KR20140023617A - Alkali-developable resins and process for producing the same - Google Patents
Alkali-developable resins and process for producing the same Download PDFInfo
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- KR20140023617A KR20140023617A KR1020120089686A KR20120089686A KR20140023617A KR 20140023617 A KR20140023617 A KR 20140023617A KR 1020120089686 A KR1020120089686 A KR 1020120089686A KR 20120089686 A KR20120089686 A KR 20120089686A KR 20140023617 A KR20140023617 A KR 20140023617A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2045—Exposure; Apparatus therefor using originals with apertures, e.g. stencil exposure masks
- G03F7/2047—Exposure with radiation other than visible light or UV light, e.g. shadow printing, proximity printing
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Abstract
Description
The present invention relates to an alkali-soluble resin and a method for producing the same. More specifically, the present invention relates to an alkali-soluble resin contained in a photosensitive resin used for various purposes such as a photosensitive material for manufacturing a color filter, an overcoat photosensitive material, a spacer, and a manufacturing method thereof.
The photosensitive composition is used in various applications such as a photosensitive material for manufacturing color filters, an overcoat photosensitive material, a column spacer, and the like. This usually includes an alkali-soluble resin, a polymerizable compound having an ethylenic unsaturated bond, a photopolymerization initiator, a solvent and the like. Such a photosensitive composition is applied onto a substrate to form a coating film, and after exposure by radiation irradiation using a photomask or the like to a specific portion of the coating film, a method of forming a pattern by removing the non-exposed part by developing treatment. Used as
By the way, in order to improve the yield per unit time of a process in the process of using the above-mentioned photosensitive composition, exposure time and image development time are reduced, and the photosensitivity and developability of the photosensitive composition itself are calculated | required.
As a method of increasing the photosensitivity of the photosensitive composition, it is typical to use a photoinitiator with high photosensitivity or to increase the amount of photoinitiator used. However, photoinitiators having high photosensitivity are relatively expensive. In addition, when the amount of the photoinitiator is increased, there is a risk that contamination of the oven or contamination of components such as liquid crystal in the LCD panel occurs due to the generation of sublimable foreign substances in the post baking process.
In recent years, in order to introduce photopolymerizable functional groups into the side chain of alkali-soluble resin used for the photosensitive composition, the method of photocrosslinking an alkali-soluble resin with an ethylenically unsaturated compound is tried.
However, since the photopolymerizable reactive group is introduced into the acid-labile part of the alkali-soluble resin, when the proportion of the photopolymerizable reactive group in the alkali-soluble resin is increased, the remaining acid group ratio is lowered and the developability is deteriorated. Therefore, researches to solve these problems are continuing.
In addition, recently, as the size of a display has been rapidly increased and a high contrast ratio has been continuously required, a dye is conventionally used instead of the pigment dispersion method used conventionally as a method of coloring a photosensitive resin composition, or a dye and a pigment are simultaneously used Methods are being studied.
However, in the case of producing a color filter using a colored photosensitive resin composition containing a dye as a coloring agent, since the light resistance and heat resistance of the dye are poor, color shifts frequently occur, the developing speed is slowed, There is a problem that the formed pattern is often peeled off during the development process.
Therefore, studies for solving the above-mentioned problems have been actively conducted. For example, Korean Patent Publication No. 10-2010-0042173 discloses a photosensitive resin obtained by further reacting a compound containing an epoxy group with a resin having a photoreactive group, and a photosensitive composition comprising the same. The said photosensitive resin composition contains the structure which can improve the heat resistance derived from the compound containing epoxy in resin, and has the characteristic which further has the alcohol group produced | generated by reaction of an epoxy group and an acidic group.
However, physical properties such as adhesiveness, developability, sensitivity, chemical resistance, strength and elasticity, such as photosensitive resins, which have recently been introduced, including the photosensitive resins, do not seem to sufficiently meet the requirements of this field. Therefore, continuous research for solving such problems is required.
The present invention is to solve the above problems of the prior art, and has excellent physical properties such as adhesion, developability, sensitivity, chemical resistance, strength and elasticity, and miscibility and separation with other organic binders, pigments, and dyes. It is an object to provide an alkali-soluble resin excellent in acidity and a method for producing the same.
