KR101177119B1 - Alkali-soluble binder resin, preparing method thereof, and photosensitive resin composition containing the same - Google Patents

Abstract

The present invention provides an alkali-soluble binder resin, a preparation method thereof, and a photosensitive resin composition comprising the same.

The photosensitive resin composition using the alkali-soluble binder resin according to the present invention has a high crosslinking density, so that a pattern having a uniform thickness can be formed even with a small exposure amount, and elasticity and ductility, residual film ratio, heat resistance, chemical resistance, CD control, and mechanical properties This is excellent.

Color filter, liquid crystal display, photosensitive, column spacer, overcoat

Description

Alkali-soluble binder resin, preparing method, and photosensitive resin composition containing the same}

The present invention relates to an alkali-soluble binder resin capable of photocuring and thermosetting simultaneously by reacting a monomer containing a urethane group and an isocyanate group simultaneously with a resin having a thermosetting group, a method for preparing the same, and a photosensitive resin composition comprising the same.

The photosensitive composition may be applied to a substrate to form a coating film, and a specific portion of the coating film may be exposed by light irradiation using a photomask or the like, and then used to form a pattern by developing and removing the non-exposed portion. Such photosensitive compositions are used for photocurable inks, photosensitive printing plates, various photoresists, color filter photoresists for LCDs, photoresists for resin black matrices, transparent photoresists, and the like because they can be polymerized and cured by irradiation with light.

The photosensitive composition usually contains an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator and a solvent.

In the photosensitive composition, the alkali-soluble resin has an adhesive force with the substrate to enable coating, dissolve in an alkaline developer to form a fine pattern, and at the same time, give a strength to the obtained pattern to prevent the pattern from being broken during the post-treatment process. Play a role. In addition, it has a great influence on heat resistance and chemical resistance.

In general, since the photosensitive composition is formed of a coating film having a thickness of 3 µm or more and most of the coating film must be developed, the photosensitive resin composition must be dissolved in a large amount in the developer in a short time. In addition, if the development is not clear, not only direct staining due to the residue but also various display defects such as poor liquid crystal alignment may occur, and thus, the photosensitive composition should be very developable. In addition, when applying to a large area glass substrate, it is difficult to collectively expose the entire surface, so that the exposure is divided into several times. However, when the sensitivity of the photosensitive composition is low, the time required for the exposure process is long, which decreases productivity. do.

In addition, even at a high temperature process of 200 ° C. or more, sufficient compressive strength and chemical resistance are required so that the shape and thickness do not change and thermal damage is not caused by external pressure. In addition, excellent stability over time is required because it is possible to stably express certain desired characteristics without changing even during long-term storage. However, there has not been developed a photosensitive composition which satisfies all of heat resistance, chemical resistance, developability, sensitivity, and stability over time.

In addition, in order to improve the yield per unit time of the process in the process of using the photosensitive composition as described above, the exposure time and development time is reduced, and the sensitivity and developability compared to the existing photosensitive composition is 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, there is a problem that the photoinitiator with high photosensitivity is relatively expensive. In addition, when the amount of the photoinitiator is increased, there is a risk that a large amount of sublimable foreign substances may be generated in the post baking process to contaminate the oven or contaminate components such as liquid crystal in the LCD panel.

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.

For example, Korean Patent Publication No. 2000-0012118 discloses a method of introducing a (meth) acryloyl group into a chain of an alkali-soluble resin by condensation reaction of a (meth) acryloyl oxy alkyl isocyanate with a carboxyl or alcohol group in the alkali-soluble resin chain. It is described.

In addition, Korean Patent Laid-Open No. 2001-0018075 discloses a method of introducing a (meth) acryloyl group into a chain of an alkali-soluble resin by condensation reaction between a carboxyl group and a glycidyl (meth) acrylate in an alkali-soluble resin chain. .

