosensitive resin composition.
0% by weight is contained. When the amount is less than 3% by weight, there is a disadvantage that various physical strengths such as the adhesive strength and heat resistance of the formed film become insufficient, and when the value exceeds 50% by weight, the amount of the photosensitive resin composition decreases. There is a disadvantage that the stability is reduced and the flexibility of the formed film is insufficient. This ratio is necessary to further improve the dissolution characteristics in the developing solution.If the ratio is out of the optimized amount range, the pattern is resolved but the monomer curing speed is increased, and scum and whiskers are generated around the pattern. Occurs. Further, outside the above range, in severe cases, re-adhesion of the resist due to partial swelling and peeling may occur, which may hinder accurate pattern formation.

Examples of the initiator include a radical polymerization initiator and a photoacid generator which generates an acid upon irradiation with light (especially at a wavelength of 190 to 410 nm).

The radical polymerization initiator is, for example, a compound that generates a free radical by the energy of ultraviolet rays, such as a benzophenone derivative such as benzoin or benzophenone, or a derivative such as an ester thereof.
Redox of xanthone and thioxanthone derivatives, chlorosulfonyl and chloromethyl polynuclear aromatic compounds as halogen-containing compounds, chloromethyl heterocyclic compounds, chloromethylbenzophenones, triazines, fluorenones, haloalkanes, photoreducing dyes and reducing agents There are couples, organic sulfur compounds, peroxides and the like, and these can be used alone or in combination of two or more. When used together, it is preferable not to impair the absorption spectral characteristics.

The amount of the radical polymerization initiator to be added is 0.1 to 20% by weight, preferably 5 to 15% by weight in the photosensitive resin composition. When the content is less than 0.1% by weight, the photocuring reaction does not proceed, and the residual film rate, heat resistance, chemical resistance, and the like tend to decrease. On the other hand, if this value exceeds 20% by weight, the solubility in the base resin reaches saturation, and initiator crystals precipitate during spin coating or leveling of the coating film, making it impossible to maintain uniformity of the film surface. Inconvenience occurs.

Next, the photoacid generator used in combination with the radical generator will be described. Examples of the photoacid generator include trichloromethyl-s-triazines, diaryliodonium salts, and triarylsulfonium salts.

The trichloromethyl-s-triazines include, for example, tris (2,4,6-trichloromethyl)
-S-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl ) -Bis (4,6
-Trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl)-
s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio Phenyl) -bis (4,6
-Trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methoxynaphthyl) -bis (4,6-
Trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl)-
s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methoxy-β-styryl) -bis (4,6-trichloromethyl)
-S-triazine, 2- (2-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4,6-trichloro Methyl) -s-triazine, 2-
(3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine and the like Is mentioned.

In particular, those represented by the following general formula (1) are preferred.

[0054]

Embedded image .

The diaryliodonium salts include diphenyliodonium tetrafluoroborate,
Diphenyliodonium hexafluorophosphonate,
Diphenyliodonium hexafluoroarsenate,
Diphenyliodonium hexafluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexa Fluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate , Bis (4-tert-
Butylphenyl) iodonium hexafluorophosphonate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert
-Butylphenyl) iodonium hexafluoromethanesulfonate, bis (4-tert-butylphenyl)
Iodonium trifluoroacetate, bis (4-te
rt-butylphenyl) iodonium-p-toluenesulfonate.

In particular, diphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluorophosphonate, 4-methoxyphenylphenyliodonium trifluoroacetate and the like are preferable.

Further, triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoromethanesulfonate, triphenylsulfonium Trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxydiphenylsulfonium tetrafluoroborate, 4-methoxydiphenylsulfonium hexafluorophosphonate, 4-methoxydiphenylsulfonium hexafluoroarsenate,
4-methoxydiphenylsulfonium hexafluoromethanesulfonate, 4-methoxydiphenylsulfonium trifluoroacetate, 4-methoxydiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-
Phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenylhexafluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate,
And phenylthiophenyldiphenyl-p-trienesulfonate.

In particular, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxydiphenylsulfonium tetrafluoromethanesulfonate, 4-methoxydiphenylsulfonium tetrafluoroacetate, 4-phenylthiophenyldiphenyl Sulfonium trifluoroacetate and the like are preferred.

The amount of the photoacid generator added is 100
The amount is 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight with respect to parts by weight. This addition amount is 0.001
When the amount is less than parts by weight, the photocuring reaction or crosslinking does not proceed because the amount of acid generated by irradiation with the photoacid generator is small, the remaining film ratio,
Heat resistance and chemical resistance tend to decrease. On the other hand, if the amount exceeds 30 parts by weight, the solubility (including the solvent) in the composition becomes saturated, and the sensitivity due to the recrystallization precipitation on the film and the decrease in light absorption efficiency due to the dimerization or trimerization of the photoacid generator. May be reduced. Two or more photoacid generators may be used as a mixture.

Commercially available photoacid generators include, for example, TAZ-100, TAZ-101, TAZ-102 and TAZ-1 as triazines manufactured by Midori Kagaku Co., Ltd.
04, TAZ-106, TAZ-107, TAZ-10
8, TAZ-110, TAZ-111, TAZ-11
3, TAZ-114, TAZ-118, TAZ-11
9, TAZ-120, TAZ-121, TAZ-122
And the like; triphenylsulfonium salts such as TPS-102, TPS-103 and TPS-10 as onium salts
5, MDS-103, MDS-105, MDS-30
5, BDS-105, DTS-102, DTS-10
3, MAT-103, MAT-105, NDS-10
3, NDS-105 and the like.

