TWI450034B - Alkali soluble binder resin and photosensitive resin composition including the same - Google Patents

Description

Resin for alkali-soluble binder and photosensitive resin composition containing the same

The present application claims priority to Korean Patent Application No. 10-2010-0033743, filed on Apr. 13, 2010, to the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference.

The present invention relates to a resin for an alkali-soluble binder which can have excellent resolubility as a cleaning solvent, can reduce the contamination of a slit nozzle, and reduce foreign matter in the substrate (alien substance) Further, the present invention relates to a method for producing the resin for an alkali-soluble binder, and a photosensitive resin composition comprising a resin for an alkali-soluble binder.

As the size of the substrate increases, a method of preparing a color filter generally using a photosensitive resin composition is gradually changed from a conventional spin coating method to a slit and spin method or a non-rotation method ( Spinless method). However, in the slit rotation method or the non-rotation method, a slit nozzle is used for the coating process. Therefore, it is likely that the slit nozzle is contaminated by the photosensitive resin composition, and thus it is required to develop a method of cleaning the slit nozzle.

This cleaning method cleans the nozzle portion of the slit using the main solvent in the photosensitive resin composition. Here, when the solubility of the resin composition to the main solvent (generally referred to as solubility) is low, the photosensitive resin composition dried at the nozzle portion will continue to exist in the form of a projection to cause foreign matter in the substrate, This in turn reduces the yield.

Therefore, in order to solve the above problems, the solubility of the solvent after drying of the photosensitive resin composition becomes more and more important.

Accordingly, an object of the present invention is to provide a method for synthesizing a resin for an alkali-soluble binder having excellent solubility and a photosensitive resin composition comprising the resin for an alkali-soluble binder, which are reduced in the step of producing a color filter. The contamination of the slit nozzle and the generation of foreign matter in the substrate.

Another object of the present invention is to provide a resin for an alkali-soluble binder which is contained in a photosensitive resin composition, and which is made of a resin having a structure which enhances solubility.

Still another object of the present invention is to provide a process for producing a resin for an alkali-soluble binder having excellent solubility.

Still another object of the present invention is to provide a photosensitive resin composition having excellent solubility which is excellent in solubility when a pattern is formed using a photosensitive resin composition containing a resin for an alkali-soluble binder. The material does not cause contamination or defects in the nozzle portion of the slit.

A further object of the present invention is to provide a color filter prepared by using the photosensitive resin composition of the present invention, which is capable of producing excellent photosensitivity, developing properties and chemical resistance due to improvement in solubility. Color filter.

When the resin for an alkali-soluble binder for a photosensitive resin composition is produced in the present invention, a carboxylic acid compound having a long alkyl chain is added to an intermediate reaction step to form a resin in an alkali-soluble binder. The longer alkyl chain replaces the side chain of the resin for the alkali-soluble binder.

After the desired pattern is formed using the photosensitive resin composition containing the resin structure of the above-described alkali-soluble binder, when the nozzle portion of the slit is cleaned by a cleaning method, the resin for the alkali-soluble binder is lifted by the long alkyl chain replacing the side chain. The flexibility of the resin composition as a main solvent is improved, and the resin composition can be left in the nozzle portion of the slit.

The resin for an alkali-soluble binder of the present invention can be used for the production of solubility because it has excellent cleaning solvent solubility while maintaining basic properties such as sensitivity, development characteristics, and chemical resistance required for the photosensitive resin composition. Excellent photosensitive resin composition.

Further, when a photosensitive resin composition having improved solubility is used, the failure of the final product can be minimized, and since the cleaning method is not required to be repeatedly performed, the effect of improving the processability is obtained.

In the following, the embodiments of the present invention will be described in more detail with reference to the accompanying drawings, and the embodiments of the present invention can be easily implemented by those skilled in the art.

Preferably, the carboxylic acid compound is added to the intermediate reaction step so that the resin for the alkali-soluble binder of the present invention has a long side chain structure. Thus, an alkyl chain having at least one carbon number will be substituted on the side chain of the structure.

