JP3509269B2 - Composition for forming light-shielding thin film and light-shielding film formed using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive alkaline aqueous solution developing type light-shielding thin film composition for forming a fine light-shielding thin film on a transparent substrate, a light-shielding film formed using the same, and a color filter. Black matrix for automobiles.

The light-shielding thin film composition of the present invention is excellent in storage stability at room temperature, and a light-shielding film formed using this composition has high light-shielding property, heat resistance, developability, adhesion, acid resistance and alkali resistance. , Excellent in solvent resistance and insulation, various multicolor display bodies such as color liquid crystal display devices, color facsimiles and image sensors, and ink as a black matrix of color filters used in optical devices, And a color filter having a black matrix formed by these, a television, a video monitor,
Alternatively, it can be suitably used for a computer display and the like.

[0003]

2. Description of the Related Art In recent years, in color filters used for colorizing liquid crystal displays, high definition image quality,
High quality is required, and a light-shielding film is used in the stripes and the dot gaps to shield unnecessary light for improving contrast and to improve other characteristics. For example, a light-shielding film is used as a black matrix formed between pixels such as red, blue, and green of a color filter, and this light-shielding film serves to prevent deterioration of contrast and color purity due to light leakage between pixels. Plays.

A vapor-deposited film of chromium or the like has been conventionally used as such a light-shielding film, but there is a problem that the forming process is complicated and expensive.
Therefore, as a solution to this problem, a photolithography method containing a photosensitive resin has been proposed (JP-A-4-177202). However, this resin light-shielding film also has a problem in terms of light-shielding property and sharpness of edge shape, and it is required to develop a resin light-shielding film having higher light-shielding property and sharp edge shape associated with a fine pattern.

Further, Japanese Patent Laid-Open No. 6-1938 proposes a photosensitive ink containing an epoxy resin for the purpose of improving alkalinity, chemical resistance and the like. However, in this photosensitive ink, the addition amount of the pigment is restricted because the epoxy resin is mixed, the improvement of the light-shielding rate is hindered, and further, the viscosity increases with the lapse of time when stored at room temperature, and the development speed increases. Another problem is that the resolution and sensitivity decrease, the dimensional accuracy of the pixel portion varies, and a stable color filter cannot be configured. Therefore, in order to store the photosensitive ink, there is also an inconvenience that it must be refrigerated until it is used.

[0006]

By the way, as a photocurable light-shielding film composition used for a conventional color filter or the like, in many cases, a light-shielding material such as carbon black, titanium black, black iron oxide or the like is used. It is known that the black organic pigments, various black dyes, and mixed color organic pigments obtained by mixing organic pigments such as red, blue, and green into a pseudo black color are dispersed alone or in a resist. ing.

However, in the conventional composition for forming a light-shielding thin film containing these, in order to achieve a desired high light-shielding rate, the composition for forming a light-shielding thin film contains a pigment or a dye for the photosensitive resin. Although it is necessary to increase the amount, in the case of producing a fine pattern, if a light-shielding material that does not have developability by itself or an epoxy resin accompanied by heat curing is excessively mixed, these light-shielding material and heat-cured epoxy will not be used. The resin or the like remains as a residue on the substrate, which not only causes the deterioration of the developing performance, but also causes a significant decrease in the sharpness of the edge shape of the pattern required in the case of a high-definition display.

When a light-shielding film containing a large amount of the light-shielding material mixed with the photosensitive resin in the composition for forming a light-shielding thin film is used, such a light-shielding film has a low electric resistance and is electrically conductive. There arises a problem that the liquid crystal driving electrode and the color filter forming electrode cannot be shared. That is, in the color filter manufacturing method such as the electrodeposition method and the micelle electrolysis method,
If the black matrix is first formed on the ITO electrode patterned for forming the color filter, the black matrix is electrically connected to the adjacent electrode, which causes a problem.