In preparing the photosensitive resin composition, the polymerization initiator system may be added to the resin composition comprising the polyfunctional acrylate-based monomer and the copolymer resin from the beginning, but a relatively long polymerization initiator system may be used. When stored for a period, it is preferable to disperse or dissolve in the resin composition immediately before use.

Further, the photosensitive resin composition of the present invention contains heat resistance, adhesion, and chemical resistance (particularly, alkali resistance).
At least one of an amino resin and an epoxy resin is contained for the purpose of improving the resin. The amino resin has a molecular weight of 100 to 10,000, preferably 300 to 1.0.
And melamine derivatives such as hexamethoxymethylolmelamine, monomethylenebismelamine, trimethylolmelamine, and 2-methylene-3-melamine, and derivatives of acetoguanamine and benzoguanamine. When the molecular weight exceeds 10,000, the compatibility with the copolymerizable resin is deteriorated and phase separation occurs, which causes problems such as a decrease in reactivity and a decrease in coating film strength.

Such an amino resin is contained in the photosensitive resin composition at a solid content ratio of 1% by weight to 20% by weight, preferably 5% by weight to 15% by weight. When the content of the amino resin exceeds 20% by weight, the reaction at the time of exposure becomes insufficient, the curing shrinkage at the time of post-baking increases, and the flatness deteriorates, which is not preferable.

In forming the protective film and the colored layer, by using an amino resin, the acid generated by the photoacid generator is used as a catalyst, and the hydroxyl group remaining in the amino resin and the copolymer resin simultaneously with the curing by light irradiation. Since the reaction with carboxylic acid or a carboxyl group is promoted, the sensitivity is improved, and the reaction further proceeds by post-baking, resulting in excellent stability such as alkali resistance. Further, as compared with the epoxy resin, the resin has a low molecular weight and is polyfunctional, and has excellent compatibility with the copolymerizable resin.

As the epoxy resin, a compound having two or more epoxy groups in a molecule, for example, a bisphenol type epoxy resin such as Epicoat 1001, 100
2, 1003, 1004, 1007, 1009, 101
0 (manufactured by Yuka Shell), such as Epicoat 807 (manufactured by Yuka Shell) as a bisphenol F type epoxy resin, and EPPN20 as a phenol novolak type epoxy resin.
1, 202 (manufactured by Nippon Kayaku), Epicoat 154 (manufactured by Yuka Shell), etc. as cresol novolac type epoxy resins such as EOCN102, 103S, 104S, 1020,
1025, 1027 (Nippon Kayaku), Epicoat 180
S (manufactured by Yuka Shell) and the like.

Further, there may be mentioned cycloaliphatic epoxy resins and aliphatic polyglycidyl ethers. Preferred among these are bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin and the like. Many of these compounds having two or more epoxy groups in the molecule are high molecular weight compounds, and more preferably, low molecular weight compounds such as glycidyl ether of bisphenol A or bisphenol F can be used.

Such an epoxy resin is contained in the photosensitive resin composition in a solid content ratio of 1% by weight to 30% by weight, preferably 5% by weight.
% By weight to 20% by weight. If the content of the epoxy resin exceeds 20% by weight, the amount of the epoxy resin that is not subjected to photocuring becomes too large, and the storage stability and development suitability of the photosensitive resin composition are undesirably reduced. Further, the epoxy resin is also effective for removing the tack of the dried coating film of the photosensitive resin composition, and a sufficient effect is exhibited when the added amount is about 3% by weight. The epoxy resin reacts with the acidic group remaining in the colored layer or the protective film by heat treatment without reacting even after exposure and alkali development, and imparts excellent alkali resistance to the colored layer and the protective film. Become.

The above-mentioned photosensitive resin composition of the present invention may optionally contain various additives such as a surfactant and a silane coupling agent as shown below.

A surfactant is blended with the composition of the present invention in order to ensure coatability and film smoothness after drying.
For example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene arylalkyl such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Ethers,
Polyoxyethylene dialkyl esters such as polyoxyethylene ethylene dilaurate and polyoxyethylene distearate, Megafac F171, 172, 1
73 (manufactured by Dainippon Ink), Florad FC430, 43
1 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, 102, 103,
Fluorinated surfactants such as 104 and 105 (manufactured by Asahi Glass) can be used. The amount of these surfactants is preferably 2 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the solid content of the composition.

The silane coupling agent is added for the purpose of improving the adhesion to the colored layer and the substrate. For example, vinyl silane, acrylic silane, epoxy silane,
Aminosilane and the like can be mentioned. More specifically, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like can be used as vinylsilane. In addition, as acrylic silane, γ
-Methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane and the like. As the epoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane and the like. Furthermore, aminosilanes include N
-Β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethylditrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Trimethoxysilane and the like can be used. As other silane coupling agents, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ
-Chloropropylmethyldiethoxysilane and the like can be used.

The photosensitive resin composition of the present invention usually contains a solvent in consideration of paintability and suitability for coating. Examples of the solvent used include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol; cellosolve solvents such as methoxy alcohol and ethoxy alcohol; carbitol such as methoxyethoxy ethanol and ethoxyethoxy ethanol. System solvent: ethyl acetate, butyl acetate,
Ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone and cyclohexanone; cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; methoxy Carbitol acetate solvents such as ethoxyethyl acetate and ethoxyethoxyethyl acetate; ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Aprotic amide solvents such as pyrrolidone; lactone solvents such as γ-butyrolactone; benzene, Ene, xylene, unsaturated hydrocarbon solvents such as naphthalene; N- heptane, N- hexane,
Organic solvents such as a saturated hydrocarbon solvent such as N-octane are exemplified. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate;
Ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol diethyl ether; ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate are particularly preferably used, and have a solid concentration of 5% by weight to 50% by weight. %.