In particular, the resin for an alkali-soluble binder of the present invention contains a repeating unit represented by the following Chemical Formula 1 to Chemical Formula 3:

In Chemical Formula 1 to Chemical Formula 3, X ₁ and X ₂ are groups which are the same or different from each other, and each group is selected from hydrogen, an alkyl group having a carbon number of 1 to 3, and an alkoxy group. A group is one or more groups selected from the group consisting of a benzyl oxy carbonyl group, a phenyl group, an isobornyl group, and a cyclohexyl group. Group), and an N-phenyl maleimide group; Y is selected from the group consisting of: an alkylene having a carbon number of 1 to 5 And ethylene oxide, and propylene oxide; Z is selected from the group consisting of an alkylene group having 1 to 5 carbon atoms, monocyclohexene, monocyclohexane, and a monophenyl group; and n is 1 to 10.

Further, the method for preparing a resin for an alkali-soluble binder in the present invention comprises the steps of: a) polymerizing a monomer represented by Chemical Formula 1 and an epoxy group-containing monomer; b) polymer formed in the polymerization step a) And a monocarboxylic acid compound; and c) adding a cyclic anhydride to add an acid group to the polymer formed in the step b).

Further, the photosensitive resin composition of the present invention comprises a resin for an alkali-soluble binder containing a repeating unit represented by Chemical Formula 1 to Chemical Formula 3.

Further, the present invention relates to a color filter having a pattern formed using a photosensitive resin composition.

Hereinafter, the contents of the present invention will be described in more detail.

The resin for an alkali-soluble binder of the present invention includes a repeating unit represented by Chemical Formula 1 to Chemical Formula 3.

In Chemical Formula 1, X ₁ is selected from the group consisting of hydrogen, an alkyl group having a carbon number of 1 to 3, and a monooxy group; and A is one or more groups selected from the group consisting of a benzyloxy group. Benzyl oxy carbonyl group, phenyl group, isobornyl group, cyclohexyl group, and N-phenyl maleimide Group);

In Chemical Formula 2, X ₁ and X ₂ are groups which are the same or different from each other, and each group is selected from hydrogen, an alkyl group having a carbon number of 1 to 3, and a alkoxy group; Is selected from the group consisting of: an alkylene having from 1 to 5 carbon atoms, ethylene oxide, and propylene oxide; and n is from 1 to 10;

In Chemical Formula 3, X ₁ and X ₂ are groups which are the same or different from each other, and each group is selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, and a alkoxy group; Y system Selected from the group consisting of: an alkylene having from 1 to 5 carbon atoms, ethylene oxide, and propylene oxide; and Z being selected from an alkylene having from 1 to 5 carbon atoms. a group, a cyclohexene, a cyclohexane, and a monophenyl group; and n is from 1 to 10.

The resin for an alkali-soluble binder containing a repeating unit represented by Chemical Formula 1 to Chemical Formula 3 can also be represented by the following Chemical Formula 4.

In Chemical Formula 4, a, b, and c are the molar ratios of the respective repeating units, each molar ratio is 10 to 90, and the total molar ratio of the molar ratios is 100 mole ratio; X ₁ and X ₂ is a group which is the same or different from each other, and each group is selected from hydrogen, an alkyl group having a carbon number of 1 to 3, and a alkoxy group; and A is selected from a benzyloxy group. a carbonyl group, a phenyl group, an isobornyl group, a cyclohexyl group, and an N-phenylmaleimido group; the Y group is selected from the group consisting of: one having a carbon number of 1 to 5 An alkylene group, an ethylene oxide, and a propylene oxide; and the Z system is selected from the group consisting of an alkylene group having 1 to 5 carbon atoms, cyclohexene, cyclohexane, and phenyl; 1 to 10.

The repeating unit a as shown in Chemical Formula 4 in the composition of the resin for an alkali-soluble binder of the present invention may contain one or more repeating units as shown in Chemical Formula 1.