An object of the present invention is to have a high light blocking rate, and
It is an object of the present invention to provide a composition for forming a light-shielding thin film in which a fine pattern can be easily formed by a photolithography method and which is also excellent in insulating property, heat resistance, adhesiveness and room temperature storage stability. Another object of the present invention is to provide a light-shielding film formed using this light-shielding thin film forming composition and a black matrix for a color filter.

[0010]

That is, the present invention is
(A) The following general formula (1)

[0011]

[Chemical 4] (However, in the formula, R ₁ and R ₂ are hydrogen atoms and have 1 to 5 carbon atoms.
Is an alkyl group or a halogen atom, and X is-
_{CO -, - SO 2 -,} - C (CF 3) 2 -, - Si (C
_{H 3) 2 -, - CH} 2 -, - C (CH 3) 2 -, - O
-,

[0012]

[Chemical 5] Or an absent, n is an integer of 0 to 10) and an epoxy compound mainly composed of a compound represented by (meta)
An unsaturated group-containing compound (A) obtained by further reacting a reaction product with acrylic acid with a polybasic acid carboxylic acid or an anhydride thereof.
Component), (B) photopolymerization initiator or sensitizer (B component), and (C) at least one or more selected from a black organic pigment, a mixed color organic pigment and a light shielding material (C component), and (D)
A compound having an epoxy group as an optional component (component D)
And a composition containing 100 parts by weight of the above-mentioned component A.
Then, the D component is 0 or 1 part by weight or less, and the B component is
0.1 to 30 parts by weight, and C component is 50 to 250 parts by weight
And a spiro orthoester group in one molecule
A light-shielding thin film-forming composition comprising no spiro orthoester compound having two or more compounds .

Further, the present invention is a light-shielding film formed by a photolithography method using such a light-shielding thin film forming composition, and a black matrix for a color filter. The light-shielding film of the present invention has a volume resistance
It has a light-shielding rate of 10 ¹³ Ω · cm or more and a light-shielding rate of 99% or more, and is suitable for the production of color filters such as the electrodeposition method and the micelle electrolysis method.

The contents of the present invention will be described in detail below. In the present invention, the unsaturated group-containing compound as the component A is a compound having both an ethylenically unsaturated double bond and a carboxyl group, and specific examples thereof include the following. First, an epoxy compound is reacted with (meth) acrylic acid (which means "acrylic acid and / or methacrylic acid"), and the obtained compound having a hydroxy group is treated with a polybasic acid carboxylic acid or an anhydride thereof. It is an epoxy (meth) acrylate acid addition product obtained by the reaction.

Specific examples of the epoxy compound used in this reaction include various aromatic epoxy compounds. For example, as its bisphenol component, bis (4
-Hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4
-Hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-
Hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-)
3,5-dichlorophenyl) hexafluoropropane,
Bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, Bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2- Bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bi (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5
-Dichlorophenyl) ether and other compounds,

[0016]

[Chemical 6] Having 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-)
3-chlorophenyl) fluorene, 9,9-bis (4-
Hydroxy-3-bromophenyl) fluorene, 9,9
-Bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, Compounds containing 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, and further 4,4'-biphenol And compounds containing 3,3′-biphenol and the like. Moreover, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, etc. can also be used. An oligomer unit is mixed into these during glycidyl etherification, but there is no problem in the performance of the present resin composition.

As the polybasic acid carboxylic acid or its acid anhydride capable of reacting with the hydroxy group in the epoxy (meth) acrylate molecule obtained by reacting such an epoxy compound with (meth) acrylic acid, , For example,
Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid and its acid anhydrides, Furthermore, aromatic polyvalent carboxylic acids such as benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid and biphenyl ether tetracarboxylic acid, and acid dianhydrides thereof can be mentioned.

