KR20070013026A - Resin having excellent mechanical physical property, and photosensitive composition comprising the same - Google Patents

Abstract

Provided are a resin, which is superior in residue characteristics, remaining rate, heat resistance, chemical resistance, CD control, and mechanical properties because a crosslinking density and a glass transition temperature are increased by photo-reactive groups and heat-reactive groups. The resin is obtained by copolymerizing alkyl 2-(hydroxymethyl) group-containing acrylate monomer represented by the following formula 2 with a resin having photo-reactive groups. In the formula 2, R is a straight or branched C1-4 alkyl group. The resin having photo-reactive groups is a compound prepared by undergoing a polymer reaction between an alkali-soluble linear copolymer and an epoxy group-containing ethylenic unsaturated compound, wherein the alkali-soluble linear copolymer is obtained by copolymerizing acid functional group-containing monomer with monomer copolymerizable therewith.

Description

Resin having excellent mechanical physical property, and photosensitive composition comprising the same}

The present invention relates to a resin obtained by copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group to a resin having a photoreactive group, and a photosensitive 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 adhesion to 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. 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 higher, sufficient compressive strength and chemical resistance are required so as not to be destroyed by external pressure, with thermal stability such that shape and thickness do not change. 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.

For example, Japanese Patent Laid-Open No. 2001-151829 discloses a photosensitive composition using a thermosetting binder. However, this 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 inventors of the present invention, while studying the alkali-soluble resin excellent in all of the heat resistance, chemical resistance, developability, sensitivity, and stability over time, the inventors of the acrylate monomer containing an alkyl 2- (hydroxymethyl) group has a resin having a photoreactive group The resin copolymerized in the present invention was confirmed to have excellent mechanical properties by improving the glass transition temperature as well as the crosslinking density, thereby completing the present invention.

The present invention aims to provide a resin obtained by copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group to a resin having a photoreactive group.

The present invention also provides a method for producing a resin obtained by copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group to a resin having a photoreactive group.

In addition, the present invention is to provide a photosensitive composition comprising the resin.

The present invention provides a resin obtained by copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group represented by the following formula (2) to a resin having a photoreactive group.

(In Formula 2, R is a C ₁ ~ C ₄ linear or branched alkyl group.)

One example of the resin according to the present invention is represented by the following formula (1).

(In Formula 1,

R is a C ₁ to C ₄ straight or branched alkyl group,

R 'and R "are each independently hydrogen or a methyl group,

X is allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2-carboxylate (endo, exo mixture), Groups derived from a compound selected from the group consisting of 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene Is,

a is 10 to 40 mol%, b is 10 to 30 mol% and c is 30 to 60 mol%.)

In Formula 1 or 2, R is methyl, ethyl, propyl or butyl.

The resin having a photoreactive group functions as a matrix when forming a thin film of the photosensitive composition, and includes a polymer material that provides solubility to a developing solution which is an aqueous alkali solution. In the present invention, by using a photopolymerizable reactive resin having excellent compatibility with other constituents as a resin having a photoreactive group, it is possible to improve the chemical resistance and stability over time of the photosensitive composition. For example, the photoreactive group may be represented by the following Chemical Formula 3.

The resin having the photoreactive group may be prepared in two steps as follows.

The first step is to prepare an alkali-soluble linear copolymer by copolymerizing monomers containing acid functional groups with monomers copolymerizable therewith. It is preferable to use those latter monomers which can increase the film strength. As a monomer for increasing film strength, a compound containing an aromatic ring may be used.

As an example of the monomer used for manufacture of the said linear copolymer, As a monomer containing an acidic radical, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, 5-norbornene -2-carboxylic acid, and the like, and monomers capable of copolymerization therewith include styrene, chlorostyrene, α-methyl styrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. , Benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) a Relate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2 -Methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (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, Tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth Acrylic Ray And the like, tribromo-phenyl (meth) acrylate.

The second step is to give a photoreactivity to the resin and to cause a polymer reaction between the alkali-soluble linear copolymer prepared in the first step and the ethylenically unsaturated compound containing an epoxy group. Examples of the ethylenically unsaturated compound containing an epoxy group used here include 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, 1,2-epoxy-9- Decene, and the like, and these may be used alone or in combination of two or more during the polymer reaction.

The present invention also provides a method for producing a resin comprising copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group to a resin having a photoreactive group.