For example, a certain proportion of a benzyloxycarbonyl group, an N-phenylmaleimido group, and a phenyl group can be used as the compound represented by A in Chemical Formula 4. When X _{1 is} hydrogen, Y is a methylene group, Z is cyclohexene, and n is 2.5, a compound of the following chemical formula 5 can be obtained.

In Chemical Formula 5, a ₁ to a ₃ , b and c are the molar ratios of the respective repeating units, a ₁ + a ₂ + a ₃ = 10 to 90 mol ratio, b = 10 to 90 mol ratio, c = 10 to 90 mole ratios, and the sum is 100 mole ratio.

Specific examples of the compound having a repeating unit represented by Chemical Formula 1 may include one or more compounds selected from the group consisting of styrene, benzyl (meth)acrylate, and methyl methacrylate ( Methyl(meth)acrylate), ethyl(meth)acrylate,isobutyl(meth)acrylate,t-butyl(meth)acrylate,A Cyclohexyl (meth) acrylate, and isobornyl group (meth) acrylate.

The repeating unit as shown in Chemical Formula 1 can improve the compatibility with other constituents in the alkali-soluble resin, and has an effect of improving coating properties and chemical resistance. Therefore, it is preferable to select an appropriate molar ratio according to the characteristics thereof, preferably a resin having an alkali-soluble binder of 100 mol ratio, and the molar ratio of each repeating unit is in the range of 10 to 90 mol ratio.

Further, a compound having a repeating unit represented by Chemical Formula 2, wherein the polymer is represented by the compound of Chemical Formula 1 and Chemical Formula 6, can be produced by a polymerization reaction of a carboxylic acid compound represented by the following Chemical Formula 7 with a polymer. The reaction of the epoxy group-containing compound is formed. That is, the compound having a repeating unit represented by Chemical Formula 2 is a compound obtained by reacting an epoxy group-containing compound formed by reacting a compound represented by Chemical Formula 7 with a permeating polymer represented by Chemical Formula 6 to carry out a reaction. .

[Chemical Formula 6]

In Chemical Formula 6, X ₁ is selected from the group consisting of hydrogen, an alkyl group having a carbon number of 1 to 3, and a monooxy group; Y is selected from the group consisting of: 1 to 5 carbon atoms An alkylene, an ethylene oxide, and a propylene oxide;

In Chemical Formula 7, X ₂ is selected from the group consisting of hydrogen, an alkyl group having a carbon number of 1 to 3, and a monooxy group; and n is 1 to 10.

The epoxy group-containing compound represented by Chemical Formula 6 is a resin for introducing a carboxylic acid compound having a long alkyl chain into an alkali-soluble binder. Here, Glycidyl (meth) acrylate can be preferably used. However, any monomer containing an epoxy group reactive with a carboxylic acid compound (as shown in Chemical Formula 7), and a monomer introduced in the second synthesis step of preparing an alkali-soluble resin in the present invention may be used as a ring-containing ring. A compound of an oxy group.

In particular, among the constituent components constituting the repeating unit represented by Chemical Formula 2, the resin for an alkali-soluble binder of the present invention includes a carboxylic acid compound having a long alkyl chain which is a compound represented by Chemical Formula 7. The purpose is to improve the flexibility of the binder resin by introducing a long alkyl chain in the carboxylic acid compound, thereby improving the solubility of the solvent.

That is, in the compound of Chemical Formula 7, the repeating unit n is from 1 to 10, preferably from 1 to 5. Even if n is 1, the alkyl chain still has an extremely long structure when viewed from the entire structure of the final polymer after completion of the reaction. Therefore, it can be said that the alkyl chain system is relatively long and has a remarkable effect as compared with general acrylic acid. When the alkyl chain is not contained in the example of the compound represented by Chemical Formula 7, when acrylic acid is used in the prior art, it is difficult to improve the flexibility of the resin for the alkali-soluble binder. However, if the repeating unit n of the compound exceeds 10 and is too long, although it has an effect of improving solubility, it causes problems such as deterioration in characteristics such as sensitivity and pattern flatness.