A photopolymerizable unsaturated group-containing compound (A having an ethylenically unsaturated double bond and a carboxyl group)
Regarding the component), only one of them can be used alone as the A component, and a mixture of two or more types can also be used as the A component. The acid anhydride and acid dianhydride used in this case may be used in any ratio, and a ratio suitable for forming a fine pattern by exposure and alkali development operations can be selected.

The method for producing the unsaturated group-containing compound of the component A by reacting the epoxy (meth) acrylate with the polybasic acid or its acid anhydride is not particularly limited, and one example thereof will be described. For example, it can be manufactured as follows. That is, first, 9,9-bis (4-
(Hydroxyphenyl) fluorene and epichlorohydrin are reacted to synthesize a bisphenolfluorene type epoxy compound represented by the following general formula (2), and the bisphenolfluorene type epoxy compound of this general formula (2) and the following general formula ( 3) is reacted with (meth) acrylic acid to synthesize a bisphenolfluorene type epoxy acrylate resin represented by the following general formula (4), and then in a cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate. The bisphenol fluorene type epoxy acrylate resin of the general formula (4) is reacted with the polybasic acid or its acid anhydride under heating to produce the desired unsaturated group-containing compound.

[0020]

[Chemical 7]

Regarding the reaction at this time, the acid anhydride is 1 / mol per 1 mol of the OH group of the epoxy acrylate resin.
It is desirable to react quantitatively so as to be 2 mol, and therefore the reaction temperature is 90 to 130 ° C, preferably 95 to 125 ° C. This reaction is the same for all compounds having the unit structure of the general formula (1).

The composition for forming a light-shielding thin film of the present invention contains a photopolymerizable unsaturated group-containing compound as the above-mentioned component A, and a photopolymerization initiator or a sensitizer as the component B for photocuring this. Including agents. The photopolymerization initiator and sensitizer of the B component are not only used for the photocuring of the A component described above, but also a photopolymerizable (meth) acrylic monomer or (meth) compounded as necessary. It is also used as a polymerization initiator for a photopolymerizable unsaturated compound such as an acrylic oligomer.

Examples of the component B photopolymerization initiators and sensitizers used for such purposes include acetophenone,
2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p
Acetophenones such as -tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, p,
Benzophenones such as p′-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and other benzoin ethers, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4 -Diethylthioxanthone, 2-
Sulfur compounds such as methylthioxanthone and 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoylper Organic peroxides such as oxide and cumene peroxide,
Examples thereof include thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole.

These photopolymerization initiators and sensitizers are
Only one species may be used alone, or two or more species may be used in combination. Further, a compound which does not act as a photopolymerization initiator or a sensitizer by itself but which can increase the ability of the photopolymerization initiator or a sensitizer by using in combination with the above compound may be added. it can. Examples of such compounds include tertiary amines such as triethanolamine, which are effective when used in combination with benzophenone.

The content of the component B is preferably 0.1 to 30 parts by weight per 100 parts by weight of the component A. When the content of the component B is less than 0.1 parts by weight, photopolymerization is performed. Slows down and reduces sensitivity. On the other hand, if the amount exceeds 30 parts by weight, it is difficult for light to reach the inside, so that the uncured portion deteriorates the physical properties, for example, the adhesion between the substrate and the resin deteriorates.

The C component black organic pigment, mixed color organic pigment and light-shielding material used in the present invention are preferably excellent in heat resistance, light resistance and solvent resistance. Here, examples of the black organic pigment include perylene black and cyanine black, and examples of the mixed color organic pigment include at least two or more selected from red, blue, green, purple, yellow, cyanine, magenta, and the like. It is a mixture of pigments and is pseudo-blackened.
Examples thereof include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. These can be used alone or in an appropriate combination of two or more.

