JPH1017779A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition causing little variation of the dissolution rate in an alkaline aqueous solution by the variation of the acid value and exhibiting extremely stable performance. SOLUTION: This photosensitive resin composition contains (a) a resin containing carboxyl group, (b) an actinic radiation-induced polymerization initiator and (c) a solvent as essential components. The component (a) is a resin having vinyl group and carboxyl group and produced by the addition reaction of (I) a polymer containing a segment having carboxyl group with (II) a compound having one or more vinyl groups and epoxy groups in one molecule. The resin contains a t-phosphine in an amount of 0.5-5wt.% based on the resin. The composition may further contain (d) a thermally crosslinking agent and/or a compound having polymerizable unsaturated bond and optionally (e) a pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition. More specifically, it is an object of the present invention to provide a photosensitive resin composition in which characteristic fluctuations due to fluctuations in the acid value of the resin are small.

[0002]

2. Description of the Related Art Conventionally, many photosensitive resin compositions which can be developed with an aqueous alkali solution, using a resin having a carboxyl group, such as a polyacrylic acid copolymer or a polymethacrylic acid copolymer, are known. For example,
JP-A-1-200353, JP-A-4-7373 and the like, photosensitive resins comprising an acrylic polymer and an azide compound, acrylate monomers and organic polymer binders as disclosed in JP-A-1-152449 and the like. There is a radical polymerization type photosensitive resin composed of a photopolymerization initiator.

However, when the resin containing a carboxyl group is applied to a photosensitive resin composition, no consideration is given to a change in dissolution rate in an alkaline aqueous solution due to a change in acid value. There is a problem that the development time, sensitivity, resolution, and the like required for patterning also fluctuate greatly with the fluctuations in the pattern.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive resin composition exhibiting extremely stable performance with little change in the dissolution rate in an aqueous alkali solution due to a change in acid value.

[0005]

The present inventors have prepared a photosensitive resin composition containing (a) a resin containing a carboxyl group, (b) a polymerization initiator irradiated with active rays, and (c) a solvent as essential components. As a result of intensive studies, as a component (a), a polymer having a segment having a carboxyl group and a resin having a vinyl group obtained by adding a compound having at least one vinyl group and an epoxy group in one molecule are used. In addition, since the resin contains tertiary phosphine at a concentration of 0.5 to 5% by weight based on the resin, the rate of dissolution in an alkaline aqueous solution due to a change in the acid value of the resin is small, and
In particular, they have found that a resin suitable for a photosensitive resin composition can be obtained, and have accomplished the present invention. Hereinafter, the present invention will be described in detail.

As described above, the present invention relates to a polymer (I) containing a segment having a carboxyl group and a carboxyl group obtained by adding a compound (II) having at least one vinyl group and an epoxy group in one molecule. It is characterized in that the resin (a) containing a tertiary phosphine at a concentration of 0.5 to 5% by weight based on the resin having a vinyl group is used.

As the polymer (I) containing a segment having a carboxyl group, a polymer represented by the following formula can be exemplified.

[0008]

Embedded image

Wherein R ₁ may be the same or different and represents a hydrogen atom or a methyl group, and R ₂ has 1 to 1 carbon atoms.
5 represents an alkyl group having a linear or side chain structure. In addition, m and n represent the degree of polymerization, and m / n is 0.5 to 2.4 (molar ratio). More specifically, methacrylic acid-acrylic acid ester copolymer, methacrylic acid-methacrylic acid ester copolymer, acrylic acid-acrylic acid ester copolymer, acrylic acid-methacrylic acid ester copolymer and the like. Examples thereof include methacrylic acid-butyl acrylate copolymer, methacrylic acid-methyl methacrylate copolymer, acrylic acid-butyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, and the like. Further, a monomer obtained by copolymerizing a monomer having an aromatic ring such as styrene or benzyl (meth) acrylate or a different monomer such as 2-hydroxymethyl (meth) acrylate with the above copolymer may be used.