A compound satisfying the above characteristics is a carboxylic acid compound represented by Chemical Formula 7, which comprises one or more compounds selected from the group consisting of 2-acryloyloxyethyl succinate Succinate), 2-methacryloyloxy ethyl succinate, 2-acryloyloxy ethyl hexahydrophthalate, phthalic acid 2-acryloyloxyethyl phthalate and ε-carboxy polycaprolactone monoacrylate. Among them, 2-propenyloxyethyl succinate or ε-carboxypolycaprolactone monoacrylate is preferred.

Further, the structure and characteristics of the final binder resin in the present invention can be regulated by controlling the timing of the addition of the carboxylic acid compound having a long alkyl chain as the compound of Chemical Formula 7. In the prior art, since the carboxylic acid compound having a longer alkyl chain is added in the early stage of the reaction of the initial polymer preparation step, the binder resin obtained by the additional reaction will have a different structure.

The carboxylic acid compound having a long alkyl chain in the present invention is not included in the initial polymer preparation step, but is added to the intermediate step so that the polymer chain after the polymerization reaction can be extended for a long time, thereby lifting the polymer chain. Flexibility. Since it imparts flexibility to the polymer chain to have an effect of improving solubility, the polymer resin can have a different structure by controlling the time point of adding the carboxylic acid compound having a long alkyl chain. To achieve the above effects.

Further, the compound having a repeating unit represented by Chemical Formula 2 has an advantage that the alkali-soluble resin has photocrosslinkability and chemical resistance due to the inclusion of an unsaturated double bond in the chain.

Further, the compound having a repeating unit represented by Chemical Formula 3 constitutes a resin for an alkali-soluble binder of the present invention, which is obtained by reacting a cyclic anhydride with a compound having a repeating unit represented by Chemical Formula 2.

That is, a cyclic anhydride is added to a hydroxyl group in the compound represented by Chemical Formula 2 to add an acid group. The cyclic anhydride is one or more compounds selected from the group consisting of succinic anhydride, adipic anhydride, phthalic anhydride, hexahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride And trimellitic anhydride and cis-5-norbornene-endo-2,3-dicarboxylic anhydride. Among them, succinic anhydride or 3,4,5,6-tetrahydrophthalic anhydride is preferably used. Here, the acid group formed by the repeating unit represented by Chemical Formula 3 can provide the alkali-soluble resin with the property of development.

Hereinafter, a method of preparing a resin for an alkali-soluble binder of the present invention will be specifically described.

The method comprises the steps of: a) polymerizing an epoxy group-containing monomer and a compound comprising a repeating unit of the formula 1 to obtain a polymer; b) polymerizing the monocarboxylic acid compound and the step a) Forming the polymer; and c) adding a cyclic anhydride to add an acid group to the polymer formed in step b).

The monomer represented by the chemical formula 1 in the step a) may be one or more compounds selected from the group consisting of styrene, benzyl methacrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, Butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate.

Further, the monomer having an epoxy group in the step a) may be any monomer having an epoxy group reactive with a carboxylic acid compound, and the monomer may be a monomer represented by the following Chemical Formula 6.

In Chemical Formula 6, X ₁ is selected from the group consisting of hydrogen, an alkyl group having a carbon number of 1 to 3, and a monooxy group; Y is selected from the group consisting of: 1 to 5 carbon atoms An alkylene, ethylene oxide, and propylene oxide.

The epoxy group-containing compound represented by Chemical Formula 6 is for introducing a carboxylic acid compound having a long alkyl chain into a resin for an alkali-soluble binder. The best use of glycidyl methacrylate. Further, any monomer containing an epoxy group reactive with a carboxylic acid compound (as shown in Chemical Formula 7), and a monomer introduced in the second synthesis step of preparing an alkali-soluble resin in the present invention may be used. Both can be used as compounds containing an epoxy group.

Further, the carboxylic acid compound having a long alkyl chain can be represented by the following Chemical Formula 7.