By the way, the photosensitivity of the photopolymerizable reactive group introduced into the alkali-soluble resin has a positive correlation, but since the photopolymerizable reactive group is introduced into the acid group of the alkali-soluble resin, the ratio of the photopolymerizable reactive group in the alkali-soluble resin increases. There is a problem that developability is lowered because the proportion of remaining acid groups is relatively low.

On the other hand, the photosensitive composition using a thermosetting binder (binder) is not only poor stability over time, but also low photosensitivity (sensitivity) 150 mJ / ㎠ There is a problem that it is difficult to implement a stable pattern with the following exposure amount.

Therefore, development of alkali-soluble resin excellent in all of said heat resistance, chemical resistance, developability, sensitivity, and stability with time is calculated | required.

Accordingly, the present inventors have been devised to solve various problems of the alkali-soluble binder resin included in the photosensitive resin composition as described above.

Accordingly, it is an object of the present invention to provide an alkali-soluble binder resin having excellent physical properties such as heat resistance, chemical resistance, developability, sensitivity, and stability over time since photocuring and thermosetting are possible at the same time.

In addition, another object of the present invention is to provide a method for producing an alkali-soluble binder resin as described above.

Further, another object of the present invention is to provide a photosensitive resin composition comprising the alkali-soluble binder resin.

In the present invention, by synthesizing a monomer containing a urethane and an isocyanate group at the same time as the alkali-soluble binder resin, and secondary reaction with a resin having a thermosetting group to develop a resin capable of photocuring and thermosetting at the same time, by applying it to the photosensitive resin composition The above problems can be solved.

According to the present invention, an alkali-soluble binder resin capable of photocuring and thermosetting simultaneously is prepared by second-reacting a monomer containing a urethane group and an isocyanate group simultaneously with a resin having a thermosetting group, and the crosslinking density is increased as the photosensitive composition is used. Also, it is possible to form a pattern having a uniform thickness, and excellent in elasticity, ductility, residual film ratio, heat resistance, chemical resistance, CD control, and mechanical properties. It can also be usefully used for photocurable inks, photosensitive printing plates, various photoresists, color filter photoresists for LCDs, photoresists for resin black matrices, or transparent photosensitive materials.

Alkali-soluble binder resin of the present invention for achieving the above object is characterized by that represented by the following formula (1).

Wherein R is hydrogen or a methyl group, X is a group derived from a thermosetting monomer, Y is a group derived from a monomer comprising an acid group, and Z and W are the same as or different from each other and are derived from aromatic and aliphatic vinyl monomers, respectively A, b, c, d and e each represent a repeating unit, assuming that the total is 100 mol%, a is 10 to 40 mol%, b is 10 to 30 mol%, c is 5 To 20 mol%, d is 5 to 20 mol%, and e is 5 to 20 mol%.

In addition, the production method of the alkali-soluble binder resin represented by the formula (1) for achieving another object of the present invention is Reacting a monomer having a hydroxy group with a diisocyanate compound to prepare a monomer having a urethane group and an isocyanate group at the same time; And copolymerizing by adding a monomer including an acid group, a thermosetting monomer, and an aliphatic or aromatic vinyl monomer to the monomer having the urethane group and the isocyanate group at the same time.

In addition, the photosensitive resin composition for achieving another object of the present invention is 5 to 20% by weight of the alkali-soluble binder resin, 5 to 25% by weight polymerizable compound, 0.5 to 4% by weight photoinitiator, and solvent 60 to 80 It is characterized by including the weight%.

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

Alkali-soluble binder resin represented by the formula (1) of the present invention comprises the steps of reacting a monomer having a hydroxy group and a diisocyanate compound to prepare a monomer having a urethane and an isocyanate group at the same time; And copolymerizing by adding a monomer including an acid group, a thermosetting monomer, and an aliphatic or aromatic vinyl monomer to the monomer having the urethane group and the isocyanate group at the same time.

The monomer containing a hydroxy group used in the first step is hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl It is preferable to use one or more compounds selected from the group consisting of α-hydroxymethyl acrylate, and butyl α-hydroxymethyl acrylate, but is not limited thereto.