The photosensitive resin composition of the present invention can be obtained by blending each of the above components with an appropriate organic solvent. The photosensitive resin composition thus obtained is in the form of a coating liquid or ink in which the organic solvent is used as a medium, and is used by diluting it by adding an organic solvent immediately before use, if necessary. .

Since the above-mentioned transparent photosensitive resin composition of the present invention uses a copolymer resin whose alkali solubility and curability are controlled, for example, as a composition for forming a protective film in a color filter, a tacky resin composition may be used. Excellent in properties, leveling properties, alkali resistance, adhesion, developability, edge shape, surface condition, and dynamic hardness.

Next, the case where the photosensitive resin composition of the present invention is used as a photosensitive resin composition for forming a colored layer in a color filter will be described.

As a photosensitive resin composition for forming a colored layer in a color filter, the above-mentioned photosensitive resin composition further contains a coloring pigment and a dispersant.

As the pigment, any of the known pigments used in the production of conventional color filters can be used. Specifically, for example, as the organic pigment, phthalocyanine-based, azo-based, condensed azo-based, anthraquinone-based,
Perinone / perylene, indigo, thioindigo,
Examples include isoindolinone type, azomethine type, azomethine azo type, dioxazine type, quinacridone type, aniline black type, triphenylmethane type, and carbon black.

Among them, a particularly preferred pigment is red (R
ed) as C.I. I. No. 9, C.I. I. No. 97,
C. I. No. 122, C.I. I. No. 123, C.I.
I. No. 149, C.I. I. No. 168, C.I. I. N
o. 177, C.I. I. No. 180, C.I. I. No. 1
92, C.I. I. No. 215, etc .; green
As C. I. No. 7, C.I. I. No. 36 as blue (B1ue). I. No. 15, C.I. IN
o. 22, C.I. I. No. 60, C.I. I. No. 64 or the like is used.

When spectral correction is performed not only independently but also in combination, a color index (T
he Society of Dyers and C
o1ourist's limb) and Pigment
Compounds classified under t) are included. That is,
C. I. Pigment Yellow 24, C.I.
I. Pigment Yellow 31, C.I. I. P
pigment Yellow 53, C.I. I. Pigm
ent Yellow 83, C.I. I. Pigment
Orange 43, C.I. I. Pigment Re
d 105, C.I. I. Pigment Red 14
9, C.I. I. Pigment Red 176, C.I. I.
Pigment Red 177, C.I. I. Pigme
nt Vio1et 14, C.I. I. Pigment
Vio1et 29, C.I. I. Pigment B1u
e 15, C.I. I. Pigment B1ue 15:
3, C.I. I, Pigment B1ue 22, C.I.
I. Pigment B1ue28, C.I. I. Pigm
ent Green 15, C.I. I. PigmentG
reen 25, C.I. I. Pigment Green
36, C.I. I. Pigme Brown 28, C.I.
I. Pigment B1ack 1, C, I. Pig
ment B1ack 7 and the like.

It is preferable that the pigment to be used is previously dispersed with a dispersant and / or a copolymer resin described below. For dispersing the pigment, any disperser may be used, for example, a ball mill, a visco mill, a roll mill, a kneader, an attritor, a high-speed mixer,
Homomixer and the like can be mentioned.

The pigment is added in an amount of 50 to 300 parts by weight, preferably 75 to 15 parts by weight, based on 100 parts by weight of the copolymer resin.
0 parts by weight. If this value is less than 50 parts by weight, the coloring power of each pixel is insufficient, and it becomes difficult to display a clear image. If this value exceeds 300 parts by weight, the light transmittance of each pixel becomes insufficient. Pigment is its kind,
Since various optical properties such as coloring power and transparency change depending on the particle size, dispersion state, etc., R, G, B and Bk
The amount to be used is determined according to the physical properties of the specific pigment selected as (black). The criterion for determining the used amount is to set the amount at which the light transmittance of the formed pixel is about 80 to 90%.

The dispersant can be appropriately selected from a wide range and used, for example, a surfactant, a pigment intermediate, a dye intermediate and the like. Such a dispersant must function to prevent aggregation of the pigment and to uniformly disperse the pigment used in the colored coating solution. Therefore, the dispersant itself must not interfere with the physical properties of the color filter to be produced, and it is necessary to select the dispersant in consideration of heat resistance and yellowing.

Specifically, anionic pigment dispersants such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators; nonionic pigment dispersants such as polyoxyethylene / polyoxypropylene block polymers; anthraquinone Organic dyes such as organic, perylene, phthalocyanine, and quinacridone organic dyes, into which substituents such as amino group, carboxyl group, sulfonate group, carboxylic acid amide group, and hydroxyl group are introduced. further,
By using an addition polymer containing a monomer having an acidic group such as (meth) acrylic acid or styrene sulfonic acid as a copolymer component together with these dispersants, dispersibility and miscibility with a resist are improved, and excellent. Resist characteristics.

The pigment dispersant, the derivative of the organic dye, or the mixture of the dispersant and the addition copolymer having an acidic group is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the pigment.

In forming the colored layer, a sensitizing dye may be contained in addition to the pigment and the dispersant. The sensitizing dye can be combined with the above-described initiator system for the purpose of further improving the sensitivity by widely utilizing the wavelength distribution of the type of the exposure light source. Dyes that can be combined are 5-nitroa manufactured by Shinko Giken.
cenaphtene, 1-nipropylene,
N-acety 1-4-nitro-1-aminon
aphthalene, N-phenyl1thioac
rydone, S-151, S-161, S-171,
S-181, S-142, S-152, S-162, S
-172, S-182, NK-134 manufactured by Nippon Kogaku Dyestuffs
2, NK-3798, NK-1473, NKX-84
6, NKX-1319, NKX-1595, NKX-6
53, NKX-1658, NKX-2990, NKX-
3906 is preferred. The sensitizing dye is preferably used in the range of 0.1 to 10% by weight based on the photopolymerizable compound.