In Chemical Formula 7, X ₂ is selected from the group consisting of hydrogen, an alkyl group having a carbon number of 1 to 3, and a monooxy group; and n is 1 to 10.

The carboxylic acid compound represented by Chemical Formula 7 may comprise one or more groups selected from the group consisting of 2-acryloyloxy ethyl succinate, 2-methyl propylene sulfonate succinate. 2-methacryloyloxy ethyl succinate, 2-acryloyloxy ethyl hexahydrophthalate, 2-propenyl methoxyethyl phthalate 2-acryloyloxyethyl phthalate) and ε-carboxy polycaprolactone monoacrylate. Among them, 2-propenyloxyethyl succinate or ε-carboxypolycaprolactone monoacrylate is preferred.

Therefore, the monomer represented by Chemical Formula 2 can be obtained by a reaction of a carboxylic acid compound represented by Chemical Formula 7 with an epoxy compound represented by Chemical Formula 6. The alkali-soluble resin transmits unsaturated double bonds in the monomer to impart photo-crosslinkability and chemical resistance.

Further, the monomer represented by Chemical Formula 3 is obtained by reacting a cyclic anhydride with a monomer represented by Chemical Formula 2 in an appropriate ratio, and the cyclic anhydride is preferably succinic anhydride or tetrahydrophthalic anhydride. At this time, the alkali-soluble resin has a developing property by permeating the formed acid group.

The alkali-soluble resin of the present invention can be produced by any of the following methods: radical polymerization, cationic polymerization, anionic polymerization, and condensation polymerization. However, in view of ease of preparation and economy, it is preferred to use a radical polymerization reaction.

When the alkali-soluble resin of the present invention is prepared by a radical polymerization method, 2,2' azobisisobutyronitrile (AIBN), 2,2'-azobis-(2,4-dimethylvaleronitrile) can be used. (2,2'-azobis-(2,4-dimethylvaleronitrile)) or benzoyl peroxide (2,2'-azobis-(2,4-dimethylvaleronitrile) or the like as a radical polymerization initiator.

Further, the polymerization hour is preferably from 1 to 48 hours, and the polymerization temperature is preferably from 50 to 150 °C.

The alkali-soluble resin is preferably used in the above mode to have an acid value of from 30 to 200 KOH mg/g. When the acid value is less than 30 KOH mg/g, development hardly occurs. When the acid value is more than 200 KOH mg/g, there is a problem of overdevelopment. The weight average molecular weight of the alkali-soluble resin in the present invention is preferably from 1,000 to 200,000 g/mol. When the weight average molecular weight is less than 1,000 g/mol, almost no reaction occurs; when the weight average molecular weight is more than 200,000 g/mol, a good fine pattern cannot be formed.

The photosensitive resin composition of the present invention may comprise an alkali-soluble resin, a polymeric compound having an ethylenically unsaturated bond, a photoinitiator, and a solvent.

Specific examples of the polymerizable compound having an ethylenically unsaturated bond may include the following compounds: pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate (pentaerythritol tetra(meth) Acetate), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono(meth)acrylate (polyethyleneglycol mono(meth)acrylate) and polypropylene glycol mono(meth)acrylate, but not limited thereto.

The photoinitiator may comprise one or more compounds selected from the group consisting of 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (2,4-trichloromethyl-(4') -methoxyphenyl)-6-triazine), 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (2,4-trichloromethyl-(4'-methoxystyryl)-6- Triazine), and 2,4-trichloromethyl-(fipronil-6-triazine) triazine compound; acetophenone Base compounds, including: 1-hydroxycyclohexyl phenyl ketone, and 4-(2-hydroxyethoxy)-phenyl(2-hydroxy)propyl ketone (4-(2-hydroxyethoxy) )-phenyl(2-hydroxy)propyl ketone); and benzophenone-based compounds, including: benzophenone, and 2,4,6-trimethylaminobiphenyl Ketone (2,4,6-trimethylaminobenzophenone), but not limited to this.