In addition, specific examples of the diisocyanate compound include 2,6-toylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3 -Butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, w, w'- diisocyanate-1,3-dimethylbenzene, w, w ' -Diisocyanate-1,4-dimethylbenzene, w, w'- diisocyanate-1,3-diethylbenzene, 1,4-tetramethyl xylene diisocyanate, 1,3-tetramethyl xylene diisocyanate, isophorone di Isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate , Methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene bisocyanate methylcyclohexane, 2,5-isocyanatemethyl bicyclo [2,2,2] heptane, and 2,6-isocyanatemethyl bicyclo One selected from the group consisting of [2,2,1] heptane, but is not limited thereto.

In the first step reaction, when a monomer containing a hydroxy group and a diisocyanate compound are reacted under an organic solvent at a temperature of 25 to 60 ° C. for 1 to 5 hours, a monomer containing both a urethane and an isocyanate group represented by the following Formula 2 is obtained. Can be.

It is preferable that the reaction equivalence ratio of the monomer containing the said hydroxyl group and a diisocyanate compound is 1.0: 1.0-1.0: 1.2.

In the above formula, R is hydrogen or methyl group.

Next, in the second step, a monomer comprising an acid functional group, a thermosetting monomer, a monomer containing a hydroxy group, and an aliphatic or aromatic vinyl monomer are added to a monomer containing both a urethane group and an isocyanate group simultaneously. By reacting, an alkali-soluble binder resin represented by Chemical Formula 1 is prepared.

Specifically, a copolymer solution is prepared by mixing and reacting a monomer including the acid group, a thermosetting monomer, a monomer including a hydroxy group, and an aliphatic or aromatic vinyl monomer under a thermal initiator, and then the urethane group and the isocyanate. The monomers containing the groups at the same time are added, followed by reaction until the isocyanate groups disappear completely.

The monomer containing an acid group is a compound selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, isoprenesulfonic acid, styrenesulfonic acid, and 5-norbornene-2-carboxylic acid. to be.

Moreover, as a thermosetting monomer, allyl glycidyl ether, glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2-carboxylate (endo, Exo mixture), 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene to be.

As the monomer containing a hydroxy group, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl ( Meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl Acrylate, and butyl α-hydroxymethyl acrylate.

In addition, the aromatic vinyl monomers are compounds selected from the group consisting of styrene, chlorostyrene, α-methyl styrene and vinyltoluene.

In addition, examples of the aliphatic vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and iso Butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-phenoxyethyl (meth) acrylic Laterate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxy Oxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, Ethoxydiethylene glycol (meta) Acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy Polyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl ( Meta) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and tribromophenyl (meth) acrylate.

The reaction may be prepared by any one of a variety of polymerization methods known in the art, such as radical polymerization, cationic polymerization, anionic polymerization, condensation polymerization, etc., but it is most preferable to use radical polymerization in view of ease of production and economical efficiency. desirable.

For example, the monomer may be prepared by mixing with a polymerization solvent and heating to an appropriate temperature, followed by removal of oxygen through nitrogen purging. In addition, it may be preferably prepared by adding a radical polymerization initiator and a chain transfer agent and maintaining the polymerization temperature as necessary. In the above method, the polymerization temperature and the polymerization time may be determined in consideration of the half-life depending on the temperature of the polymerization initiator to be used.

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'- Bis- (bis-t-butylperoxy) cyclohexane and the like.

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, but are not limited thereto, and those known in the art may be used.