The present invention provides an alkali-soluble resin comprising a repeating unit represented by the following formula (1):
[Formula 1]
In the above formula, R1 is hydrogen or an alkyl group of C1 ~ C4, R2 is hydrogen or a compound represented by the following formula (2),
(2)
In the above formula, R3 is a residue containing a carboxylic acid derived by hydrogen or an acid anhydride, and R4 is hydrogen or an alkyl group of C1 to C4.
Moreover, this invention provides the manufacturing method of the said alkali-soluble resin.
The alkali-soluble resin of the present invention is excellent in physical properties such as adhesion, developability, sensitivity, chemical resistance, strength and elasticity, and excellent in miscibility and dispersibility with other organic binders, pigments, and dyes. It can be usefully used for various applications such as overcoat photoresist, column spacer, and the like.
The present invention relates to an alkali-soluble resin comprising a repeating unit represented by the following general formula (1):
[Formula 1]
In the above formula, R1 is hydrogen or an alkyl group of C1 ~ C4, R2 is hydrogen or a compound represented by the following formula (2),
(2)
In the above formula, R3 is a residue containing a carboxylic acid derived by hydrogen or an acid anhydride, and R4 is hydrogen or an alkyl group of C1 to C4.
Examples of alkyl groups of C1 to C4 in Chemical Formulas 1 and 2 include methyl, ethyl, propyl and butyl groups, preferably methyl or ethyl groups, and more preferably methyl groups.
Acid anhydride in the formula (2) is not particularly limited, specific examples are succinic anhydride, glutaric anhydride, 3-methyl glutaric anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, butyl succinic anhydride, 4 -Methylcyclohexane-1,2-dicarboxylic acid anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, 1,1-cyclopentanediacetic acid anhydride, (2-methyl-2-prop Phenyl) succinic anhydride, 3,3-dimethylglutaric anhydride, 2,2-dimethylglutaric anhydride, 1,1-cyclohexanediacetic anhydride, 2-buten-1-ylsuccinic anhydride, 3-methyl-4 -Cyclohexene-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, n- Octyl succinic anhydride, allyl succinic anhydride, bicyclo [2.2.2] octa-5-ene-2,3-dicarboxylic anhydride, phthalic anhydride, 4-methylphthalic anhydride, 2,3-naphthalenedicarboxylic anhydride , 1,2- Naphthalenedicarboxylic acid anhydride, 3-methylphthalic anhydride, diphenic acid anhydride, 1-cyclohexene-1,2-dicarboxylic acid anhydride, 6-dihydro-1,4-diyne-2,3-dicar Acid anhydride, 2,3-dimethylmaleic anhydride, maleic anhydride, 4-tert-butylphthalic anhydride, citraconic anhydride and the like.
In the alkali-soluble resin, the repeating unit represented by Chemical Formula 1 may be included in a molar fraction of 5 to 100 mol% based on the total moles of the repeating units included in the alkali-soluble resin, and may be included in 20 to 70 mol%. More preferred. When the repeating unit is included in the above-described range, the colored photosensitive resin composition of the present invention can achieve the desired properties, that is, properties such as excellent adhesion, developability, sensitivity, chemical resistance, strength and elasticity.
The alkali-soluble resin of the present invention comprises (1) a monomer of the following formula (3); (2) polymerizing a monomer represented by the following formula (3) and further reacting the polymer with a compound represented by the following formula (4); (3) polymerizing a monomer represented by the following formula (3) and further reacting the polymer with a compound represented by the following formula (4):
(3)
Wherein R 1 is hydrogen or an alkyl group of C 1 to C 4,
[Chemical Formula 4]
In the above formula, R4 is hydrogen or an alkyl group of C1 ~ C4.
The alkali-soluble resin may be prepared by copolymerizing at least one monomer other than the monomer (3) in the method (1) to (3).
The one or more other monomers mentioned above are not particularly limited, but may be monomers having unsaturated bonds capable of copolymerization.