The compound (II) having one or more vinyl groups and epoxy groups in one molecule includes (3,4-epoxycyclohexyl) methyl methacrylate, (3,4
4-epoxycyclohexyl) methyl acrylate, glycidyl methacrylate, allyl glycidyl ether and the like. These may be used alone or in combination of two or more. The molecular weight (Mw) of the resin having a carboxyl group and a vinyl group obtained by reacting the polymer (I) with the compound (II) is 10,000
It is preferably in the range of 0 to 80,000, especially 1
More preferably, it is in the range of 5,000 to 50,000. The acid value of the reaction product was 40 to 100 KOH mg /
g, preferably 45 to 70 KOH
More preferably it is in mg / g. A resin having a carboxyl group and a vinyl group obtained by reacting a polymer having a segment having a carboxyl group with a compound having one or more vinyl groups and an epoxy group in one molecule is produced as follows. Can be. With respect to 1 equivalent of the carboxyl group of the polymer (I), the epoxy group of the compound (II) is 0.7-1.3 equivalent, preferably 0.9-1.1 equivalent to a desired acid value. Charge in the ratio and perform addition reaction.

In the present invention, as the catalyst, for example,
Primary phosphines, tertiary amines, quaternary ammonium salts and the like are used. Specifically, triphenylphosphine,
Examples include triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, and the like, and a plurality of these can be used in combination.

The amount of the above-mentioned catalyst to be used is as follows: Compound (I)
0.1 to 10 based on the combined weight of
It is preferably used in the range of 0.5% by weight, more preferably in the range of 0.5 to 5% by weight. After the addition reaction, the resin having a carboxyl group and a vinyl group may be used in the form of a solution without isolation, or may be purified by removing a solvent, reprecipitating, or the like. However, in the photosensitive resin composition of the present invention, the tertiary phosphine is preferably contained in an amount of 0.5 to 5% by weight based on the weight of the resin having a carboxyl group and a vinyl group.
Tertiary phosphine may be added so as to have the above ratio.

During the above reaction, it is desirable to use a diluent. As the diluent, various solvents such as esters, alcohols, ethers, and ketones can be used, and they can be used alone or as a mixture. Specific examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, methoxybutanol, methyldipropylene glycol, butyl lactone, and the like.

In order to prevent polymerization of vinyl groups during the reaction, it is preferable to use a polymerization inhibitor. Specifically, methylhydroquinone, hydroquinone, phenothiazine, t
-Butylmethoxyphenol and the like can be exemplified, and its use amount is from 0.01 to 0.5% by weight, particularly preferably from 0.05 to 0.2% by weight, based on the raw material mixture. The reaction temperature is generally between 70 and 140C.

As the actinic ray irradiation polymerization initiator (b), various compounds such as halomethyl oxazole compounds, halomethyl-s-triazine compounds, onium salts, benzoin ethers, benzophenones, xanthones, acetophenone derivatives, and azides can be used. Can be used. More specifically, examples of the halomethyloxazole-based compound include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole and 2-trichloromethyl-5- (p-cyanostyryl) -1,3. , 4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,
4-oxadiazole and the like.

The halomethyl-s-triazine compound is particularly preferably a trihalomethyl-s-triazine compound such as 2,4-bis (trichloromethyl) -6-p.
-Methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-dimethylaminophenyl-1,3-butadienyl) -s-triazine,
4-bis (trichloromethyl) -6- (p-phenylstyryl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2,4-bis (trichloromethyl) -6 -Phenyl-s-triazine, 2 [2 '(5 "-methylfuryl) ethylidene]-
4,6-bis (trichloromethyl) -s-triazine,
2 (2′-furylethylidene) -4,6- (trichloromethyl) -s-triazine, 5,7-bis (tribromomethyl) -s-triazolo [1,5-a] pyrimidine and the like.

These may be used alone or in combination of two or more. Examples of benzoin ethers include benzoin methyl ether and benzoin isobutyl ether. Examples of the benzophenones include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, Michler's ketone, o-benzoylmethylbenzoate and the like. As xanthones,
For example, xanthone, thioxanthone, 2-chlorothioxanthone, 2-alkylthioxanthone, 2,4-dialkylthioxanthone and the like can be mentioned.

Examples of the acetophenone derivative include acetophenone, trichloroacetophenone, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2-phenylacetophenone. As azide, for example, 4,4′-diazidostilbene, 4,4′-
Diazidostilbene-2,2-disulfonic acid-N, N-
Examples thereof include diethyleneoxyethylamide, p-azidobenzalacetophenone, and azidochalcone.