As one example, the method for producing a resin according to the present invention,

1) After dissolving the thermal initiator in a solvent, the acrylate monomer containing the alkyl 2- (hydroxymethyl) group represented by the formula (2) is added thereto, and maintained at 50 ~ 70 ℃ in nitrogen atmosphere for 10 to 15 hours Reacting, and

2) raise the temperature of the acrylate monomer copolymer solution containing the alkyl 2- (hydroxymethyl) group obtained in step 1) to 100-150 ° C., and then react the resin having a photoreactive group to the copolymer resin. Manufacturing step.

Completion of the reaction of the prepared copolymer resin can be seen that the epoxy group of the resin having a photoreactive group completely disappears, which can be known by measuring the acid value with a pH meter. The acid value of the prepared copolymer resin was calculated, and when the measured value came close to the calculated value by measuring the acid value of the copolymer resin with a pH meter during the reaction, it was found that the epoxy group disappeared during the reaction.

In addition, the present invention

1) a resin obtained by copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group to a resin having a photoreactive group,

2) polymerizable compounds,

3) photopolymerization initiator, and

4) It provides the photosensitive composition containing a solvent.

The resin obtained by copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group used in the composition of the present invention to a resin having a photoreactive group has an acid value of about 70 to 140 KOH mg / g and a weight average molecular weight of 5,000 It is preferable that it is -100,000, and it is more preferable that it is the range of 8,000-50,000. The resin may be used alone or in combination of two or more, the amount of the resin is preferably 5 to 20 parts by weight based on 100 parts by weight of the total photosensitive composition. If it is less than 5 parts by weight, the adhesion of the formed film is inferior, and if it is 20 parts by weight or more, there is a disadvantage in that the developing speed is low and the sensitivity is low.

The polymerizable compound used in the composition of the present invention is a substance containing two or more reactive groups in a molecule, and is a compound capable of forming a three-dimensional network structure by causing a polymerization reaction by radically active species formed from a photopolymerization initiator. In the present invention, a functional monomer having an ethylenically unsaturated bond can be used as the polymerizable compound. The functional monomer which has an ethylenically unsaturated bond has the unsaturated group which can carry out at least 1 addition polymerization in a molecule | numerator, and the compound whose boiling point is 100 degreeC or more is preferable. Specific examples of the functional monomer having an ethylenically unsaturated bond include monofunctional monomers such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate and polyethylene glycol ( Meta) acrylate, polypropylene glycol (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetraacrylate, Pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like. In addition, functional monomers having caprolactone as an example of the functional monomer having an ethylenically unsaturated bond include those introduced into dipentaerythritol in the form of KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA- 120, KAYARAD TC-110S introduced to tetrahydroperfuryl acrylate, KAYARAD HX-220, KAYARAD HK-620 introduced to neopentylglycol hydroxy pivalate, and the like. Other functional monomers having ethylenically unsaturated bonds include epoxy acrylates of bisphenol A derivatives, novolak-epoxy acrylates, and urethane-based polyfunctional acrylates, such as U-324A, U15HA, and U-4HA. have. 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 used in the composition of the present invention is preferably 5 to 25 parts by weight based on 100 parts by weight of the total photosensitive composition. If the amount is less than 5 parts by weight, the photosensitivity or the strength of the coating film is lowered. If the amount is more than 25 parts 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 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- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- {4- [2 Triazine compounds such as, 4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5 Biimidazole compounds such as 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, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl Acetophenone-based compounds such as) -butan-1-one; Benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3 Benzophenone compounds such as 3,3-dimethyl-4-methoxybenzophenone and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; Fluorenone compounds such as 9- fluorenone, 2-chloro-9- fluorenone and 2-methyl-9- fluorenone; Thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone compound; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bisclo [2,2,1] heptane-2,3-dione, 9,10-phenanthrenequinone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide Phosphine oxide compounds such as these; Methyl 4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2,5-bis (4-diethylaminobenzal) Amine synergists such as cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, and 2,6-bis (4-diethylaminobenzal) -4-methyl-cyclohexanone; 3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl] Coumarin-based compounds such as -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 composition of the present invention is preferably 0.5 to 4 parts by weight based on 100 parts by weight of the total photosensitive composition. If the amount is less than 0.5 parts by weight, the sensitivity is lowered, if more than 4 parts by weight it is difficult to control the developability, pattern thickness, 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-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 ether, methyl car Tol, 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 -Methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propyl acetate, ethyl acetate, and the like. It can be mixed and used. In consideration of viscosity adjustment, the amount of the solvent is preferably 60 to 80 parts by weight based on 100 parts by weight of the total 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.

The resins according to the invention have thermally reactive groups derived from acrylate monomers containing alkyl 2- (hydroxymethyl) groups. Therefore, as shown in Scheme 1 below, the hydroxy group and the ester group in the thermoreactive group during the thermal curing to form a lactone by the cyclization reaction, thereby increasing the glass transition temperature (Tg), thereby improving the mechanical properties. In addition, the resin according to the present invention has a high crosslinking density due to the photoreactive group, further improves the residue properties, residual film ratio, heat resistance, chemical resistance, CD control, 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.