Further, the solvent may comprise one or more compounds selected from the group consisting of methyl ethyl ketone, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate. , cyclohexanone, 2-heptanone, isobutyl acetate, isopropylbutyrate, and 3-methoxybutyl acetate ), but not limited to this.

The content of the alkali-soluble resin may be 1 to 20% by weight based on the total weight of the photosensitive resin composition, the content of the polymerizable compound having an ethylenically unsaturated bond may be 1 to 10% by weight, and the content of the photoinitiator may be It is 0.1 to 5 wt%, and the content of the solvent may be 65 to 95 wt%.

When the photosensitizer is used in the example of a negative color filter and a black matrix, a colorant may be further included. Here, the pigment as the colorant may be one or more selected from the group consisting of black pigment, red pigment, yellow pigment, blue pigment, and violet pigment. Black pigments include carbon black and titanium black. Color pigments include phthalocyanine green, phthalocyanine blue, perylene blue, linol yellow, and Victoria pure blue. Further, the content of the colorant may be from 1 to 20% by weight in the total resin composition.

Hereinafter, the contents of the present invention will be described in more detail in conjunction with the embodiments of the present invention. However, the following examples are merely illustrative of the invention and are not intended to limit the invention to the following examples. It will be readily apparent to those skilled in the art that the same effects as the present invention can be attained by using the specific materials used in the examples and equivalents thereof.

Synthesis Example 1

32 g of benzyl methacrylate, 5 g of N-phenyl maleimide, 4 g of styrene, 36 g of glycidyl methacrylate, and 2.5 g of dodecanethiol 300 g of propylene glycol monomethyl ether acetate was mixed, and the temperature of the reactor was raised to 65 ° C under a nitrogen atmosphere. When the temperature of the mixture reached 65 ° C, 4 g of AIBN (i.e., thermal polymerization initiator) was charged, and stirring was continued for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 98%, a molecular weight of 10,000 g/mol, and a solid content of 20% was obtained.

0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ (i.e., thermal polymerization inhibitor) were charged into the polymer solution, and stirring was continued at 80 ° C for 30 minutes. Next, 40 g of 2-propenyloxyethyl succinate was charged and stirring was continued at 120 ° C for 24 hours. After 24 hours, a polymer resin binder solution having a molecular weight of 17,000 g/mol and a solid content of 30% was obtained.

In the final synthesis step, 20 g of tetrahydrophthalic anhydride was charged into the polymer solution and stirring was continued at 90 ° C for 15 hours. According to this, a desired alkali-soluble resin solution (1) having a molecular weight of 25,000 g/mol, an acid value of 100, and a solid system of 35% was obtained.

Synthesis Example 2

32 g of benzyl methacrylate, 5 g of N-phenyl maleimide, 4 g of styrene, 36 g of glycidyl methacrylate, and 2.5 g of dodecanethiol 300 g of propylene glycol monomethyl ether acetate was mixed, and the temperature of the reactor was raised to 65 ° C under a nitrogen atmosphere. When the temperature of the mixture reached 65 ° C, 4 g of AIBN (i.e., thermal polymerization initiator) was charged, and stirring was continued for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 98%, a molecular weight of 10,000 g/mol, and a solid content of 20% was obtained.

0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ (i.e., a thermal polymerization inhibitor) were charged into the polymer solution, and stirring was continued at 80 ° C for 30 minutes. Next, 65 g of ε-carboxypolycaprolactone monoacrylate was charged, and stirring was continued at 120 ° C for 24 hours. After 24 hours, a polymer resin binder solution having a molecular weight of 19,000 g/mol and a solid content of 32% was obtained.

In the final synthesis step, 28 g of tetrahydrophthalic anhydride was charged into the polymer solution and stirring was continued at 90 ° C for 15 hours. According to this, a desired alkali-soluble resin solution (2) having a molecular weight of 27,000 g/mol, an acid value of 100, and a solid system of 37% was obtained.