Examples of the onium salt include various sulfonium salts, iodonium salts, and diazonium salts. Specific examples include triphenylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, α-
Naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate (or hexafluoroantimonate), diphenyl-t-butylphenylsulfonium trifluoromethanesulfonate, diphenylmethoxyphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, di- t-butylphenyliodonium trifluoromethanesulfonate (or hexafluoroantimonate or tetrafluoroborate), methoxyphenylphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, aminophenylbenzenediazonium tetrafluoroborate, pyrylene azonium tetrafluoroborate And the like. These may be used alone or in combination.

In the composition of the present invention, in combination with the component (a) as a binder component, a halomethyl-s-triazine compound, particularly trihalomethyl-s-triazine, is used as a polymerization initiator in view of image forming properties. Is preferred. In the present invention, a sensitizer may be used in combination for improving the sensitivity. Examples of the sensitizer include 2-nitrofluorene, 2,4,7-trinitrofluorenone, benzuanthrone, picramide, and 1,2-
Benzanthraquinone, 11-chloro-6-hydroxybenzanthrone, phenanthraquinone, 4- (4-butoxyphenyl) -2,6-diphenylthiopyrylium perchlorate and the like are exemplified.

Further, in order to improve crack resistance, solvent resistance, etc., various heat crosslinking agents and / or compounds having a polymerizable unsaturated bond may be added to the mixture of the present invention. Examples of the thermal crosslinking agent include compounds having at least two same or different residues such as alkoxy and acyloxy, which react with the binder to form a crosslinked matrix, for example, bis, tris or tetra (hydroxymethyl) -substituted aromatic compounds. Group or heterocyclic aromatic compound, bis, tris or tetra (acetoxymethyl) -substituted aromatic compound or heterocyclic aromatic compound, melamine having N-hydroxymethyl group, melamine having N-alkoxymethyl group or N -Melamine having an acyloxymethyl group, a compound containing an epoxy group such as a novolak type epoxy resin, a bisphenol A type epoxy resin, a halogenated bisphenol A type epoxy resin, an alicyclic epoxy resin, an acetal resin such as polyvinyl butyral, and benzoyl Peroxide, Lachlorobenzoyl peroxide, acetyl peroxide, peroxides such as lauroyl peroxide, blocked isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, cyclohexylene diisocyanate, and various blocking agents such as ethanol, butanol, dimethyl malonate, imidazole, ε-caprolactam , Methylcellosolve, ethylene glycol and the like. These may be used alone or 2
It may be used in combination of more than one kind.

Examples of the compound having a polymerizable unsaturated bond include various vinyl monomers and vinyl oligomers. Specific examples include acrylate monomers and methacrylate monomers, and esters of polyhydric alcohols such as ethylene glycol and trimethylolpropanol with acrylic acid and methacrylic acid, and polymers and oligomers having an alcoholic hydroxyl group such as polyvinyl alcohol. And the above-mentioned esters. In addition, acrylate melamine, methacrylate melamine, urethane methacrylate, urethane acrylate and the like are also included in the present invention.

More specifically, mention may be made of 2-hydroxyethyl methacrylate, n-butyl methacrylate, glycidyl methacrylate, 2-ethylhexyl acrylate, diethylene glycol dimethacrylate, polyethylene glycol methacrylate, trimethylolethanetetramethacrylate, tetramethylolmethanetetraacrylate and the like. Can be These may be used alone or in combination of two or more.

The pigment used in the present invention includes:
For example, condensed polycyclic pigments such as anthraquinone-based and perylene-based pigments, phthalocyanine pigments, and organic pigments such as azo pigments,
Inorganic pigments such as carbon black can also be used. These can be used alone or in combination of two or more. In the present invention, it is preferable to use a dispersant to disperse the pigment in the mixture. The pigment can be used by being internally added to the pigment in a form where the pigment is subjected to a surface treatment in advance, or can be used by being externally added to the pigment. As such, nonionic, anionic or cationic dispersants are used. In addition, rosin, rosin modified with an unsaturated carboxylic acid, and the like are also used. The dispersant is added in an amount of 0 to 50% by weight, preferably 0 to 35% by weight, based on the pigment.

In the present invention, as the solvent, ethyl cellosolve, propylene glycol methyl ether acetate (PGMEA), ethyl lactate, polyethylene glycol, polypropylene glycol, cyclohexanone, propylene glycol methyl ether and the like are used. May be used.
Incidentally, a stabilizer, an antioxidant and the like can be further added to the mixture of the present invention.