Wherein R is as defined in Formula 1 above.

Hereinafter, preferred examples are provided to aid in understanding 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  : Alkyl  2-( Hydroxymethyl Containing group Acrylate Monomers  To resin having photoreactive group Copolymerized  Preparation of Resin and Photosensitive Composition Comprising the Same

Example  One  :

1-1. Preparation of Resin 1: Ethyl 2- ( Hydroxymethyl ) Acrylate Of Methyl methacrylate Copolymers containing Yttrate / Styrene / Methacrylic Acid / Photoreactive Group

After dissolving 3 parts by weight of a thermal initiator in a solvent, ethyl 2- (hydroxymethyl) acrylate / methylmethacrylate / styrene / methacrylic acid was added at a molar ratio of 35/12/13/40, and then in a nitrogen atmosphere. The reaction was carried out for 12 hours while maintaining the ℃. A 35/12/13/40 copolymer solution of the above-mentioned reactive resin [ethyl 2- (hydroxymethyl) acrylate / methylmethacrylate / styrene / methacrylic acid] was added to a flask with a stirrer and the temperature was 110. Oligo Glycidyl methacrylate was added to the temperature and then reacted until the epoxy group disappeared completely to prepare a 5-component copolymer (35/12/13/22/18).

The disappearance of the epoxy group can be determined by measuring the acid value with a pH meter, and calculating the acid value of the copolymer resin prepared above, and measuring the acid value of the copolymer resin with a pH meter during the reaction. It was found that the epoxy group disappeared.

Acid value 92 KOH mg / g, Molecular weight = 8,900

1-2. Preparation of the photosensitive composition

5-20 wt% of the resin 1 prepared in 1-1 above, 5-20 wt% of the polyfunctional monomer (dipentaerythritol hexaacrylate), and a photoinitiator (brand name: Iga) Cure 907) 0.5 to 3% by weight, silane epoxy compound (brand name: KBM 502) 0.1 to 3% by weight, a small amount of thermal polymerization inhibitor (4-methoxyphenol) and leveling agent (brand name: BYK 331) sequentially added To prepare a photosensitive composition, followed by stirring. Propylene glycol methyl ether acetate was then added to the composition to adjust the viscosity of the composition to 13 cps.

Example  2  :

2-1. Preparation of Resin 2: Ethyl 2- ( Hydroxymethyl ) Acrylate / Styrene / Metaarch Copolymer with Lylic Acid / Photoreactive Group

After dissolving 3 parts by weight of a thermal initiator in a solvent, ethyl 2- (hydroxymethyl) acrylate / styrene / methacrylic acid was added at a molar ratio of 30/30/40, followed by reaction at 60 ° C. under a nitrogen atmosphere for 12 hours. I was. 30/30/40 copolymer of the reactive resin [ethyl 2- (hydroxymethyl) acrylate / styrene / methacrylic acid] obtained above was added to a flask with a stirrer and the temperature was raised to 110 ° C. and glycidyl methacryl. After adding the rate, the reaction was carried out until the epoxy group completely disappeared to prepare a four-component copolymer (30/30/22/18).

Acid value 106 KOH mg / g, Molecular weight = 9,200

2-2. Preparation of the photosensitive composition

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

Example  3  :

3-1. Preparation of Resin 3: Ethyl 2- ( Hydroxymethyl ) Acrylate / Styrene / Metaarch Copolymer with Lylic Acid / Photoreactive Group

Ethyl 2- (hydroxymethyl) acrylate / styrene / methacrylic acid dissolved in 3 parts by weight of a thermal initiator in a solvent was added at a molar ratio of 35/15/50, followed by reaction for 12 hours at 60 ° C. in a nitrogen atmosphere. . The 35/15/50 copolymer of the reactive resin [ethyl 2- (hydroxymethyl) acrylate / styrene / methacrylic acid] obtained above was added to a flask with a stirrer and the temperature was raised to 110 ° C. and glycidyl methacryl. After adding the rate, the reaction was performed until the epoxy group disappeared completely to prepare a four-component copolymer (30/15/32/18).