Specific examples of the monomer having an unsaturated bond capable of copolymerization include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. , Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) Acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3- Alkyl ester compounds in which carboxylic acids bonded to unsaturated groups such as methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, pentadienyl (meth) acrylate and the like are substituted; (Meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (Meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl Acrylate, norbornyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexyl Unsaturated carboxylic acid ester compounds containing alicyclic substituents such as methyl (meth) acrylate and methyl glycidyl (meth) acrylate; Methoxy triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy polyethylene glycol ( Monosaturated carboxylic acid ester compounds of glycols such as meta) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, and oligoethylene glycol monoalkyl (meth) acrylate; Unsaturated carboxylic acid esters having a substituent having an aromatic ring such as benzyl (meth) acrylate, phenoxy (meth) acrylate, 2-phenoxyethyl (meth) acrylate and tetrahydroperfuryl compound; Aromatic vinyl compounds such as styrene, chlorostyrene,? -Methylstyrene and vinyltoluene; Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile; Maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide; (Meth) acrylates such as tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl ) Acrylate, and halogenated compounds such as tribromophenyl (meth) acrylate.
The monomers exemplified as the polymerizable monomers having an unsaturated bond capable of copolymerization may be used singly or in combination of two or more.
When the alkali-soluble resin of the present invention further includes one or more other monomers as other repeating units in addition to the repeating unit represented by Formula 1, the one or more other monomers may be mole fraction based on the total moles of repeating units included in the alkali-soluble resin. 5 to 95 mol%, and more preferably 30 to 80 mol%.
The unsaturated double bond contained in the alkali-soluble resin (A) of the present invention may play a role of imparting light / thermosetting property.
The alkali-soluble resin can be given an acid value in order to have solubility with respect to the alkali developer used in the development treatment step when forming the pattern. When giving an acid value, it is preferable that the acid value of the said alkali-soluble resin is 30-150 mgKOH / g. If the acid value is less than 30 mgKOH / g, it is difficult to secure a sufficient developing speed, and when the acid value is more than 150 mgKOH / g, adhesion to the substrate is reduced, and a pattern short circuit is likely to occur.
The alkali-soluble resin may be used that the weight average molecular weight in terms of polystyrene is 3,000 to 100,000, it may be used more preferably 5,000 to 50,000. When the weight average molecular weight is included in the above-described range, film reduction is prevented at the time of development, so that the omission of the pattern portion becomes good, which is preferable.
Hereinafter, the method for producing the alkali-soluble resin of the present invention will be described in more detail.
The first step in the production method of the alkali-soluble resin of the present invention is to prepare a polymer of a monomer represented by the following formula (3) containing an acid functional group (acid functional group).
(3)
In the above formula, R1 is hydrogen or an alkyl group of C1 ~ C4.
The reaction can be carried out by any one of various polymerization methods known in the art such as radical polymerization, cation polymerization, anion polymerization, condensation polymerization, etc. However, in view of easiness of production and economical efficiency, desirable.
For example, the monomer may be prepared by mixing with a polymerization solvent, heating to an appropriate temperature, and then removing oxygen through nitrogen purging. Further, it can be prepared preferably by adding a radical polymerization initiator and a chain transfer agent as necessary and maintaining the polymerization temperature. In the above method, the polymerization temperature and the polymerization time can be determined in consideration of the half life period of the polymerization initiator to be used depending on the temperature.
For example, since the half life of 2,2'-azobisisobutyronitrile (AIBN) at 70 ° C is 4.8 hours, the polymerization time when using this is preferably 6 hours or more. In general, the polymerization temperature is preferably between 50 ° C. and 150 ° C., and the polymerization time is preferably between 30 minutes and 48 hours.
As the radical polymerization initiator, those known in the art may be used, and specific examples thereof include 2,2'-azobisisobutyronitrile (AIBN) and 2,2'-azobis- (2,4-dimethylvalle. Ronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'- And bis- (bis-t-butylperoxy) cyclohexane.
The chain transfer agent is used to control the weight average molecular weight, and specific examples thereof include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid. , 3-mercaptopropionic acid, a-methylstyrene dimer, and the like.
In addition, at the time of polymerization of the monomer represented by Formula 3, it is also possible to further copolymerize one or more other monomers. At this time, one or more other monomer may be the same as described above.
The second step is, optionally, a step of adding and reacting a compound of formula 4 to introduce a photoreactive group into the (co) polymer produced in the first step.
[Chemical Formula 4]
In the above formula, R4 is hydrogen or an alkyl group of C1 ~ C4.
Examples of the ethylenically unsaturated compound containing the epoxy group include glycidyl (meth) acrylate.