Further, if it is desired to improve the light sensitivity, a sensitizer may be added. As the sensitizer used,
A styryl compound or a coumarin compound is preferable, and specifically, 2- (p-dimethylaminostyryl)
Quinoline, 2- (p-diethylaminostyryl) quinoline, 4- (p-dimethylaminostyryl) quinoline,
-(P-diethylaminostyryl) quinoline, 2- (p
-Dimethylaminostyryl) -3,3-3H-indole, 2- (p-diethylaminostyryl) -3,3-3
H-indole, 2- (p-dimethylaminostyryl)
Examples include benzoxazole, 2- (p-diethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzimidazole, 2- (p-diethylaminostyryl) benzimidazole and the like.

The coumarin compounds include 7-diethylamino-4-methylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, 4,6-diethylamino-7-ethylaminocoumarin, and 3- (2-benzene). Imidazolyl) -7-N, N-diethylaminocoumarin, 7-diethylaminocyclopenta (c) coumarin,
7-amino-4-trifluoromethylcoumarin, 1,
2,3,4,5,3H, 6H, 10H-tetrahydro-
8-trifluoromethyl (1) benzopyrano- (9,9
A, 1-gh) -Quinolidin-10-one, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 1,2,3,4,5,3H, 6H, 10H-tetrahydro-9-carbethoxy (1) Benzopyrano (9,9
a, 1-gh) -quinolizin-10-one and the like.

The photosensitive resin composition of the present invention can be obtained by blending the above-mentioned components and an appropriate organic solvent, stirring and mixing. The photosensitive resin composition thus obtained is in the form of a coating liquid or ink in which an organic solvent is used as a medium, and is diluted with an organic solvent immediately before use, if necessary. Is also good.

The method of forming a color filter pattern using the photosensitive resin composition of the present invention may be a conventionally known method, for example, R, G, B and Bk in an appropriate order.
The photosensitive resin (colored) composition is spin-coated on a transparent substrate, and the entire surface is coated using a low-speed rotation coater, a roll coater, a knife coater, or the like.
When using a spin coater, the rotation speed is 500 to 15
It is preferable to set within the range of 00 times / minute. Also,
It is also possible to perform full-scale printing by various printing methods or partial printing slightly larger than the pattern.

After pre-drying, the coating film is adhered to a photomask, exposed and cured using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a far ultraviolet lamp, and a visible light laser to print a pattern. I do.

Next, the coating film irradiated with light is coated with an aqueous alkali solution (an aqueous solution of a base such as an alkali metal carbonate such as sodium carbonate, an alkali metal hydroxide such as sodium hydroxide, or an organic alkali such as tetramethylammonium hydroxide). , Organic solvents (organic halides such as trichloroethylene, perchloroethylene, and methylene chloride; ketones such as methyl isobutyl ketone and cyclohexanone; and esters such as ethyl cellosolve acetate)
Develop and wash in running or shower water,
Dissolve the uncured parts. This process is repeated for each color.

In the photosensitive resin composition of the present invention, a copolymer resin, an amino resin such as melamine, and an initiator system comprising a radical initiator and a photoacid generator (cationic initiator system) are combined. Upon exposure, a reaction between an amino resin such as melamine and a residual hydroxyl group or carboxyl group in the copolymer resin of the present invention can be caused by using an acid generated by the cationic initiator system as a catalyst. For this reason, the sensitivity is improved, and if necessary, the reaction can be further promoted by further post-baking, whereby the stability such as alkali resistance can be improved. In addition, since no carboxyl group or hydroxyl group remains, a stable protective film having excellent chemical resistance (eg, alkali resistance) can be formed. Further, it has a low molecular weight and is polyfunctional, and has excellent compatibility with a copolymer resin.

Further, in the photosensitive resin composition of the present invention, the heat treatment (post-bake) performed after the exposure of the coating film and the alkali development are completed is usually 120 to 25.
The reaction can be performed at 0 ° C. for about 5 to 90 minutes.

When the photosensitive resin composition of the present invention contains an epoxy resin, it reacts with the remaining acidic groups by this heat treatment. The photosensitive resin composition is exposed, even after alkali development, the unreacted acidic groups remain in the photosensitive resin composition, but the epoxy resin contained in the photosensitive resin composition, Since the residual acidic group reacts with the heat treatment, the protective film formed by the heat treatment (post-baking) has no alkali group capable of reacting with an alkali and has excellent alkali resistance. .

The photosensitive resin composition of the present invention uses a copolymer resin whose alkali solubility and curability are controlled by being used for a colored layer, so that tackiness, leveling property, alkali resistance, and adhesion are used. A colored layer having excellent developability, edge shape, surface state, and dynamic hardness can be obtained.

Next, a color filter using the photosensitive resin composition of the present invention will be described. FIG. 1 is a schematic configuration diagram showing an example of the color filter of the present invention. In FIG. 1, a color filter 1 of the present invention includes a colored layer 3 and a black matrix 4 formed in a predetermined pattern on a transparent substrate 2, and a protective film 5 formed so as to cover the colored layer 3.
And a transparent electrode 6 for driving a liquid crystal is formed on the protective film 5.