In the finally prepared alkali-soluble binder resin represented by Formula 1 of the present invention, X is a part constituting the thermosetting monomer, specifically, allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclo Hexylmethyl (meth) acrylate, glycidyl 5-norbornene-2-carboxylate (endo, exo mixture), 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), 1,2 A group derived from a compound selected from the group consisting of epoxy-5-hexene, and 1,2-epoxy-9-decene,

Y is a part constituting the monomer containing an acid group, specifically, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, isoprenesulfonic acid, styrenesulfonic acid, 5-norbornene-2- A group derived from a compound selected from the group consisting of carboxylic acids,

Z and W are portions constituting an aliphatic or aromatic vinyl monomer, Z is a group derived from a compound selected from the group consisting of styrene, chlorostyrene, α-methyl styrene, vinyltoluene,

W is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpryl (meth) acrylic Rate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyl octyl Oxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, Methoxytriethylene glycol (meth ) Acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p- Nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl ( Group derived from a compound selected from the group consisting of meth) acrylate, heptadecafluorodecyl (meth) acrylate, and tribromophenyl (meth) acrylate.

The alkali-soluble binder resin represented by Chemical Formula 1 may have a matrix function when forming a thin film of the photosensitive composition, and includes a polymer material that provides solubility to a developer which is an aqueous alkali solution.

In addition, the present invention provides a photosensitive composition comprising an alkali-soluble binder resin represented by the formula (1), a polymerizable compound, a photopolymerization initiator, and a solvent.

The alkali-soluble binder resin used in the composition of the present invention has an acid value of about 70 to 140 KOH mg / g, preferably a weight average molecular weight of 5,000 to 100,000, more preferably in the range of 8,000 to 50,000.

The binder resin may be used alone or in combination of two or more thereof, the content of which is preferably 5 to 20% by weight of the total photosensitive composition. If less than 5% by weight, the adhesion of the formed film is inferior, and if it exceeds 20% by weight, there is a disadvantage in that the developing speed is slow and the sensitivity is lowered.

The polymerizable compound used in the composition of the present invention is a substance having a boiling point of 100 ° C. or more and containing two or more reactive groups in a molecule, and is polymerized by radical active species formed from a photopolymerization initiator to form a three-dimensional network structure. It is a functional monomer which has an ethylenically unsaturated bond.

Specific examples of the functional monomer having an ethylenically unsaturated bond include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, and polyethylene glycol (meth) acrylate. , Polypropylene glycol (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetraacrylate, pentaerythritol tri At least one member selected from the group consisting of acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

More specifically, the functional monomers to which caprolactone is introduced include KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and the like introduced to dipentaerythritol, and tetrahydrofurfuryl. KAYARAD TC-110S introduced to acrylate, KAYARAD HX-220 and KAYARAD HK-620 introduced to neopentylglycol hydroxy pivalate.

In addition, examples of the epoxy acrylate, novolak-epoxy acrylate and urethane-based polyfunctional acrylate of bisphenol A derivatives include U-324A, U15HA, and U-4HA.

The functional monomer which has the said ethylenically unsaturated double bond can be used individually or in mixture of 2 or more types. The amount of the polymerizable compound in the composition of the present invention is preferably 5 to 25% by weight of the total photosensitive composition. If the amount is less than 5% by weight, the photosensitivity or the strength of the coating film is lowered. If the amount is more than 25% by weight, the adhesiveness of the photosensitive resin layer is excessive, and foreign matters are easily attached, and residues may occur during the development process.

The photopolymerization initiator used in the photosensitive resin composition of the present invention is a compound capable of generating a photopolymerization reaction by absorbing light upon irradiation of light such as UV and generating radical active species by a photochemical reaction.