The composition of the present invention preferably contains components other than the solvent (c) and the pigment (e) in the following proportions. Polymer (a): 70 to 98% by weight, compound (b):
2-30% by weight. When the thermal crosslinking agent and / or the compound (d) having a polymerizable unsaturated bond is used, if the amount of the compound is too large, the viscosity of the composition increases and the composition becomes sticky. ) 1 part by weight, 0.010
To 0.25 parts by weight, preferably 0.025 to 0.20 parts by weight, more preferably 0.030 to 0.15 parts by weight, and a polymer (a) and a thermal crosslinking agent and / or a polymerizable polymer. For the combined compound (d) having a saturated bond,
It is preferable to add 2 to 30% by weight of the compound (b).
The amount of the pigment is 0.1 to 2 parts by weight based on 1 part by weight of the mixture. In addition, it is desirable to use 1 to 15 parts, preferably 2 to 10 parts of the solvent (c) with respect to 1 part of the total of the non-solvent components by weight.

In the present invention, the pattern can be obtained as described above because the compound (b) generates radicals or ions by irradiation with actinic rays, and this reacts with the unsaturated bond in the polymer (a). To form a crosslinked matrix, and insolubilize the irradiated portion with an aqueous alkaline solution. In the above, for example, a silicate, a metasilicate, a hydroxide, a hydrogen phosphate, an ammonia, or the like of an alkali metal and / or an alkaline earth metal, particularly, an ammonium ion is used as the developer. As a developer containing no metal ion, for example, USP 4,729,94
No. 1, EP-A62,733 and the like can be used. In addition, a surfactant, a detergent, an organic solvent, and the like may be added to the developer for the purpose of assisting the removal of the pigment residue during development. Examples of the additives added to the developer for the above purpose include nonionic activators, ionic activators, alcohols, carboxylic acids, amines and derivatives thereof, and specifically, polyalkylene glycols and esters thereof, Examples include a polyhydric alcohol ester alkylene oxide adduct, an alcohol alkylene oxide adduct, an alkylphenol alkylene oxide adduct, a sulfonic ester, a sulfonate, a carboxylate, a carboxylate, an alkylamide alkylene oxide adduct, and an alkylamine. These may be added alone or in combination of two or more. In this case, the amount of addition is preferably 0.1 to 30% by weight based on the developer.

As a suitable substrate on which the composition of the present invention is applied, any material that constitutes or manufactures a capacitor, a semiconductor, a multilayer printed circuit, or an integrated circuit can be used. In particular, it may be a thermally oxidized silicon material and / or optionally doped. Examples thereof include a silicon material coated with aluminum, and other substrates commonly used in semiconductor technology such as silicon nitride, potassium arsenide, and indium phosphide. Further, a glass substrate, a glass substrate provided to an electrode such as indium tin oxide, a metal plate,
Metal foil (eg aluminum, copper or zinc) or metallized surface, optionally aluminum coated Si
An O ₂ material or the like is used as a base material.

These substrates may be subjected to heat treatment, surface polishing, etching, or treatment with a reagent to improve properties, for example, to enhance hydrophilicity. As a specific example, in order to improve the adhesion between the composition and the substrate, an adhesion promoter may be included, and in the case of silicon or silicon dioxide, 8-aminopropyltriethoxysilane, hexamethyldisilazane, or the like. A silane coupling agent can be applied. The layer thickness is
Depending on the field of application, for example, 0.1-100 μm,
In particular, it is in the range of 0.5 to 10 μm.

As a method of applying the composition of the present invention to a substrate, the composition can be applied to a substrate by spraying, flow coating, roll coating, spin coating, or dip coating. Next, the solvent is removed by evaporation, and the pattern forming material is left on the substrate. Removal of the solvent can be accelerated by heating or / and reduced pressure, if desired. It is important that the heating temperature does not cause deterioration of the pattern forming material and the substrate, and the heating temperature can be, for example, 150 ° C. Next, the layer is irradiated with actinic radiation so as to project a pattern. The layer is then treated with a developer to render the irradiated portions insolubilized and the unirradiated portions to dissolve to reveal the pattern. Further, after irradiation, heating and development may be performed. By this heating, for example, the sensitivity can be further improved. As the heating temperature, it is desirable that the shape of the pattern and the deterioration of the base material do not occur, for example, 200 ° C.
The following can be performed. As a light source used for the irradiation, for example, 190 to 450 nm, preferably 200 to 450 nm
UV irradiation in the 00 nm region may be mentioned, and electron beam or X-ray irradiation may also be used.