As the transparent substrate 2 constituting such a color filter 1, quartz glass, Pyrex glass,
An inflexible rigid material such as a synthetic quartz plate or a flexible material such as a transparent resin film or an optical resin plate can be used. Among them, Corning 7059 glass is a material having a small coefficient of thermal expansion, and has excellent dimensional stability and workability in high-temperature heat treatment.
In addition, since the glass is an alkali-free glass containing no alkali component, it is suitable for a color filter used in a color liquid crystal display device.

The color layer 3 constituting the color filter 1 and formed by using the photosensitive resin composition of the present invention has a mosaic type, a stripe type, a triangle type, a red type 3R, a green type 3G and a blue type 3B. The black matrix 4 is arranged in a desired form such as a four-pixel arrangement type.
It is provided in a predetermined area outside the formation area. The black matrix 4 may be formed using the photosensitive resin composition of the present invention similarly to the coloring layer, but may be formed by a dyeing method, a printing method, an electrodeposition method, or a chromium vapor deposition method. Is also good.

The protective film is formed by coating the photosensitive resin composition of the present invention with
A dry film thickness of 0.5 to 20 μm, preferably 1 to 8 μm is applied on a transparent substrate on which the coloring layer and the black matrix are formed by a method such as spin coater, roll coater, spraying, printing, and the like, and then a predetermined photo It is formed by exposing through a mask and developing. When a spin coater is used, the number of rotations is preferably set within a range of 500 to 1500 times / minute. The exposure and development processing for the protective film is the same as that for the above-described colored layer. When the photosensitive resin composition of the present invention is used for a protective film, it can be excellent in tackiness, leveling property, alkali resistance, adhesion, developability, edge shape, surface state, and dynamic hardness.

The transparent electrodes on the protective film are made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (Sn oxide).
O) and its alloys, and is formed by a general film forming method such as a sputtering method, a vacuum evaporation method, or a CVD method, and is formed into a predetermined pattern by etching using a photoresist as necessary. is there. The thickness of this transparent electrode is about 20 to 500 nm, preferably 100 to 30 nm.
It is about 0 nm. Hereinafter, the present invention will be described in detail with reference to examples.

[0100]

EXAMPLES (Synthesis example 1 of copolymer resin) Composition: benzyl methacrylate: 250 g (15.6 mol%) Styrene: 350 g (37.0 mol%) Acrylic acid: 200 g (30.5 mol%) 2-hydroxyethyl methacrylate ... A solution of 200 g (16.9 mol%) dissolved in 650 g of 3-methoxybutyl acetate together with 5 g of azobisisobutyronitrile was converted to acetic acid-3-
In a polymerization tank containing 1000 g of methoxybutyl, 100
At 6 ° C., the mixture was added dropwise over 6 hours and polymerized to obtain a polymer solution.

Next, a mixture of the composition, 2-methacryloyloxyethyl isocyanate, 240 g, dibutyltin laurate, 1 g, 3-methoxybutyl acetate, 2260 g was added to the obtained polymer solution. Was added dropwise over 5 hours. In addition, the addition amount of 2-methacryloyloxyethyl isocyanate is equivalent to 16.9 mol% with respect to 100 mol% of the copolymer composition before adding 2-methacryloyloxyethylisocyanate (hereinafter, referred to as copolymer composition).

While monitoring the progress of the reaction by IR (infrared absorption spectrum), the reaction was continued until the peak at 2200 cm ^{-1 due to} the isocyanate group disappeared.

The obtained reaction solution had a solid content of 25.5% by weight and a viscosity of 77.3 mPa · s / 25 ° C. After applying the obtained polymer solution on a glass plate, it was left overnight at room temperature. The solvent was removed by drying under reduced pressure. The acid value of the obtained solid was 125.5 mgKOH / g, the weight average molecular weight was 42,
500.

Hereinafter, methods for measuring these physical properties will be described. Solid: 0.7 g to 0.8 of the polymer solution in an aluminum dish
g. After weighing the sample, the sample was dried with a hot air dryer at 105 ° C. for 6 to 7 hours, immediately weighed, and the ratio of the obtained dry weight to the polymer solution weight was determined. Viscosity (mPa · s / 25 ° C.): Rotor No. Measured at 60 rotations using 1. Acid value: The acid value was determined by dissolving the sample in acetone and performing a neutralization titration with 1 / 10N NaOH using cresol red as an indicator. Weight average molecular weight: GPC measurement conditions and column Column: Shodex GPC KF-805L (Showa Denko KK) Flow rate: 1.0 (ml / min.), 40 ° C, detector: R
I, eluent: After diluting tetrahydrofuran ⁽¹ H-NMR analysis of the copolymer resin) (Preparation of Sample) obtained polymer solution 5g in tetrahydrofuran 5g, portionwise poly dropper with stirring in isopropanol 300g It was dropped. The supernatant was discarded, and the solid content solidified on the bottom was completely dissolved in 5 g of tetrahydrofuran, and the solution was dropped in isopropanol in the same manner. The obtained solid component was completely dissolved in 20 g of tetrahydrofuran and dropped in 300 g of hexane in the same manner. The precipitated solid was filtered and dried under reduced pressure at room temperature overnight to prepare a sample. The weight average molecular weight of this sample was 94.0
00.

[0105] to completely dissolve the sample in deuterated DMSO, ¹
The results of H-NMR analysis are shown below.

¹ H-NMR (DMSO-d) σ ppm σ 0.2 to 1.1 (m, 12H) σ 1.1 to 1.8 (m, 19H) σ 1.85 (s, 3H) σ 3.27 (b , 2H) σ3.27 (b, 2H) σ3.51 (b, 2H) σ3.90 (b, 2H) σ4.08 (b, 2H) σ4.75 (b, 1H) σ4.90 (b, 2H) ) S 5.63 (s, 1H) s 6.05 (s, 1H) s 7.11 (b, 23H) s 7.31 (b, 6H) s 12.04 (b, 2H)
.