Examples of photopolymerization initiators include 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine, 2 , 4-trichloromethyl- (pipelonyl) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, and 3- {4- [ Triazine compounds selected from the group consisting of 2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, and 2,2'-bis (2,3-dichlorophenyl) -4,4', Biimidazole compounds selected from the group consisting of 5,5'-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxy Methoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexylphenyl ketone, benzoinmethyl ether, benzoinethyl ether, benzoin isobutyl ether, benzoinbutyl ether, 2,2-dimethoxy- 2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholino Acetophenone compounds selected from the group consisting of phenyl) -butan-1-one; O-acyl oxime compounds selected from the group consisting of Irgacure OXE 01, and Irgacure OXE 02 from Ciba Geigy; Benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3 Benzophenone compounds selected from the group consisting of, 3-dimethyl-4-methoxybenzophenone, and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; Fluorenone compounds selected from the group consisting of 9- fluorenone, 2-chloro-9- fluorenone, and 2-methyl-9- fluorenone; From the group consisting of thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone, and diisopropyl thioxanthone. Selected thioxanthone compound; Xanthone compounds such as xanthone or 2-methylxanthone; Anthraquinone compounds selected from the group consisting of anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; With 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, and 1,3-bis (9-acridinyl) propane Acridine-based compound selected from the group consisting of; Dicarbonyl compounds selected from the group consisting of benzyl, 1,7,7-trimethyl-bisclo [2,2,1] heptan-2,3-dione, and 9,10-phenanthrenequinone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, and bis (2,6-dichlorobenzoyl) propyl phosphine Phosphine oxide compounds selected from the group consisting of oxides; Methyl 4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2,5-bis (4-diethylaminobenzal) Amine system selected from the group consisting of cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, and 2,6-bis (4-diethylaminobenzal) -4-methyl-cyclohexanone Synergy; 3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, and 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl Coumarin-based compounds selected from the group consisting of] -benzopyrano [6,7,8-ij] -quinolizin-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; One or more selected from the group consisting of 2-benzoylmethylene and 3-methyl-β-naphthothiazoline may be used, but a photopolymerization initiator known in the art may be used without being limited thereto.

The amount of the photopolymerization initiator used in the photosensitive resin composition of the present invention is preferably 0.5 to 4% by weight in the total photosensitive composition. If the amount of use is less than 0.5% by weight, the sensitivity is lowered. If the amount is more than 4% by weight, it is difficult to control developability, pattern thickness, and CD (critical dimension).

The solvent used in the composition of the present invention is to dissolve other components in order to provide coating properties to the photosensitive composition, the viscosity can be adjusted according to the amount used. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl Ether, propylene glycol diethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethane , 1,2,3-trichloropropane, hexane, heptane, octane, cyclopentane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monomethyl ether, methyl car Bitol, ethyl carbitol, propyl carbitol, butyl carbitol, cyclopentanone, cyclohexanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether propionate, 3-methoxybutyl acetate, 3 Single or two selected from the group consisting of -methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propyl acetate, and ethyl acetate The above can be mixed and used. In consideration of viscosity adjustment, the amount of the solvent is preferably 60 to 80% by weight in the total photosensitive composition.

The photosensitive composition of the present invention may be hydroquinone, 4-methoxyphenol, quinone, pyrocatechol, t-butyl catechol, phenothiazine, etc. as necessary in addition to the essential components. Thermal polymerization inhibitors; Plasticizers; Silicone adhesion promoters; Other additives commonly used in fillers or coatings.

Since the resin according to the present invention includes a thermally reactive group and a urethane-based photoreactive group at the same time, the composition using the resin according to the present invention has a high crosslinking density, so that a pattern having a uniform thickness can be formed even with a small exposure amount. Excellent heat resistance, chemical resistance, CD control and mechanical properties.

Therefore, the photosensitive composition which concerns on this invention can be usefully used for a photocurable ink, the photosensitive printing plate, various photoresists, the color filter photoresist for LCD, the photoresist for resin black matrix, or a transparent photosensitive material.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Example  One

1-1. Urethane tile  Simultaneously containing isocyanate groups Monomeric  synthesis

106.9 g of hydroxyethyl methacrylate and 143.1 g of 2,6-toylene diisocyanate were added to the reactor, and 250 g of hexane solvent was added thereto, followed by reaction for 2 hours while maintaining the temperature at 50 ° C. After the reaction was terminated, the precipitated white solid was filtered, washed several times with hexane and dried to obtain 210 g of a monomer containing urethane and isocyanate groups simultaneously represented by the following formula (3). (Yield 84%)

1-2. Preparation of Binder Resin 1

After dissolving 3 parts by weight of a thermal initiator in a solvent, hydroxyethyl acrylate / benzyl methacrylate / styrene / methacrylic acid / glycidyl methacrylate was added in a molar ratio of 10/15/15/25/35. The reaction was carried out for 12 hours while maintaining at 60 ° C. in a nitrogen atmosphere.