The third step is optionally a step of reacting by adding an acid anhydride to the compound produced in the second step.
The compound of the acid anhydride is subjected to an esterification ring opening reaction with the copolymer having the hydroxyl group, thereby forming a photocurable alkali-soluble copolymer containing at least one photopolymerizable unsaturated bond in the molecule.
It is preferable that it is 1.0-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alkali-soluble resin of this invention, it is more preferable that it is 1.3-4.0. If the molecular weight distribution is 1.5 to 6.0, it is preferable because it is excellent in developability.
Hereinafter, the present invention will be described in more detail based on examples. However, the embodiments of the present invention described below are illustrative only, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In addition, "%" and "part" which show content in a following example and a comparative example are a basis of weight unless there is particular notice.
Synthetic example 1: Synthesis of Compound of Formula 3a
40.0 weight part of 4-hydroxybenzoic acid, 13.9 weight part of sodium hydroxide, and 300.0 weight part of tetrahydrofuran were put into the 4-necked round flask equipped with a cooling tube and the stirrer, and the inside temperature of the reactor was cooled to 0 degreeC, stirring. Subsequently, 36.33 parts by weight of methacryloyl chloride was added dropwise over 30 minutes. After dropping, the reaction temperature was raised to room temperature. The reaction was then continued for 3 hours. After completion of the reaction, 120 parts by weight of a saturated sodium hydrogencarbonate aqueous solution was added to the reaction mixture, and then 300 parts by weight of ethyl acetate was added to the reaction mixture. It was washed with 150 parts by weight of saturated brine, dried over anhydrous magnesium sulfate and filtered. Subsequently, the organic solvent was removed using a rotary evaporator, and the obtained solid substance was subjected to column purification using n-heptane and ethyl acetate to obtain a compound of Chemical Formula 3a.
1 H-NMR (300 MHz, DMSO-d6): 2.03 (s, 3H), 5.72 (d, 1H), 6.32 (d, 1H), 7.28 (d, 2H), 8.12 (d, 2H), 12.09 (br, 1H)
[Chemical Formula 3]
Example 1: Synthesis of Alkali Soluble Resin
120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 23.0 parts by weight of the compound of Formula 3a, in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube. 57.0 parts by weight of 4-methylstyrene, 10 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate and 3 parts by weight of n-dodecyl mercapto were added, and the flask atmosphere was replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the alkali-soluble resin thus synthesized was 64.7 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 16,170.
Example 2: Synthesis of Alkali Soluble Resin
120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 10.0 parts by weight of the compound of Formula 3a, in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot, and a nitrogen introduction tube. 62.0 parts by weight of 4-methylstyrene, 10 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, 8 parts by weight of methacrylic acid, and 3 parts by weight of n-dodecyl mercapto were added, and the flask atmosphere was replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the alkali-soluble resin thus synthesized was 80.4 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 17,290.
Example 3: Synthesis of Alkali-Soluble Resin
120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 10.0 parts by weight of the compound of Formula 3a, in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot, and a nitrogen introduction tube. 48.3 parts by weight of 4-methylstyrene, 10 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, 8 parts by weight of methacrylic acid, and 3 parts by weight of n-dodecyl mercapto were added, and the flask atmosphere was replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and the flask atmosphere was replaced with nitrogen from air, followed by 0.2 parts by weight of triethylamine, 0.1 parts by weight of 4-methoxy phenol, and 8.0 parts by weight of glycidyl methacrylate at 100 ° C. The reaction was carried out for 6 hours. Thereafter, the reaction solution was cooled to room temperature, 5.7 parts by weight of succinic anhydride was added and reacted at 80 ° C. for 12 hours. The solid acid value of the alkali-soluble resin thus synthesized was 78.8 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 16,850.
Example 4: Synthesis of alkali-soluble resin
120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 10.0 parts by weight of the compound of Formula 3a, in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot, and a nitrogen introduction tube. 60.0 parts by weight of 4-methylstyrene, 15 parts by weight of benzyl methacrylate, 15 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecyl mercapto were added, and the flask atmosphere was replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the alkali-soluble resin thus synthesized was 27.9 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 21,520.