From ¹ H-NMR analysis, the unit ratio (molar ratio) of each structural unit in the purified copolymer resin was benzyl methacrylate: styrene: hydroxyethyl methacrylate: acrylic acid: 2-methacryloyloxyethyl isocyanate = 2: 5 : 2: 4: 1. The methacryloyloxy group-introduced structural unit amount in the purified copolymer resin was 8.23 mol% (10.5% by weight) based on 100 mol% of the copolymer composition. After coating (2-methacryloyloxy Determination of oxyethyl isocyanate dimer) obtained polymer solution on a glass plate, remove the solvent and dried in vacuo at room temperature overnight, scraped resulting solid from the glass plate, ¹ As a result of 1 H-NMR analysis, the amount of 2-methacryloyloxyethyl isocyanate dimer was 3.% based on 100 mol% of the copolymer composition.
09 mol%.

In the polymerization reaction in Synthesis Example 1, 2-
As shown in Synthesis Examples 2 to 4, the addition ratio of methacryloyloxyethyl isocyanate was changed.

(Synthesis Example 2 of Copolymer Resin) In the polymerization reaction in Synthesis Example 1, when adding 2-methacryloyloxyethyl isocyanate, 8.45 mol% was added to 100 mol% of the copolymer composition. Except for the above, a methacryloyloxy group was introduced in the same manner as in Synthesis Example 1.

The obtained reaction solution had a solid content of 24.1% by weight and a viscosity of 74.7 mPa · s / 25 ° C. After the obtained polymer solution was applied on a glass plate, it was left overnight at room temperature. The solvent was removed by drying under reduced pressure to remove the solvent. The obtained solid had an acid value of 133.6 mgKOH / g and a weight average molecular weight of 41,6.
00.

(Synthesis Example 3 of Copolymer Resin) In the polymerization reaction in Synthesis Example 1, when adding 2-methacryloyloxyethyl isocyanate, 20.3 mol% was added to 100 mol% of the copolymer composition. Except for the above, a methacryloyloxy group was introduced in the same manner as in Synthesis Example 1.

The obtained reaction solution had a solid content of 26.2% by weight and a viscosity of 83.8 mPa · s / 25 ° C. After applying the obtained polymer solution on a glass plate, it was left overnight at room temperature. The solvent was removed by drying under reduced pressure to remove the solvent. The obtained solid had an acid value of 119.2 mgKOH / g and a weight average molecular weight of 42.6 mgKOH / g.
00.

(Synthesis Example 4 of Copolymer Resin) In the polymerization reaction in Synthesis Example 1, when adding 2-methacryloyloxyethyl isocyanate, 25.4 mol% was added to 100 mol% of the copolymer composition. Except for the above, a methacryloyloxy group was introduced in the same manner as in Synthesis Example 1.

The obtained reaction solution had a solid content of 26.9% by weight and a viscosity of 88.9 mPa · s / 25 ° C. After applying the obtained polymer solution on a glass plate, it was left overnight at room temperature. The solvent was removed by drying under reduced pressure to remove the solvent. The obtained solid had an acid value of 113.4 mgKOH / g and a weight average molecular weight of 45.2.
00.

The polymer solutions obtained in Synthesis Examples 2 to 4 were used and treated in the same manner as in Synthesis Example 1, and ¹ H-NMR analysis was performed. The results shown in the following table were obtained. In addition, in the following table, the order in which the addition amount of 2-methacryloyloxyethyl isocyanate is small, that is, Synthesis Example 2, Synthesis Example 1, Synthesis Example 3, and Synthesis Example 4 is shown.

[0116]

[Table 1] .

As is clear from Synthesis Examples 1 to 4,
It can be seen that the copolymer resin in the present invention is a copolymer resin whose content of a radical polymerizable group such as an alkali-soluble group and a (meth) acryloyloxy group can be controlled.

Next, as structural units, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), and acrylic acid (A
A), methacrylic acid (MAA), styrene (St), benzyl methacrylate (BzMA), 4-butyl acrylate (HBA), 2-ethyl acrylate (HE)
A) Using a methyl methacrylate (MMA), a reaction product obtained by performing a polymerization reaction in the same manner as described above,
Table 2 below shows the monomer composition (mol%), and the solid content (% by weight) and viscosity (mPa · s / 25) of the polymer solution obtained in Table 3.
° C), acid value (mgKOH / g), weight average molecular weight (M
w) is shown.

[0119]

[Table 2] .

The amount of 2-methacryloyloxyethyl isocyanate added to each reactant was 16.9 mol% for reactant (1) and 16.2 mol% for reactant (2) based on 100 mol% of the copolymer composition. 9 mol%, reactant (3) is 1
7.9 mol%, reaction product (4) 17.9 mol%, reaction product (5) 17.2 mol%, reaction product (6) 16.7 mol%, reaction product (7) 15. 9 mol%, reactant (8) was 1
8.5 mol%.

[0121]

[Table 3] .

(Example 1) A red photosensitive resin having the following composition was applied to a 1.1 mm thick glass substrate (AL material manufactured by Asahi Glass Co., Ltd.) by a spin coating method (application thickness: 1.5 μm). Then, it was dried in an oven at 70 ° C. for 30 minutes.