The copolymer solution obtained above was added to a flask equipped with a stirrer, and the monomer containing the urethane and isocyanate group prepared in 1-1 at the same time was added thereto, followed by reaction until the isocyanate group disappeared completely, thereby preparing a photosensitive thermosetting copolymer. . The acid value of the prepared alkali-soluble binder resin was 95KOHmg / g, the weight average molecular weight was 13,500.

1-3. Preparation of Photosensitive Resin Composition

In the reaction mixing tank equipped with the ultraviolet ray blocker and the stirrer, 7% by weight of the alkali-soluble binder resin prepared in the above 1-2, 13% by weight of the polyfunctional monomer (dipentaerythritol hexaacrylate), a photoinitiator (brand name: OXE-02 ) 2.0% by weight, silane epoxy compound (trade name: KBM 503) 0.25% by weight, a small amount of thermal polymerization inhibitor (4-methoxyphenol) and a leveling agent (trade name: BYK 331) was added sequentially to prepare a photosensitive composition After stirring. Subsequently, 77.6 g of propylene glycol methyl ether acetate was added to the composition, and the viscosity of the composition was adjusted to 13 cps.

Example  2

2-1. Preparation of Binder Resin 2

After dissolving 3 parts by weight of a thermal initiator in a solvent, hydroxyethyl methacrylate / benzyl methacrylate / styrene / dicyclopentanyl methacrylate / methacrylic acid / glycidyl methacrylate is 10/10/10/10. The mixture was added at a molar ratio of / 25/35, and the reaction was carried out for 12 hours while maintaining at 60 ° C. in a nitrogen atmosphere.

The copolymer solution obtained above was added to a flask with a stirrer, and the monomer containing the urethane group and the isocyanate group prepared in Example 1-1 was added at the same time, and then reacted until the isocyanate group disappeared completely. Was prepared. The acid value of the prepared alkali-soluble binder resin was 90 KOH mg / g, the weight average molecular weight was 12,300.

2-2. Preparation of Photosensitive Resin Composition

Except for using the binder resin 2 prepared in Example 2-1 instead of the binder resin 1, a photosensitive resin composition was prepared in the same manner as in Example 1-3.

Comparative example  One

1-1. Photoreactivity  Preparation of Resin

Five-component copolymer ring-opened and added in the same manner as in Example 1 to the copolymer of the reactive resin [benzyl methacrylate / N-phenylmaleimide / styrene / methacrylic acid] using glycidyl methacrylate (20 / 15/15/25/25). The acid value of the prepared copolymer was 115 KOH mg / g, the weight average molecular weight was 13,000.

1-2. Preparation of the photosensitive composition

A photosensitive composition was prepared in the same manner as in Example 1 to 1-3, except that the photoreactive group resin prepared in Comparative Example 1-1 was used instead of binder resin 1.

Comparative example  2

2-1. Preparation of Thermosetting Resin

A four-component copolymer (20/20 // 25/35) of [benzyl methacrylate / styrene / methacrylic acid / glycidyl methacrylate] was prepared. The acid value of the prepared copolymer was 110 KOH mg / g, the weight average molecular weight was 13,000.

2-2. Preparation of the photosensitive composition

A photosensitive composition was prepared in the same manner as in Example 1-3, except that the thermosetting resin prepared in Comparative Example 2-1 was used instead of the binder resin 1.

Experimental Example

The physical properties of the photosensitive compositions prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1 below.

 (1) residue characteristics

After the development, the presence or absence of the remaining residue was observed without being washed off at the site to be developed. It was good when there was no residue and evaluated as defective if there was a residue.