The blending ratio of the component C is 50 to 250 parts by weight, preferably 70 to 230 parts by weight, based on 100 parts by weight of the component A. If the amount is less than 50 parts by weight, the light-shielding property becomes insufficient, and the film thickness must be increased to obtain the desired contrast, and the surface smoothness of the color filter cannot be obtained. On the other hand, when the amount exceeds 250 parts by weight, the dispersion stability of the light-shielding film forming composition containing the component C decreases, and the content of the photosensitive resin serving as the original binder also decreases, which impairs the development characteristics. In addition to the undesirable problem that the film-forming ability is impaired, the light-shielding film is electrically conductive (volume resistance is 10 ¹³
( Less than Ω · cm ), the insulation is poor and the production of a color filter becomes impossible, which is not preferable.

Further, the epoxy compound of the component D of the present invention should not be compounded, or even if it is compounded, it should be kept in the range of 1 part by weight or less, preferably 0.5 part by weight or less, relative to 100 parts by weight of the component A. is there. Within this range, there is no problem in maintaining the light shielding property and room temperature storage stability. That is, since the content of the C component can be increased, it has a high light-shielding property, the viscosity is stable for a long time even at room temperature storage, the developing speed and the resolution at the time of patterning are stable, and the dimensional accuracy is further improved. An excellent color filter can be produced.

The composition for forming a light-shielding thin film of the present invention comprises a photopolymerizable unsaturated group-containing compound of component A having an ethylenically unsaturated double bond and a carboxyl group, and component B for curing this component A. Of the photopolymerization initiator or sensitizer, at least one selected from the component C black organic pigment, the mixed color organic pigment and the light shielding material exhibiting light shielding properties, and the component D epoxy compound in a solvent. It is a composition prepared by mixing and mixing at a predetermined ratio.

The composition for forming a light-shielding thin film of the present invention may be used as a coating agent or an adhesive,
In such a case, it is diluted with a solvent for the purpose of adjusting viscosity and the like. Examples of the solvent at that time include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve such as cellosolve acetate, and lactones such as γ-butyrolactone.

Further, in the composition for forming a light-shielding thin film of the present invention, a monomer or an oligomer having a photopolymerizable ethylenically unsaturated group other than the above-mentioned component A is added within a predetermined range depending on the purpose of use. It can be blended. As the monomers and oligomers that can be blended for this purpose,
For example, 2-hydroxyethyl (meth) acrylate,
Monomers having hydroxyl groups such as 2-hydroxypropyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene Glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acryle And (meth) acrylic acid esters such as glycerol (meth) acrylate. These compounds can be used alone or in combination of two or more. .

It is necessary to add these monomers and oligomers to the extent that the properties of the composition of the present invention and the cured product thereof are not impaired.
It is used in the range of 0 parts by weight or less. If the amount used exceeds 50 parts by weight, tackiness after pre-curing will be a problem.

In addition, the composition for forming a light-shielding thin film of the present invention may contain a curing accelerator, a thermal polymerization inhibitor, a plasticizer, if necessary.
Additives such as fillers, solvents, leveling agents and defoamers can be added. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and the like, and examples of the plasticizer include dibutylphthalate, dioctylphthalate, tricresyl, and the like. Can include glass fiber, silica, mica, alumina, and the like, and examples of the defoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic-based compounds.

The light-shielding film of the present invention is formed by the photolithography method using the above-described composition for forming a light-shielding thin film of the present invention. As the manufacturing process, first,
The photosensitive light-shielding thin film-forming composition is applied as a solution to the surface of the substrate, and then the solvent is dried by precure (prebaking), and then a photomask is applied onto the coating film thus obtained, The exposed area is cured by irradiating with actinic rays, and the unexposed area is further developed with a weak alkaline aqueous solution to form a pattern, and post-baking is performed as post-drying.

As a substrate on which the solution of the composition for forming a light-shielding thin film is applied, a transparent electrode such as ITO or gold is vapor-deposited or patterned on glass or a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.). Items such as tatami are used.