Acid value 113 KOH mg / g, Molecular weight = 11,000

3-2. Preparation of the photosensitive composition

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

Example  4  :

4-1. Preparation of Resin 4: Ethyl 2- ( Hydroxymethyl ) Acrylate Of Dicyclopentanylme Copolymers containing other acrylate / methacrylic acid / photoreactive groups

After dissolving 3 parts by weight of a thermal initiator in a solvent, ethyl 2- (hydroxymethyl) acrylate / dicyclopentanyl methacrylate / methacrylic acid was added at a molar ratio of 40/20/40, and then maintained at 60 ° C. in a nitrogen atmosphere. And reacted for 12 hours. 40/20/40 copolymer of the above-mentioned reactive resin [ethyl 2- (hydroxymethyl) acrylate / dicyclopentanyl methacrylate / methacrylic acid] was added to a flask with a stirrer and the temperature was raised to 110 ° C. Glycidyl methacrylate was added and then reacted until the epoxy group disappeared completely to prepare a four-component copolymer (40/20/22/18).

Acid value 79 KOH mg / g, Molecular weight = 11,500

4-2. Preparation of the photosensitive composition

Except for using Resin 4 instead of Resin 1 in the composition component of Example 1, a photosensitive composition was prepared in the same manner as in Example 1-2.

Example  5  :

5-1. Preparation of Resin 5: Ethyl 2- ( Hydroxymethyl ) Acrylate / N- Phenylmaleimide Copolymers containing styrene / methacrylic acid / photoreactive groups

After dissolving 3 parts by weight of a thermal initiator in a solvent, ethyl 2- (hydroxymethyl) acrylate / N-phenylmaleimide / styrene / methacrylic acid was added at a molar ratio of 30/10/10/50, and then in a nitrogen atmosphere. The reaction was carried out for 12 hours while maintaining 60 ° C. 30/10/10/50 copolymer of the reactive resin [Ethyl 2- (hydroxymethyl) acrylate / N-phenylmaleimide / styrene / methacrylic acid] obtained above was added to a flask with a stirrer and the temperature was 110 Oligo Glycidyl methacrylate was added to the temperature and then reacted until the epoxy group completely disappeared to prepare a 5-component copolymer (30/10/10/34/16).

Acid value 91 KOH mg / g, Molecular weight = 11,800

5-2. Preparation of the photosensitive composition

Except for using the resin 5 instead of the resin 1 of the composition component of Example 1, a photosensitive composition was prepared in the same manner as in Example 1-2.

Example  6 :

6-1. Preparation of Resin 6: Ethyl 2- ( Hydroxymethyl ) Acrylate / N- Phenylmaleimide / Dicyclopentanyl methacrylate / methacrylic acid / copolymer containing photoreactive group

3 parts by weight of the thermal initiator was dissolved in a solvent in a reaction vessel, and ethyl 2- (hydroxymethyl) acrylate / N-phenylmaleimide / dicyclopentanyl methacrylate / methacrylic acid was added at a molar ratio of 30/10/10/50. After the reaction was carried out for 12 hours while maintaining at 60 ℃ in a nitrogen atmosphere. The 30/10/10/50 copolymer of the reactive resin [ethyl 2- (hydroxymethyl) acrylate / N-phenylmaleimide / dicyclopentanyl methacrylate / methacrylic acid] obtained above was added to a flask with a stirrer. The mixture was heated up to 110 ° C., and glycidyl methacrylate was added thereto, followed by reaction until the epoxy group disappeared completely, thereby preparing a 5-component copolymer (30/10/10/32/18).

Acid value 92 KOH mg / g, Molecular weight = 12,000

6-2. Preparation of the photosensitive composition

Except for using the resin 6 instead of the resin 1 of the composition component of Example 1, a photosensitive composition was prepared in the same manner as in Example 1-2.

Comparative example  One  :

One. Photoreactive group  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).

Acid value 115 KOH mg / g, Molecular weight = 13,000

2. Preparation of Photosensitive Composition

A photosensitive composition was prepared in the same manner as in Example 1-2, except that the photoreactive group resin prepared in 1 was used instead of the resin 1 in the composition component of Example 1.

Experimental Example  Evaluation of Physical Properties of Photosensitive Compositions According to the Present Invention

The physical properties of the photosensitive compositions prepared in Examples and Comparative Examples were measured by the following method.

(1) glass transition temperature

The glass transition temperature was observed by using DSC (Differential Scanning Calorimetry), heated to 150 ° C, cooled to room temperature, reheated to 220 ° C, and cooled to room temperature.

(2) 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. When there is no residue, it is said to be good and if there is a residue, it was evaluated as bad.

(3) 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-treatment) / (film thickness before post-treatment) x 100 (%).

The higher the residual film ratio, the better.

When the residual film ratio was more than 85%, the result was good.

(4) 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 thickness change ratio was 90% or more.

(5) 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. 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 immersed for 1 hour at room temperature for 1 hour, it was determined that 103% or less was good, and more than that, poor.