(2) residual film rate

By measuring the thickness before and after the post heat treatment, the difference in thickness was evaluated by the following equation (1).

Residual film ratio = (film thickness after post-heat treatment) / (film thickness before post-heat treatment) X 100 (%)

The higher the residual film ratio, the better. When the residual film ratio was more than 95%, the evaluation was excellent, 95-93% good, and less than that.

(3) thermal resistance

After the final pattern was formed, the thickness change due to thermal shock was confirmed by Equation 2 below.

Thickness change rate = (film thickness after heat treatment) / (film thickness before heat treatment) X 100 (%)

Given the heat of high temperature, a certain amount of change in thickness after a certain period of time can be said to be good. When heat was applied at 240 ° C. for 1 hour, the rate of change in thickness was 90% or more.

(4) chemical resistance

When left in various chemicals (10% NaOH aqueous solution, 10% HCl aqueous solution, NMP), the chemical resistance test was performed by observing the thickness change. The thickness change rate was calculated by the above equation (3). As with thermal resistance, the lower the rate of change of thickness when exposed to chemicals, the better. When submerged for 1 hour at room temperature for 1 hour, it was determined that 103% or less was good, and more than that, poor.

(5) CD (Critical Dimension) Control

Finally, upon pattern formation, it was determined that the control of the top and bottom CD of the pattern was as easy as possible, and not easy, by controlling the content and components in the composition.

(6) mechanical properties

After the pattern formation, when the deformation of 10% of the thickness (or depending on the conditions) is given, the degree of return is called an elastic recovery rate, and the absolute value greatly varies depending on the conditions of the pattern. The result of the Example and the comparative example which formed the pattern on the same conditions was compared comparatively, and the lowest thing was shown as defect, the more excellent and excellent.

Residue characteristics Residual film ratio Heat resistance Chemical resistance CD control Mechanical properties Example 1 Good Good Good Great ease Great Example 2 Good Good Good Great ease Great Comparative Example 1 Good Bad Good Good ease Good Comparative Example 2 Bad Great Good Good ease Good

As shown in Table 1, it was confirmed that the photosensitive composition according to the present invention is excellent in residue properties, residual film ratio, heat resistance, chemical resistance, CD control, mechanical properties by applying a resin capable of photocuring and thermosetting at the same time to the composition .

Claims (20)

Alkali-soluble binder resin represented by following General formula (1). Formula 1