As a method for applying the solution of the composition for forming a light-shielding thin film of the present invention to a substrate, a known solution dipping method, a spray method, a roller coater machine, a land coater machine or a spinner machine can be used. Either method can be adopted. By these methods, after coating to a desired thickness, the solvent is removed (prebaking) to form a film.

Prebaking is performed by heating with an oven, a hot plate or the like. The heating temperature and heating time in prebaking are appropriately selected according to the solvent used, and for example, the heating is performed at a temperature of 80 to 150 ° C. for 1 to 30 minutes.

Further, the exposure performed after the pre-baking is performed by an exposure device, and by exposing through a photomask, only the resist in the portion corresponding to the pattern is exposed. The exposure machine and its exposure irradiation conditions are appropriately selected, and for the light to be irradiated, for example, visible light, ultraviolet rays, X-rays and electron beams can be used, and the irradiation amount is, for example, 1 to 1000 m.
It is selected within the range of J / cm ² , but is not particularly limited.

The alkali development after exposure is carried out for the purpose of removing the resist in the unexposed portion, and a desired pattern is formed by this development. Examples of the developer suitable for this alkali development include an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. In particular, sodium carbonate, potassium carbonate, carbonate, etc. Using a weak alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as lithium,
The development is preferably carried out at a temperature of 20 ° C., preferably 20 to 40 ° C., and a fine image can be precisely formed by using a commercially available developing machine, ultrasonic cleaning machine or the like.

After developing in this way, 80 to 220
Heat treatment (post-baking) under conditions of ℃ and 10 to 120 minutes
Is done. This post-baking is performed for the purpose of increasing the adhesion between the patterned light-shielding film and the substrate. This is performed by heating with an oven, a hot plate or the like as in the pre-baking. The patterned light-shielding film of the present invention is formed through the above-mentioned steps by the photolithography method.

As described above, the composition for forming a light-shielding thin film of the present invention is suitable for forming a fine pattern by operations such as exposure and alkali development, but it is possible to form a pattern by conventional screen printing. Also, it is possible to obtain a light-shielding film having excellent light-shielding properties, adhesion, electrical insulation properties, heat resistance, and chemical resistance.

The composition for forming a light-shielding thin film of the present invention is
The ink can be preferably used as a coating material, and in particular, a color filter ink used in a liquid crystal display device or a photographing element, and a light-shielding film formed by the ink are useful as a color filter, a black matrix for liquid crystal projection, and the like. Furthermore, the composition for forming a light-shielding thin film of the present invention is, in addition to the color filter ink of the color liquid crystal display as described above, various multicolor display material ink materials for color liquid crystal display devices, color facsimiles, image sensors and the like. Can also be used as

[0043]

EXAMPLES The present invention will be described in detail below with reference to synthesis examples of unsaturated group-containing compounds as component A, and examples and comparative examples of compositions for forming light-shielding thin films and light-shielding films using the same. To do.

Synthesis Example 1 In a 500 ml four-necked flask, 231 g of a bisphenolfluorene type epoxy resin (epoxy equivalent 231) and 450 m of triethylbenzylammonium chloride were added.
g, 100 mg of 2,6-di-isobutylphenol,
72.0 g of acrylic acid was charged and mixed, and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature of the solution was gradually increased in a cloudy state and heated to 120 ° C. to completely dissolve the solution. The solution gradually became clear and viscous, and stirring was continued in that state. The acid value of this solution was measured, and heating and stirring were continued until it became less than 2.0 mgKOH / g. It took 8 hours for the acid value to reach the target (acid value 0.8). And it cooled to room temperature and obtained the colorless and transparent solid.

Next, 2 kg of cellosolve acetate was added to 303 g of the bisphenol fluorene type epoxy acrylate resin obtained above to make a solution, and then 1, 2, 3,
38 g of 6-tetrahydrophthalic anhydride, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to 1
Compound 1 was obtained by reacting at 10 to 115 ° C for 2 hours. The reaction of the acid anhydride during this reaction was confirmed by the disappearance of the 1780 cm ⁻¹ peak in the IR spectrum. The obtained compound 1 had an inherent viscosity of 0.3 dl / g (η _inh
= 0.3).