(6) 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.

(7) 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.

The results are shown in Table 1.

Composition Glass transition temperature (Tg *) Residue properties Residual rate Heat resistance Chemical resistance CD control Mechanical properties After the first heating After the second heating Example 1 135 140 Bad Good Good Good ease Good Example 2 110 118 Good Good Good Good ease Great Example 3 134 143 Good Good Good Good ease Great Example 4 127 152 Good Good Good Good ease Good Example 5 135 137 Good Good Good Good ease Good Example 6 148 160 Good Great Good Good ease Great Comparative Example 1 135 135 Good Good Good Good ease Good  * Glass transition temperature change after the first heating and after the second heating

As shown in Table 1, the photosensitive composition according to the present invention has a high crosslinking density due to the photoreactive group and a high glass transition temperature after the second heating due to the thermal reactive group. Excellent control and mechanical properties.

The resin obtained by copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group to a resin having a photoreactive group has a high crosslinking density due to a photoreactive group and a high glass transition temperature due to a thermal reactive group. Because of this superiority, it can be usefully used for photocurable inks, photosensitive printing plates, various photoresists, color filter photoresists for LCDs, photoresists for resin black matrices, transparent photoresists, and the like.

Claims (11)

A resin obtained by copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group represented by the following formula (2) to a resin having a photoreactive group. <Formula 2>

In Formula 2, R is a C ₁ ~ C ₄ linear or branched alkyl group. The resin of claim 1, wherein the photoreactive group is represented by the following Chemical Formula 3. <Formula 3>

The method of claim 1, wherein the resin having a photoreactive group is a polymer reaction between an monomer containing an acid functional group and an alkali-soluble linear copolymer obtained by copolymerizing monomers copolymerizable therewith with an ethylenically unsaturated compound containing an epoxy group. Resin, characterized in that the compound produced. 4. The monomer of claim 3, wherein the monomer containing an acid functional group includes (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, isoprenesulfonic acid, styrenesulfonic acid and 5-norbornene Resin characterized by comprising at least one member selected from the group consisting of 2-carboxylic acids. The method of claim 3, wherein the monomer copolymerizable with the monomer containing an acid functional group includes styrene, chlorostyrene, α-methyl styrene, vinyltoluene, methyl (meth) acrylate, and ethyl (meth) acryl. Rate, 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-hydrate Hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethyl Hexyl acrylic , 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (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) acrylic Laterate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl A resin comprising at least one member selected from the group consisting of (meth) acrylate and tribromophenyl (meth) acrylate. The method of claim 3, wherein the ethylenically unsaturated compound containing an epoxy group is 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 And at least one member selected from the group consisting of -9-decene. The resin of claim 1, wherein the resin is represented by the following Chemical Formula 1. <Formula 1>

In Chemical Formula 1, R is a C ₁ to C ₄ straight or branched alkyl group, R 'and R "are each independently hydrogen or a methyl group, X is allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2-carboxylate (endo, exo mixture), Groups derived from a compound selected from the group consisting of 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene Is, a is 10-40 mol%, b is 10-30 mol%, c is 30-60 mol%. A method for producing a resin comprising copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group represented by Formula 2 to a resin having a photoreactive group. <Formula 2>

In Formula 2, R is a C ₁ ~ C ₄ linear or branched alkyl group. The method according to claim 8, wherein 1) the thermal initiator is dissolved in a solvent, and then an acrylate monomer containing an alkyl 2- (hydroxymethyl) group is added thereto and maintained at 50 to 70 ° C. in a nitrogen atmosphere for 10 to 15 hours. Reacting, and 2) raise the temperature of the acrylate monomer copolymer solution containing the alkyl 2- (hydroxymethyl) group obtained in step 1) to 100-150 ° C., and then react the resin having a photoreactive group to the copolymer resin. Method of producing a resin comprising the step of producing. 1) A resin obtained by copolymerizing an acrylate monomer containing an alkyl 2- (hydroxymethyl) group according to any one of claims 1 to 7 to a resin having a photoreactive group, 2) polymerizable compounds, 3) photopolymerization initiator, and 4) A photosensitive composition comprising a solvent. The method according to claim 10, wherein the acrylate monomer containing the alkyl 2- (hydroxymethyl) group according to any one of claims 1 to 7 is copolymerized with a resin having a photoreactive group based on 100 parts by weight of the composition. 5 to 20 parts by weight of the resin, 2) 5 to 25 parts by weight of the polymerizable compound, 3) 0.5 to 4 parts by weight of the photopolymerization initiator, and 4) 60 to 80 parts by weight of the solvent.