Next, 1 layer was obtained from the coating film of the photosensitive resin composition.
A photomask is arranged at a distance of 00 μm, and a proximity liner uses a 2.0 kW ultra-high pressure mercury lamp to apply ultraviolet rays to only the region corresponding to the region where the colored layer is formed.
Irradiated for seconds. Then, the film was immersed in a 0.05% aqueous solution of potassium hydroxide (solution temperature: 23 ° C.) for 1 minute to perform alkali development,
Only the uncured part of the coating film of the photosensitive resin composition was removed. After that, the substrate was left in an atmosphere of 180 ° C. for 30 minutes to perform a heat treatment to form a red relief pattern in a region where a red pixel was to be formed.

Next, using a green photosensitive resin having the following composition, a green relief pattern was formed in a region where a green pixel was to be formed in the same process as that for forming a red relief pattern.

Further, using a blue photosensitive resin having the following composition, a blue relief pattern is formed in a region where a blue pixel is to be formed by the same process as that for forming a red relief pattern, and red (R) and green (G), a colored layer composed of three colors of blue (B) was prepared. (Composition of red photosensitive resin) C.I. I. Pigment Red 177: 10 parts by weight ・ Polysulfonic acid type polymer dispersant: 3 parts by weight ・ The following photosensitive resin composition: 5 parts by weight ・ 3-methoxybutyl acetate: 82 parts by weight (composition of green photosensitive resin) C. I. Pigment Green 36: 10 parts by weight-Polysulfonic acid type polymer dispersant: 3 parts by weight-The following photosensitive resin composition: 5 parts by weight-3-methoxybutyl acetate: 82 parts by weight (composition of blue photosensitive resin) C. I. Pigment Blue ... 10 parts by weight-Polysulfonic acid type polymer dispersant ... 3 parts by weight-The following photosensitive resin composition ... 5 parts by weight-3-methoxybutyl acetate ... 82 parts by weight (preparation of photosensitive resin composition) Composition • The reaction product obtained in the above Synthesis Example 1 (solid content: 25.5% by weight)… 9.0 parts by weight • Dipentaerythritol pentaacrylate (manufactured by Sartomer, SR399) ... 7.0 parts by weight • Hexamethoxymethylol Melamine (manufactured by Mitsui Cytec Co., Ltd., Cymel 300) ... 1.0 part by weight ・ 2-methyl-1-[(4-methylthio) phenyl] -2-morpholinopropanone-1 ... 2.4 parts by weight ・ 2.2 '-Bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole 1.0 part by weight Triazine (midori Gakusha Ltd., TAZ110) ... 0.4 parts by weight of diethylene glycol dimethyl ether ... 39.1 parts by weight of 3-methoxybutyl acetate ... 41.0 parts by weight was stirred and mixed at room temperature to obtain a photosensitive resin composition.

Next, the photosensitive resin composition having the above composition was applied to the glass substrate having the above-mentioned colored layer formed thereon by spin coating (dry film thickness: 1.2 μm).

(Exposure / Development Step) A photomask is arranged at a distance of 100 μm from the coating film of the photosensitive resin composition, and corresponds to a region where a colored layer is formed by using a 2.0 kW ultra-high pressure mercury lamp by a proximity liner. Only the region to be irradiated was irradiated with ultraviolet rays for 10 seconds. Then, the film is immersed in a 0.05% aqueous solution of potassium hydroxide (solution temperature 23 ° C.) for 1 minute to carry out alkali development to remove only the uncured portion of the coating film of the photosensitive resin composition. Heat treatment was performed for 30 minutes to form a protective film, and a color filter of the present invention was obtained.

(Example 2) Instead of the photosensitive resin composition in Example 1, a photosensitive resin composition prepared below was used in the same manner.
A colored layer was formed in the same manner except that a curing treatment was performed by heating at 0 ° C. for 30 minutes.

(Preparation of Photosensitive Resin Composition) The following composition: The reactant obtained in the above Synthesis Example 1 (solid content: 25.5% by weight): 8.8 parts by weight. Orthocresol novolak type epoxy resin (oilification) 3.9 parts by weight-Dipentaerythritol pentaacrylate (DPPA, manufactured by Nippon Kayaku) ... 6.8 parts by weight-Radical polymerization initiator (Irgacure 907, Ciba Specialty Chemical Co., Ltd.) 3.3 parts by weight-Photoacid generator (pentadecyloxyphenylphenyliodonium heisafluorantimony)-0.3 parts by weight-Propylene glycol monomethyl ester-76.9 parts by weight are stirred and mixed at room temperature. Thus, a photosensitive resin composition was obtained.

Next, on a glass substrate having a colored layer formed thereon,
The photosensitive resin composition having the above composition was applied by a spin coating method (dry film thickness: 1.2 μm).

(Exposure / Development Step) A photomask is arranged at a distance of 100 μm from the coating film of the photosensitive resin composition. Only the region to be irradiated was irradiated with ultraviolet rays for 10 seconds. Next, it was immersed in a 0.05% aqueous solution of potassium hydroxide (solution temperature: 23 ° C.) for 1 minute to carry out alkali development to remove only the uncured portion of the coating film of the photosensitive resin composition.

Thereafter, the film was left to stand in an atmosphere of 180 ° C. for 30 minutes to perform a heat treatment to form a protective film, thereby obtaining a color filter of the present invention.

(Comparative Example) A colored layer and a protective film were formed in the same manner as in Example 1, except that the photosensitive resin composition prepared below was used instead of the photosensitive resin composition. Created.

(Preparation of photosensitive resin composition) The following composition: o-cresol novolak epoxy acrylate (50% of hydroxyl groups reacted with phthalic anhydride) 8.8 parts by weight Dipentaerythritol hexaacrylate 8 0.8 parts by weight Orthocresol novolac epoxy resin 2.0 parts by weight Initiator (Irgacure-369) 0.4 parts by weight Acetic acid-3-methoxybutyl alcohol 80 parts by weight is stirred and mixed at room temperature. Then, a photosensitive resin composition was prepared.