Synthesis Example 2 Compound 2 was obtained in the same manner as in Synthesis Example 1 except that 153 g of biphenyl type epoxy resin (epoxy equivalent 153) was used in place of the bisphenol fluorene type epoxy resin in Synthesis Example 1. The obtained compound 2 had an inherent viscosity of 0.2 dl / g (η _inh = 0.2).

Synthesis Example 3 Instead of the bisphenolfluorene type epoxy resin in Synthesis Example 1, 163 g of benzophenone type epoxy resin
Compound 3 was obtained in the same manner as in Synthesis Example 1 except that (epoxy equivalent 163) was used. The obtained compound 3 had an inherent viscosity of 0.3 dl / g (η _inh = 0.3).

Synthesis Example 4 A compound 4 was obtained in the same manner as in Synthesis Example 1 except that 181 g of a sulfone type epoxy resin (epoxy equivalent 181) was used instead of the bisphenol fluorene type epoxy resin in Synthesis Example 1. The reaction of the acid anhydride was confirmed by IR spectrum. The inherent viscosity of the obtained compound is
It was 0.3 dl / g (η _inh = 0.3).

Synthesis Example 5 Compound 5 was obtained in the same manner as in Synthesis Example 1 except that 221 g of hexafluoropropane type epoxy resin (epoxy equivalent 221) was used in place of the bisphenol fluorene type epoxy resin in Synthesis Example 1. The obtained compound 5 had an inherent viscosity of 0.4 dl / g (η _inh
= 0.4).

Synthesis Example 6 Instead of the bisphenol fluorene type epoxy resin used in Synthesis Example 1, 163 g of dimethylsilane type epoxy resin.
Compound 6 was obtained in the same manner as in Synthesis Example 1 except that (epoxy equivalent 163) was used. The obtained compound 6 had an inherent viscosity of 0.2 dl / g (η _inh = 0.
2).

Synthesis Example 7 Instead of the bisphenolfluorene type epoxy resin in Synthesis Example 1, biphenylmethane type epoxy resin 156.
Compound 7 was obtained in the same manner as in Synthesis Example 1 except that g (epoxy equivalent 156) was used. The obtained compound 7 had an inherent viscosity of 0.4 dl / g (η _inh = 0.
4).

Synthetic Example 8 Instead of the bisphenol fluorene type epoxy resin in Synthetic Example 1, a biphenylpropane type epoxy resin 17 was used.
Synthesis Example 1 except that 0 g (epoxy equivalent 170) was used
Compound 8 was obtained in the same manner as. The obtained compound 8 had an inherent viscosity of 0.4 dl / g (η _inh =
0.4).

Synthesis Example 9 Compound 9 was obtained in the same manner as in Synthesis Example 1 except that 157 g of biphenyl ether type epoxy resin (epoxy equivalent 157) was used in place of the bisphenol fluorene type epoxy acrylate resin in Synthesis Example 1. The obtained compound 9 had an inherent viscosity of 0.3 dl / g (η _inh = 0.3).

Examples 1 to 10 and Comparative Examples 1 to 3 Next, the A component obtained in the above Synthesis Examples 1 to 9 was used, and the B component, the C component, and the D component were added thereto, and if necessary, Example 1 in which a photopolymerizable acrylic monomer or oligomer was blended and an organic solvent was further mixed to prepare a resist solution having a blending ratio (parts by weight) shown in Tables 1 and 2, respectively.
10 to 10 and Comparative Examples 1 to 3 were used as light-shielding thin film forming compositions.