"Synthesis Comparative Example 1"

32 g of benzyl methacrylate, 5 g of N-phenyl maleimide, 4 g of styrene, 36 g of glycidyl methacrylate, and 2.5 g of dodecanethiol 300 g of propylene glycol monomethyl ether acetate was mixed, and the temperature of the reactor was raised to 65 ° C under a nitrogen atmosphere. When the temperature of the mixture reached 65 ° C, 4 g of AIBN (i.e., thermal polymerization initiator) was charged, and stirring was continued for 12 hours. After 12 hours, a polymer resin binder solution having a polymerization yield of 98%, a molecular weight of 10,000 g/mol, and a solid content of 20% was obtained.

0.5 g of tetrabutylammonium bromide and 0.1 g of MEHQ (i.e., thermal polymerization inhibitor) were placed in the polymer solution, and stirring was continued at 80 ° C for 30 minutes. Next, 20 g of acrylic acid was charged and stirring was continued at 120 ° C for 24 hours. After 24 hours, a polymer resin binder solution having a molecular weight of 15,000 g/mol and a solid system of 28% was obtained.

In the final synthesis step, 15 g of tetrahydrophthalic anhydride was charged into the polymer solution and stirring was continued at 90 ° C for 15 hours. According to this, a desired alkali-soluble resin solution (3) having a molecular weight of 23,000 g/mol, an acid value of 100, and a solid system of 33% was obtained.

"Embodiment 1"

5 g of the alkali-soluble resin (1) formed in Synthesis Example 1 and 30 g of a green pigment dispersion, 1.5 g of a photoinitiator I-369, 0.5 g of a photoinitiator CGI-242, 3.5 G of dipentaerythritol hexaacrylate, 40 g of propylene glycol monomethyl ether acetate and 0.1 g of 2-methacrylate oxypropyl trimethoxysilane (ie, an additive) are mixed and stirred. One hour was made to prepare a photosensitive resin composition.

<<Example 2》

The mixture was mixed using the same composition as in Example 1 except that 5 g of the alkali-soluble resin (2) formed in Synthesis Example 2 was used instead of the alkali-soluble resin (1) in Example 1, and stirred for about 1 hour. To prepare a photosensitive resin composition.

Comparative Example 1

The mixture was mixed using the same composition as in Example 1 except that the alkali-soluble resin (3) formed in Synthesis Comparative Example 1 was replaced with 5 g of the alkali-soluble resin (3) of Example 1, and stirred for about 1 An hour was made to prepare a photosensitive resin composition.

"Experimental Example 1 - Development Characteristics, Chemical Resistance, and Sensitivity Test"

Each photosensitive resin composition solution prepared in Example 1, Example 2, and Comparative Example 1 was spin-coated on a glass substrate, and then pre-baked at 90 ° C for 100 seconds to prepare a conductive film having a thickness of 1.5 μm. . The film was placed under a mask of an exposure gap of 200 μm, exposed to a high-pressure mercury lamp of 60 mJ/cm ² , and the substrate was developed using a 0.04% KOH aqueous solution at 25 ° C for 60 seconds. Next, after the development step, the washing and drying steps were carried out and post-baked in a convection heat transfer furnace at 230 ° C for 25 minutes. Thereafter, the pattern state of the pattern is monitored.

The various pattern patterns described above were monitored using an optical microscope. The development characteristics, sensitivity, and chemical resistance of the NMP solution of the pattern were evaluated, and the evaluation and comparison results are shown in Table 1 below.

The development characteristics were measured by monitoring the progress of the exposed substrate through development of 0.04% KOH aqueous solution for 60 seconds. The development characteristics are judged by how fast the development reaches the edge portion of the substrate. When the development step can be made apparent, it is judged to be acceptable.

Sensitivity is obtained by measuring each final pattern pattern with an optical microscope to measure the remaining minimum pattern size. The smaller the remaining minimum pattern size, the better the sensitivity.