Further, as a method of producing a color filter using the mixture to which the pigment of the present invention is added, for example, a method of forming a color filter having a thickness of, for example, 0.5 to 10 μm on a glass substrate by an appropriate method in the coating method described above. To form a coat layer. In addition, as the glass substrate, a glass substrate having a black matrix formed on its surface can be used. After that, the layer is irradiated with the actinic radiation so that a pattern necessary for a color filter is projected. After the irradiation, the coat layer is treated with a developing solution to dissolve the unirradiated portion of the coat layer, so that a necessary pattern appears on the color filter. By repeating such a process according to the required number of colors, a color filter having a desired pattern can be obtained. Further, the image pattern obtained by the development in the above step can be further cured by heating or irradiation with actinic rays to improve crack resistance, solvent resistance and the like.

[0032]

The present invention will be described in more detail with reference to the following examples. Note that the present invention is not limited to this embodiment. The methods for synthesizing the resins used in the examples and comparative examples are shown below. A) Synthesis of a resin having a carboxyl group and an epoxy group Synthesis example 1 : methacrylic acid-butyl acrylate copolymer (copolymerization ratio 0.58: 0.43 (molar ratio), average molecular weight ( _Mw ) about 15,000) 5) 1: 1 mixed solvent solution of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether containing 56.4 g
1.3 g of triphenylphosphine as a catalyst in 60 g,
0.05 g of methoxyhydroquinone as a polymerization inhibitor,
43.6 g of (3,4-epoxycyclohexyl) methyl methacrylate was dissolved and heated at 80 ° C. in a nitrogen atmosphere to obtain an adduct. After completion of the reaction, the acid value of the resin was 52.
7 KOH mg / g and an average molecular weight (M _w ) of 24, 20
It was 0. This resin solution was used as it is in the following examples.

Synthesis Examples 2 and 3: The reaction was carried out in the same manner as in Synthesis Example 1 except that the amount of (3,4-epoxycyclohexyl) methyl methacrylate was changed so as to obtain a predetermined acid value. It was used in the examples as they were.
The physical properties of the polymer of Synthesis Example 1 are shown in Table 1 below.

Synthesis Examples 4 to 6 : The reaction was carried out in the same manner as in Synthesis Examples 1 to 3, except that the amount of triphenylphosphine was changed to 0.15 g, and the resin solution was used as it was in Comparative Examples. Table 1 Abbreviations Acid value (KOHmg / g) Molecular weight (Mw) ポ リ マ ー Polymer 1 52. 724,200 Polymer 2 55.4 22,300 Polymer 3 63.126,100 Polymer 4 51.227,300 Polymer 5 55.9 924,100 Polymer 6 59.125,000 B) Resin dissolution test Examples 1-3 : A solution containing the resin synthesized in Synthesis Examples 1-3 was spin-coated on a silicon substrate to about 1 μm, and then dried on a hot plate at 100 ° C. for 1 minute. The silicon substrate on which the resin layer was formed was immersed in a 0.0054N tetramethylammonium hydroxide aqueous solution, and the dissolution rate was calculated from the time required for complete dissolution and the initial film thickness.

Comparative Examples 1 to 3 : Using the solutions containing the resins synthesized in Synthesis Examples 4 to 6, the dissolution rates were calculated in the same manner as in Examples 1 to 3. Table 2 and FIG. 1 show the resin dissolution rates calculated in Examples 1 to 3 and Comparative Examples 1 to 3.

Table 2 : No. Resin dissolution rate (nm / min) ───────────────────────── Example 1 Polymer 1, 1,080 Example 2 Polymer 2 1,300 Example 3 Polymer 3 1,450 Comparative Example 1 Polymer 4 700 Comparative Example 2 Polymer 5 1,600 Comparative Example 3 Polymer 6 2,180 C) Preparation and Use of Photosensitive Composition Example 4 : The following samples were prepared as colored photosensitive compositions.

(1) Red Composition: 87.5 parts by weight of polymer 1 7.5 parts by weight of trimethoxymethyltri (2-hydroxyethyl acrylatemethyl) melamine 2,4-bis (trichloromethyl) -6 Styryl-s-triazine 5 parts by weight Red pigment dispersion containing dispersant 290 parts by weight (pigment content 17% by weight) Propylene glycol methyl ether acetate is added as a solvent to the above composition, and the non-solvent component is 20% by weight. The contained composition was prepared.