The resist solutions thus obtained were applied on a degreased and washed glass plate having a thickness of 1.2 mm to a thickness of about 1 μm using a spin coater and dried, and then a photomask was brought into close contact with it to give 500 W. Ultraviolet light having a wavelength of 365 nm and an illuminance of 10 mW / cm ² was irradiated for 50 seconds using the high pressure mercury lamp. After the exposure, the film was developed with a 0.4 wt% sodium carbonate aqueous solution at 23 ° C. for 60 seconds to remove the unexposed portion of the coating film, and then heat-dried at 200 ° C. for 30 minutes using a hot air dryer. . The shape of the obtained black matrix was very good.

With respect to the obtained sample, each of the drying property of the coating film, the developing property with respect to an alkaline aqueous solution, the light-shielding rate, the electrical characteristics (volume resistance value), the exposure sensitivity, the adhesiveness with the substrate, the heat resistance and the chemical resistance was obtained. The physical properties were evaluated. The results are shown in Tables 1 and 2. Further, as a comparative example, the composition shown in Table 2 was used to form a light-shielding thin film in the same manner as in the example, and the respective physical properties were examined. The results are shown in Table 2.

The data of each physical property were measured by the following methods and conditions. (1) Dryability of coating film The drying property of the coating film was evaluated according to JIS-5400.
The evaluation ranks are as follows. ◯: No tack was observed at all Δ: Slight tack was observed x: Significant tack was observed

(2) Developability in Alkaline Aqueous Solution The sample was immersed in an aqueous 0.4% by weight sodium carbonate solution for 60 seconds for development, and after development, magnified 400 times and evaluated. The evaluation ranks are as follows. ◯: Good developability (no residue left on the glass and good pattern shape) X: Poor developability (some residue left on the glass,
(The pattern shape is bad)

(3) Light-shielding rate The light-shielding rate of the light-shielding film was measured by measuring the transmittance at a wavelength of 550 nm at a film thickness of 1 μm with a spectrophotometer, and the light-shielding rate (%) = 100.
-Calculated by the formula of transmittance (%).

(4) Volume resistance The volume resistance was evaluated according to JIS-K6911.

(5) Exposure sensitivity Kodak step tablet No. 2 (manufactured by Eastman Kodak Co., negative film having optical density steps of 0.15 and 21 steps) was adhered to the coating film, and a light amount of 500 mJ / cm ² was irradiated using a 500 W high-pressure mercury lamp. Next, the number of steps of the step tablet with respect to the weak alkaline aqueous solution described above was examined for this coating film (in this evaluation method, the higher the sensitivity, the greater the number of remaining steps).

(6) Adhesion with Substrate After exposure and development, the coating film heated at 200 ° C. for 30 minutes
A cross-cut was made so as to make at least 100 crosses, and then a peeling test was performed using cellophane tape, and the state of peeling of the crosses was visually evaluated.
The evaluation ranks are as follows. ◯: No peeling was observed at all ×: Peeling was observed even a little

(7) Heat-resistant exposure After development, the coating film heated at 200 ° C. for 30 minutes
It was placed in an oven at 50 ° C. for 3 hours and the state of the coating film was evaluated. The evaluation ranks are as follows. ◯: There is no abnormality in the appearance of the coating film ×: There are cracks or peeling in the appearance of the coating film

(8) Chemical resistance After exposure and development, a coating film which was heated at 200 ° C. for 30 minutes was used.
It was immersed in the following chemicals under the following conditions, and the appearance and adhesion after immersion were evaluated. Acid resistance: 5% HCl, 25 ° C for 24 hours Alkali resistance: 5% NaOH, 25 ° C for 24 hours 4% KOH, 50 ° C for 10 minutes 1% NaOH, 80 ° C for 5 minutes Solvent resistance: NMP, 40 ° C -10 minutes NMP, 80 ° C-5 minutes (NMP: N-methylpyrrolidone)

(9) Storage stability at room temperature The composition for forming a light-shielding thin film after 30 days of storage at 25 ° C. was evaluated by the same method as in the initial evaluation of developability (2).