R is hydrogen or a methyl group, X is a group derived from a thermosetting monomer Y is a group derived from a monomer containing an acid group, Z and W are the same or different and are groups derived from aromatic and aliphatic vinyl monomers, respectively, and a, b, c, d and e each represent a repeating unit, assuming that the total is 100 mol%. 10-40 mol%, b is 10-30 mol%, c is 5-20 mol%, d is 5-20 mol%, e is 5-20 mol%. The method of claim 1, wherein the thermosetting monomer is allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2-carboxyl Consisting of late (endo, exo mixture), 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene Alkali-soluble binder resin, characterized in that the compound selected from the group. According to claim 1, wherein the monomer containing an acid group (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, 5-norbornene-2-carboxylic acid Alkali-soluble binder resin, characterized in that the compound selected from the group. The alkali-soluble binder resin according to claim 1, wherein the aromatic vinyl monomer is a compound selected from the group consisting of styrene, chlorostyrene, α-methyl styrene, and vinyltoluene. The method of claim 1, wherein the aliphatic vinyl monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, iso Butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-phenoxyethyl (meth) acrylic Laterate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxy Oxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, Ethoxydiethylene glycol (meth) a Relate, methoxy triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy Polyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl ( Alkali-soluble binder resin, characterized in that the compound selected from the group consisting of meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate . The alkali-soluble binder resin according to claim 1, wherein the alkali-soluble binder resin has a weight average molecular weight of 5,000 to 100,000 and an acid value of 70 to 140 KOHmg / g. Reacting a monomer having a hydroxy group with a diisocyanate compound to prepare a monomer having a urethane group and an isocyanate group at the same time; A method for producing an alkali-soluble binder resin according to claim 1, comprising adding and copolymerizing a monomer including an acid group, a thermosetting monomer, and an aliphatic or aromatic vinyl monomer to a monomer having an urethane group and an isocyanate group at the same time. The monomer according to claim 7, wherein the monomer having a hydroxy group is hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxy Hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α- A method for producing an alkali-soluble binder resin, characterized in that the compound selected from the group consisting of hydroxymethyl acrylate, and butyl α-hydroxymethyl acrylate. The diisocyanate compound according to claim 7, wherein the diisocyanate compound is 2,6-toylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3 -Butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, w, w'- diisocyanate-1,3-dimethylbenzene, w, w ' -Diisocyanate-1,4-dimethylbenzene, w, w'- diisocyanate-1,3-diethylbenzene, 1,4-tetramethyl xylene diisocyanate, 1,3-tetramethyl xylene diisocyanate, isophorone di Isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, mesocyanate -2,6-cyclohexane diisocyanate, 4,4'-methylene bis isocyanate methylcyclohexane, 2,5-isocyanatemethyl bicyclo [2,2,2] heptane, and 2,6-isocyanatemethyl bicyclo [2 , 2,1] heptane is a process for producing an alkali-soluble binder resin, characterized in that more than selected from the group consisting of. The method of claim 7, wherein the thermosetting monomer is allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2-carboxyl Consisting of late (endo, exo mixture), 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene A method for producing an alkali-soluble binder resin, which is a group derived from a compound selected from the group. 8. The monomer according to claim 7, wherein the monomer containing an acid group is composed of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, isoprenesulfonic acid, styrenesulfonic acid, 5-norbornene-2-carboxylic acid. Method for producing an alkali-soluble binder resin, characterized in that at least one member selected from the group. 8. The method of claim 7, wherein the aromatic vinyl monomer is a compound selected from the group consisting of styrene, chlorostyrene, α-methyl styrene and vinyltoluene. The method of claim 7, wherein the aliphatic vinyl monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate , Tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxy Sidiethylene glycol (meta) a Relate, methoxy triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy Polyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl ( Alkali-soluble binder resin, characterized in that the compound selected from the group consisting of meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate Manufacturing method. 8. The method of claim 7, wherein the reaction is carried out by radical polymerization. Alkali-soluble photosensitive resin composition containing 5-20 weight% of alkali-soluble binder resins of Claim 1, 5-25 weight% of polymeric compounds, 0.5-4 weight% of photoinitiators, and 60-80 weight% of solvents. The method of claim 15, wherein the polymerizable compound is polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (Meth) acrylate, trimethylol ethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, di An alkali-soluble photosensitive resin composition characterized by at least one member selected from the group consisting of pentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. The method of claim 15, wherein the photopolymerization initiator is a triazine compound; Biimidazole compounds; Acetophenone compounds; O-acyl oxime compound; Benzophenone compounds; Fluorenone compounds; Thioxanthone type compounds; Xanthone compounds; Anthraquinone compounds; Acridine-based compounds; Dicarbonyl compounds; Phosphine oxide compounds; Amine synergy; Coumarin compound; Chalcone compound; An alkali-soluble photosensitive resin composition, which is at least one selected from the group consisting of 2-benzoylmethylene and 3-methyl-β-naphthothiazoline. The method of claim 15, wherein the solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl Ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2 Trichloroethene, 1,2,3-trichloropropane, hexane, heptane, octane, cyclopentane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monomethyl Tere, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, cyclopentanone, cyclohexanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether propionate, 3-methoxy 1 type selected from the group consisting of butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propyl acetate, and ethyl acetate Alkali-soluble photosensitive resin composition characterized by the above-mentioned. The color filter obtained from the alkali-soluble photosensitive resin composition of any one of Claims 15-18. A liquid crystal display device comprising the color filter of claim 19.