Example 5: Synthesis of alkali-soluble resin
120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 10.0 parts by weight of the compound of Formula 3a, in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot, and a nitrogen introduction tube. 47.0 parts by weight of 4-methylstyrene, 10 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, 23 parts by weight of methacrylic acid, and 3 parts by weight of n-dodecyl mercapto were added, and the flask atmosphere was replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the alkali-soluble resin thus synthesized was 179.9 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 22,507.
Comparative Example One: Synthesis of alkali-soluble resin
120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 68.0 parts by weight of 4-methylstyrene in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot, and a nitrogen introduction tube. , 10 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, 12 parts by weight of methacrylic acid, and 3 parts by weight of n-dodecyl mercapto were added, and the flask atmosphere was replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. The solid acid value of the alkali-soluble resin thus synthesized was 77.6 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 19,380.
Test Example One.
Using the alkali soluble resins of Examples 1 to 5 and Comparative Example 1, photoresist compositions were each prepared in compositions as shown in Table 1 below. On the other hand, for comparison with the photoresist, the copolymer of methacrylic acid and benzyl methacrylate [the molar ratio of the methacrylic acid unit and the benzyl methacrylate unit is 27:73, the acid value is 83, and the weight average molecular weight is 18,000. Photoresist composition 7 was prepared in the same manner and composition using a general alkali soluble resin having a solid content of 30.2% (solvent: propylene glycol monomethyl ether acetate).
(Unit: parts by weight)
Co., Ltd. photopolymerizable compound (B): KAYARAD DPHA [manufactured by Nippon Kayaku]
Photoinitiator (C): (C-1) Irgacure 907 (made by BASF Corporation), (C-2) OXE-01 (made by BASF Corporation)
Solvent (D): Propylene glycol monomethyl ether acetate
The photoresist compositions prepared above were coated on a 2-inch angle glass substrate ("EAGLE XG" manufactured by Corning Corporation) by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film. Subsequently, a test photomask having a pattern for changing the transmittance stepwise in a range of 1 to 100% and a line / space pattern of 1 μm to 50 μm was placed on the thin film and the distance from the test photomask was 100 μm. Was investigated. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 100 mJ / cm 2, and no special optical filter was used. The UV-irradiated thin film was developed by soaking in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The thin plate coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200 ° C. for 25 minutes to prepare a coating film. The film thickness of the coating film produced above was 2.0 micrometers.
The coating film thus obtained was measured and evaluated as described below for sensitivity, adhesion, developability, and chemical resistance, and the results are shown in Table 2 below.
≪ Adhesion >
The generated pattern was evaluated through an optical microscope and evaluated by the following criteria.
○: no tearing on the pattern
△: 1 to 3 tears on the pattern
×: 4 or more tearing pattern
≪ Development speed >
The time taken for the unexposed area to completely dissolve in the developing solution at the time of development was measured.
<Pattern Straightness>
The shape of the pixel surface was observed using SEM (10,000 magnification).
○: linearity deviation of pattern edge is less than 1um
X: deviation of linearity of pattern edge is over 1um
<Elastic restoration rate>
After the formation of the spacer pattern, the maximum and final displacements were measured under the following conditions using a micro hardness tester (FISC HERSCOPE H100 manufactured by Fischer Installation Co., Ltd.), and then the elastic recovery rate was calculated by the following equation (1). .
[Formula 1]
Elastic recovery rate R (%) = (maximum displacement-final displacement) / maximum displacement x 100
Measurement conditions: Using a planar indenter with a temperature of 23 ° C. and a diameter of 50 μm, the spacer was loaded at a constant speed (2 mN / sec), held at the point where the maximum load of 80 (mN) was reached for 5 seconds, and then loaded at the same speed. The maximum displacement and final displacement were measured by removing.
As confirmed in Table 2, in the case of the photoresist compositions 1 to 5 using the alkali-soluble resins (Examples 1 to 5) according to the present invention, the photoresist composition 6 and the general alkali using the alkali-soluble resin of Comparative Example 1 Excellent results were obtained in all evaluation items compared to photoresist composition 7 using soluble resin.
Claims (11)
[Chemical Formula 1]
In the above formula, R1 is hydrogen or an alkyl group of C1 ~ C4, R2 is hydrogen or a compound represented by the following formula (2),
(2)
In the above formula, R3 is a residue containing a carboxylic acid derived by hydrogen or an acid anhydride, and R4 is hydrogen or an alkyl group of C1 to C4.