[0066]

[Table 1]

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[Table 2]

As is clear from the results shown in Tables 1 and 2, the light-shielding thin film-forming fat compositions according to Examples 1 to 10 of the present invention and the light-shielding films formed from the same were evaluated for their developability, light-shielding rate, and
It was confirmed that the electrical characteristics (volume resistance value), exposure sensitivity, adhesion to the substrate, heat resistance, chemical resistance, and room temperature storage stability were excellent. In Comparative Example 1, the room temperature storage stability of the epoxy resin mixture was lowered, and in Comparative Example 2, the room temperature storage stability and the light blocking rate were poor.
Further, in Comparative Example 3, due to the excessive mixing of the black pigment, the initial developability, the adhesiveness, and the volume resistance were extremely poor.

[0069]

The composition for forming a light-shielding thin film of the present invention is excellent in storage stability at room temperature. When it is used, the coating film becomes tack-free after drying with a solvent, has a high light-shielding property, and is also excellent in developability. A fine resist pattern can be drawn on the substrate. Further, after curing, a light-shielding film having excellent adhesiveness, heat resistance, solvent resistance, and insulating properties as compared with conventional ones is provided.

Therefore, forming a black matrix for producing a color filter for a liquid crystal display by using the composition for forming a light-shielding thin film of the present invention has the advantages that the steps are simple and can be formed at low cost. Yes,
Furthermore, a color filter having a high contrast and an extremely excellent quality can be obtained, and a liquid crystal color display, a liquid crystal color television, a color facsimile, a color image sensor and the like can be easily manufactured.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenichi Kitamura Kenichi Kitamura 1618 Ida, Nakahara-ku, Kawasaki-shi, Kanagawa, Nippon Steel Corporation Advanced Technology Research Laboratories (56) Reference JP-A-7-64281 (JP, A) JP-A-6-1938 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 004-7/18

Claims (6)

(57) [Claims] 1. (A) The following general formula (1): (However, in the formula, R ₁ and R ₂ are hydrogen atoms and have 1 to 5 carbon atoms.
Is an alkyl group or a halogen atom, and X is-
_{CO -, - SO 2 -,} - C (CF 3) 2 -, - Si (C
H ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, and Or an absent, n is an integer of 0 to 10) and an epoxy compound mainly composed of a compound represented by (meta)
An unsaturated group-containing compound (A) obtained by further reacting a reaction product with acrylic acid with a polybasic acid carboxylic acid or an anhydride thereof.
Component), (B) photopolymerization initiator or sensitizer (B component), and (C) at least one or more selected from a black organic pigment, a mixed color organic pigment and a light shielding material (C component), and (D)
A compound having an epoxy group as an optional component (component D)
A composition comprising and (provided that the spiro orthoester group is
Containing spiro orthoester compounds having two or more
It is not), and with respect to 100 parts by weight of the component A,
Component D is 0 or 1 part by weight or less, and component B is 0.1 to 0.1 parts by weight.
30 parts by weight, and C component is 50 to 250 parts by weight, the composition for forming a light-shielding thin film. 2. The C component is added to 100 parts by weight of the A component.
70 to 230 parts by weight, and D component is 0 or 0.5 parts by weight
The composition for forming a light-shielding thin film according to claim 1, which is not more than 1 part . 3. X in the general formula (1) is The composition for forming a light-shielding thin film according to claim 1 or 2. 4. A light-shielding film formed by curing the composition for forming a light-shielding thin film according to claim 1. 5. A light-shielding film formed by photolithography using the light-shielding thin film-forming composition according to claim 1, having a volume resistance of 10 ¹³ Ω · cm.
The light-shielding film has the above-mentioned properties and a light-shielding ratio of 99% or more. 6. A black matrix for a color filter, which is patterned into a black matrix shape for a color filter using the composition for forming a light-shielding thin film according to claim 1.