(2) Blue Composition: 175 parts by weight of a blue pigment dispersion containing a dispersant (pigment content: 17% by weight) is used instead of the red pigment dispersion in each component of the red composition. Except for the above, the preparation was carried out in the same manner as the composition for red color. (3) Green composition: except that 290 parts by weight of a green pigment dispersion containing a dispersant (pigment content 17% by weight) was used instead of the red pigment dispersion in each component of the red composition. Was prepared in the same manner as the red composition.

Each of the above compositions was exposed in the same manner as in Example 4 and developed with a 0.0008 N aqueous solution of tetramethylammonium hydroxide containing 1% polyoxyethylene phenyl ether. Example 5 : Polymer 1 in each color composition of Example 4
A colored photosensitive resin composition was prepared, exposed, and developed in the same manner as in Example 4, except that Polymer 2 was used instead of.

Example 6 A colored photosensitive resin composition was prepared and exposed in the same manner as in Example 4 except that Polymer 3 was used instead of Polymer 1 in each color composition of Example 4. Development was performed. Comparative Example 4 : Polymer 1 in each color composition of Example 4
A colored photosensitive resin composition was prepared, exposed and developed in the same manner as in Example 4, except that Polymer 4 was used instead of.

Comparative Example 5 A colored photosensitive resin composition was prepared and exposed in the same manner as in Example 4 except that Polymer 5 was used instead of Polymer 1 in each color composition of Example 4. Development was performed. Comparative Example 6 : In each color composition of Example 4, polymer 1
A colored photosensitive resin composition was prepared, exposed and developed in the same manner as in Example 4 except that polymer 6 was used instead of.

Examples 7 to 9 : In Comparative Examples 4 to 6, 1.5% by weight of triphenylphosphine was added to the weight of polymer 4 to 6, and a colored photosensitive resin composition was prepared in the same manner as in Example 4. Prepared, exposed and developed. Example 4-
Table 3 shows the results of Comparative Example 9 and Comparative Examples 4 to 6.

Table 3 : No. Developing time (second) Sensitivity (mJ / cm ₂ )例 Example 4 80 75 (red), 90 (blue), 85 (green) Example 5 80 75 (red), 90 (blue), 85 (green) Example 6 80 75 (red), 90 (Blue), 85 (green) Example 7 80 70 (red), 90 (blue), 80 (green) Example 8 80 70 (red), 90 (blue), 80 (green) Example 9 80 70 ( Red), 90 (blue), 80 (green) Comparative Example 4 80 Neither red nor blue or green could be developed.

Comparative Example 5 80 80 (Red), 100 (Blue), 90 (Green) Comparative Example 6 80 120 (Red), 150 (Blue), 160 (Green) Example 10 : As a photosensitive composition, Was prepared. Polymer 1 92 parts by weight Trimethoxymethyltri (2-hydroxyethyl acrylatemethyl) melamine 3 parts by weight 2,4-bis (trichloromethyl) -6- (p-styrylphenyl) -s-triazine 5 parts by weight The above composition To the product, propylene glycol methyl ether acetate was added as a solvent to prepare a composition containing 20% by weight of a non-solvent component.

The above composition was applied on a glass substrate to a thickness of about 1.5.
It was spin-coated to a thickness of μm. Then, 1 on a hot plate
Dry at 00 ° C. for 1 minute. The photosensitive resin layer was exposed with a high-pressure mercury lamp through a step tablet. Then
The colored photosensitive resin layer subjected to pattern exposure is
The film was developed with an aqueous solution of tetramethylammonium hydroxide, and the exposure energy amount at which the residual film ratio became 100% was defined as the sensitivity.

Example 11 The same procedure was performed as in Example 10 except that Polymer 2 was used instead of Polymer 1. Example 12 : The same procedure was performed as in Example 10 except that Polymer 3 was used instead of Polymer 1.

Comparative Example 7 : Polymer 1 in Example 10
Was carried out in the same manner using polymer 4 instead of Comparative Example 8 : The same procedure was performed as in Example 10 except that Polymer 5 was used instead of Polymer 1.

Comparative Example 9 : Polymer 1 in Example 10
Was carried out in the same manner using polymer 6 instead of Examples 13 to 15 : Polymers 4 to in Comparative Examples 7 to 9
The procedure of Example 10 was repeated, except that 1.5% by weight of triphenylphosphine was added to the weight of Example 6.