Further, after immersing each of the substrates obtained in the examples and the comparative examples in an NMP solution at 45 ° C for 30 minutes, the change in appearance of the coating film was monitored to measure the chemical resistance thereof. Marked as good (○) when there is no change in appearance. When a slight change in appearance is observed, the mark is normal (Δ). When the appearance is peeled off or the solvent color is deteriorated, it is marked as unacceptable (X).

<Experimental Example 2 - Solubility Test>

Each of the photosensitive resin composition solutions prepared in Example 1, Example 2, and Comparative Example 1 was spin-coated on a glass substrate, respectively, and then prebaked at 80 ° C for 300 seconds. Next, the substrate was immersed in a PGMEA solution at 25 ° C for 5 minutes and then taken out from the PGMEA solution. Thereafter, the solubility was measured by monitoring the state of the solution. The evaluation results of the solubility are shown in Table 1. When the prebaked conductive film was apparently melted in the PGMEA solution, it was marked as good (○). When the prebaked conductive film is only partially melted in the PGMEA solution and some precipitation occurs, it is marked as normal (?). When the prebaked conductive film was not melted in the PGMEA solution or many precipitates appeared, it was marked as unacceptable (X). Further, the solution state is as shown in FIGS. 1 to 3.

As apparent from the above Table 1, the alkali-soluble resin polymer of the present invention has the same development characteristics, chemical resistance and sensitivity as the conventional alkali-soluble resin, but it has an excellent solvent solubility, so that it can be effectively improved. The solubility of the photosensitive resin composition.

In particular, in FIGS. 1 to 3, Synthesis Comparative Example 1 (FIG. 3) is a resin for an alkali-soluble binder containing a structure in which an alkyl chain of a carboxylic acid is not long, and a long alkyl chain is contained in the present invention. The resin of the carboxylic acid-based alkali-soluble binder cannot have good flexibility compared with the resin (Figs. 1 and 2). Therefore, it is shown that the solubility of the resin is low.

1 to 3 are the results of the solubility evaluation of the compositions of Example 1, Example 2 and Comparative Example 1.

Claims (8)

A resin for an alkali-soluble binder, which is represented by the following Chemical Formula 5: In Chemical Formula 5, a ₁ to a ₃ , b, and c are the molar ratios of the respective repeating units, a1+a2+a3=10 to 90 mole ratio, b=10 to 90 mole ratio, c = a 10-90 molar ratio, and the sum is a 100 molar ratio. The resin for an alkali-soluble binder according to the first aspect of the invention, wherein the acid value of the resin for the alkali-soluble binder is 30 to 200 KOH mg/g, and the weight average molecular weight of the resin for the alkali-soluble binder (Mw) is from 1,000 to 200,000 g/mol. A method for preparing a resin for an alkali-soluble binder, comprising the steps of: a) polymerizing a glycidyl methacrylate, benzyl methacrylate, N-phenylmaleimide, and a styrene monomer, Obtaining a polymer; b) polymerizing ε-carboxy polycaprolactone monoacrylate and the polymer formed in the step a); and c) adding 3,4,5,6-tetrahydrophthalic anhydride (3,4,5,6-tetrahydrophthalic acid anhydrides) to add a monoacid group to the polymer formed in the step b). The method of claim 3, wherein the alkali-soluble binder is prepared by a radical polymerization reaction using a resin. The method of claim 3, wherein the polymerization is carried out at 50 to 150 ° C for 1 to 48 hours. A photosensitive resin composition comprising the resin for an alkali-soluble binder according to item 1 of the patent application. The photosensitive resin composition according to claim 6, wherein the photosensitive resin composition further comprises a polymerization-series compound having a ethylenically unsaturated bond, a photoinitiator, and a Solvent. The photosensitive resin composition according to claim 6, wherein the photosensitive resin composition comprises from 1 to 20% by weight of an alkali-soluble resin, from 1 to 10% by weight of a polymerizable compound having an ethylenically unsaturated bond, 0.1 to 5% by weight of a photoinitiator, and 65 to 95% by weight of a solvent.