For each of the obtained color filters, tackiness, leveling, adhesion, developability and edge shape were evaluated under the following conditions when forming a colored layer and a protective layer. , Alkali resistance, surface condition and dynamic hardness were evaluated.

(Alkali Resistance, Surface Condition, Dynamic Hardness) A sample was immersed in a 1% aqueous solution of sodium hydroxide (solution temperature: 23 ° C.) for 24 hours and then pulled up to measure the hardness of the protective film with a dynamic hardness tester (Shimadzu Dynamic Ultra Fine). Small hardness tester D
UH-201S, constant indentation load test: triangular indenter: 1
15 °, load: 5 mN, load speed constant: 6, holding time:
5 seconds), and the appearance was evaluated according to the following evaluation criteria.

Evaluation criteria of external appearance ：: No change is observed in the protective film. 表面: The surface of the protective film is roughened and bubbles are generated. X: Part or all of the protective film is peeled off.

(Developability, Edge Shape) The outer peripheral shape of the pattern when the unexposed portion was completely removed by immersion in a 0.05% aqueous potassium hydroxide solution (23 ° C.) for 1 minute was evaluated according to the following criteria. ：: The outer peripheral shape keeps linearity, and no undulation, wrinkles, etc. are observed. ×: The outer peripheral shape has no linearity, and undulations, wrinkles, etc. are generated.

(Tackiness) The tackiness on the surface of the coating film before exposure was observed and evaluated according to the following criteria. ：: There is no tack. ×: There is tack.

(Leveling property) The surface condition of the coated film after coating and drying was observed and evaluated according to the following criteria. ：: Flat. ×: lacks flatness and the surface has a citron texture.

(Adhesion) After the cross-cut, a peeling test was carried out using an adhesive tape (3M, No. 610), and evaluated according to the following criteria. ：: No peeling in each square. X: Peeling occurred in each of the squares. The results are shown in Table 4 below.

[0142]

[Table 4]

[0143]

The photosensitive resin composition of the present invention uses a copolymer resin having alkali solubility and curability controlled, so that tackiness, leveling property, alkali resistance, adhesion,
Excellent in developability, edge shape, surface condition, and dynamic hardness. Further, by using this photosensitive resin composition for forming a colored layer, a highly reliable color filter having excellent display quality can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating an example of a color filter of the present invention.

[Explanation of symbols]

1 ... color filter, 2 ... transparent substrate, 3 ... colored layer, 4 ...
Black matrix, 5: protective film, 6: transparent electrode

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/027 513 G03F 7/027 513 F term (Reference) 2H025 AA00 AA01 AA04 AA08 AA14 AB13 AB16 AB17 AC01 AD01 BC14 BC42 BC53 BC81 BC83 BC85 BC86 BC92 BE00 CA01 CA14 CA18 CA28 CA30 CA37 CC20 FA03 FA17 FA29 2H048 AA09 BA45 BA48 BB44 2H091 FA02Y FA35Y FB02 FB12 FB13 FC10 FC23 GA16 LA02 4J027 AA02 BA19 BA20 BA21 CA10 CB23 CC05 CD10

Claims (3)

[Claims] 1. A product obtained by partially reacting a structural unit represented by the following general formula (1) or (2) with a (meth) acryloylalkyl isocyanate compound via a carboxyl group or a hydroxyl group, respectively. The structural unit derived from the following general formula (1) is 5 mol% to 55 mol%, and the structural unit derived from the following general formula (2) is 5 mol% to 5 mol%.
95 mol%, containing 5 mol% to 95 mol% of a (meth) acryloyl group-introduced structural unit, and having an acid value of 5 mgKOH /
g to 400 mgKOH / g and a weight average molecular weight in terms of polystyrene of 10,000 to 1,000,000.
And a polyfunctional photopolymerizable acrylate monomer having two or more functional groups, at least one resin selected from an epoxy resin and an amino resin, and an initiator comprising a radical polymerization initiator and a photoacid generator. A photosensitive resin composition comprising: Embedded image (Wherein, R is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ₁ represents an alkylene group having 2 to 4 carbon atoms. a and b represent an integer corresponding to each mol%. ) 2. A product in which a structural unit represented by the following general formulas (1) and (2) partially reacts with a (meth) acryloylalkyl isocyanate compound via a carboxyl group or a hydroxyl group as a structural unit. The structural unit derived from the following general formula (1) is 5 mol% to 55 mol%, and the structural unit derived from the following general formula (2) is 5 mol% to 5 mol%.
95 mol%, containing 5 mol% to 95 mol% of a (meth) acryloyl group-introduced structural unit, and having an acid value of 5 mgKOH /
g to 400 mgKOH / g and a weight average molecular weight in terms of polystyrene of 10,000 to 1,000,000.
A copolymer resin, a bifunctional or higher polyfunctional photopolymerizable acrylate monomer, at least one resin selected from an epoxy resin and an amino resin, an initiator comprising a radical polymerization initiator and a photoacid generator, a pigment, A photosensitive resin composition comprising a dispersant. Embedded image (Wherein, R is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ₁ represents an alkylene group having 2 to 4 carbon atoms. a and b represent an integer corresponding to each mol%. ) 3. A copolymer resin as a copolymer component.
A structural unit represented by the following general formula (3)
75 mol%, the structural unit represented by the following general formula (4)
2. The composition of claim 1, wherein the content is from about mol% to about 75 mol%.
The photosensitive resin composition as described in the above. Embedded image(Wherein, R is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R_TwoIs an aromatic carbocycle, R _ThreeIs an alkyl group or aral
Represents a kill group. c and d correspond to the respective mol%
Represents an integer. )