Table 4 shows the results of Examples 10 to 15 and Comparative Examples 7 to 9. No. Development time (second) Sensitivity (mJ / cm ₂ ) ──────────────────────────────── Example 10 140 85 Example 11 140 85 Example 12 140 85 Example 13 140 80 Example 14 140 80 Example 15 140 80 Comparative Example 7 140 Unable to develop Comparative Example 8 140 85 Comparative Example 9 140 120 From the above Examples and Comparative Examples , The following things become clear. (1) Comparing Examples 1 to 3 and Comparative Examples 1 to 3, polymers 1 to 3 containing a large amount of triphenylphosphine are:
It is apparent that the variation of the dissolution rate in the aqueous alkali solution is smaller than that of the polymers 4 to 6 with respect to the change of the acid value. (2) When Examples 4 to 6 and Comparative Examples 4 to 6 are compared, the photosensitive resin compositions prepared using Polymers 1 to 3 show a change in the acid value as compared with those prepared using Polymers 4 to 6. It can be seen that the characteristics due to are hardly affected. (3) When Examples 10 to 12 and Comparative Examples 7 to 9 are compared, the photosensitive resin compositions containing no pigments using polymers 1 to 3 similarly show polymers 4 to 6
It can be seen that the characteristics due to the change in the acid value are less likely to be affected than those prepared using. (4) From Examples 7 to 9 and Examples 13 to 15, it can be seen that the addition of triphenylphosphine is also effective for making the characteristics hardly affected by the fluctuation of the acid value.

[0050]

The photosensitive resin composition of the present invention comprises a polymer having a segment having a carboxyl group and a compound having at least one vinyl group and an epoxy group in one molecule. Tertiary phosphine is added to a resin having a group in an amount of 0.5 to 5% by weight based on the resin.
By containing at a concentration of 0.15 g, the change in the dissolution rate in an aqueous alkali solution due to a change in the acid value is small, and the characteristics are stabilized. Therefore, by using the present composition, in the production process of the color filter, the fluctuation of the lot-to-lot performance of the photosensitive resin composition is reduced, the process can be greatly stabilized, and the industrial utility value is Extremely large.

[Brief description of the drawings]

FIG. 1 compares the dissolution rates of the polymers of Examples 1 to 3 and Comparative Examples 1 to 3.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuki Nanjo 1-3-2 Minamidai, Kawagoe-shi, Saitama Prefecture Inside the Advanced Materials Research Laboratory, Hextoin Industry Co., Ltd. (72) Inventor Yasumi Bunko 1-3-1, Minamidai, Kawagoe-shi, Saitama Prefecture 2 Advanced Materials Technology Laboratory, Hextoin Industry Co., Ltd. (72) Yuko Nozaki 1-3-2 Minamidai, Kawagoe-shi, Saitama Prefecture Innovative Materials Technology Laboratory, Hextoin Industry Co., Ltd. (72) Hiroto Miyake Kuba, Otake City, Hiroshima Prefecture 6-8-2

Claims (4)

[Claims] (1) a resin containing a carboxyl group, (b)
In a photosensitive resin composition containing an actinic ray irradiation polymerization initiator and (c) a solvent as essential components, component (a) is a polymer (I) containing a segment having a carboxyl group and one or more vinyls per molecule. A resin having a vinyl group and a carboxyl group obtained by adding a compound (II) having a group and an epoxy group, and the resin contains 0.5 to 5% by weight of a tertiary phosphine based on the resin. A photosensitive resin composition comprising: 2. The photosensitive resin composition according to claim 1, further comprising (d) a thermal crosslinking agent and / or a compound having a polymerizable unsaturated bond as an additional component. 3. The components (a) to (c) or the components (a) to (c)
The photosensitive resin composition according to claim 1, further comprising (e) a pigment in addition to the component (d). 4. The resin (a) having a vinyl group and a carboxyl group is used as a polymer (I) containing a segment having a carboxyl group in a polymer containing a segment represented by the following general formula (3,4-epoxy). 2. A resin obtained by adding a compound (II) having at least one vinyl group and an epoxy group in one molecule selected from cyclohexyl) methyl methacrylate and (3,4-epoxycyclohexyl) methyl acrylate. 4. The photosensitive resin composition according to any one of items 1 to 3. Embedded image (Wherein, R _{1 s} may be the same or different and each represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group having a linear or side chain structure having 1 to 5 carbon atoms, and m and n represent And m / n = 0.5 to 2.4 (molar ratio).)