The repeating unit represented by the formula (1) is an alkali-soluble resin, characterized in that contained in 5 to 100 mol% by mole fraction with respect to the total number of moles of the repeating unit included in the alkali-soluble resin.
Alkali-soluble resin, characterized in that the alkyl group of C1 ~ C4 in the formula (1) and (2) is a methyl group.
Wherein the acid anhydride is selected from the group consisting of succinic anhydride, glutaric anhydride, 3-methylglutaric anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, butylsuccinic anhydride, 2-dicarboxylic acid anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, 1,1-cyclopentanediacetic anhydride, (2- 3-dimethylglutaric anhydride, 2,2-dimethylglutaric anhydride, 1,1-cyclohexane diacetic anhydride, 2-butene-1-ylsuccinic anhydride, 3-methyl- Norbornene-2,3-dicarboxylic acid anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, n-octylsuccinic anhydride, allylsuccinic anhydride , Bicyclo [2.2.2] octa-5-ene-2,3-dicarboxylic acid anhydride, phthalic anhydride, 4-methylphthalic anhydride, 2,3-naphthalene dicarboxylic acid anhydride, 1,2- A carboxylic acid anhydride, a 3-methyl Deoxidized anhydride, diphenic anhydride, 1-cyclohexene-1,2-dicarboxylic acid anhydride, 6-dihydro-1,4-dichine-2,3-dicarboxylic acid anhydride, 2,3-dimethylmale Alkali soluble resin, characterized in that it is selected from the group consisting of acid anhydride, maleic anhydride, 4-tert-butylphthalic anhydride, and citraconic anhydride.
The alkali-soluble resin is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, amino ethyl (meth) acrylate , Dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, acyl octyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate , Ethoxydiethylene glycol (meth) acrylate, pentadienyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) Acrylate, Cloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylic Rate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, glycidyl (meth) acrylate, 3,4- Epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol ( Meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxy polypropylene glycol (meth ) Acrylate, oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril (meth) acrylate , Styrene, chlorostyrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, (meth) acrylonitrile, α-chloroacrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide, tetrafluoro Propyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate And at least one monomer selected from the group consisting of tribromophenyl (meth) acrylate.
Wherein the alkali-soluble resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000.
Wherein the alkali-soluble resin has an acid value of 30 to 150 mgKOH / g.
Alkali-soluble resin characterized by being used as binder resin of the photosensitive material for color filter manufacture, the overcoat photosensitive material, and photosensitive material for spacer manufacture.
(2) polymerizing the monomer of the following formula (3), and further reacting the polymer of the formula (4) with the polymer;
(3) The method for producing an alkali-soluble resin of claim 1, wherein the monomer of formula (3) is polymerized, and the polymer is further reacted with a polymer of formula (4).
(3)
In the above formula, R1 is hydrogen or an alkyl group of C1 ~ C4.
[Chemical Formula 4]
In the above formula, R4 is hydrogen or an alkyl group of C1 ~ C4.
When polymerizing the monomer of the formula (3) in (1) to (3), at least one other monomer is added to copolymerize the production method of the alkali-soluble resin.
The at least one other monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, aminoethyl (meth) acrylic Rate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, acyl octyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acryl Ethylenediethylene glycol (meth) acrylate, pentadienyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl ( Meta) acrylic , Cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) ) Acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, glycidyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene Glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (Meth) acrylate, oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril (meth) Acrylate, styrene, chlorostyrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, (meth) acrylonitrile, α-chloroacrylonitrile, N-cyclohexylmaleimide, N-phenylmaleimide, tetra Fluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) A method for producing an alkali-soluble resin, characterized in that it is selected from the group consisting of acrylate, and tribromophenyl (meth) acrylate.
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| KR1020120089686A KR20140023617A (en) | 2012-08-16 | 2012-08-16 | Alkali-developable resins and process for producing the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20220105322A (en) * | 2021-01-20 | 2022-07-27 | 엑시노 주식회사 | Resin for photosensitive composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20220105322A (en) * | 2021-01-20 | 2022-07-27 | 엑시노 주식회사 | Resin for photosensitive composition |
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