KR20100127903A - Photosensitive resin composition for column spacer having enhanced storage stability, paten stiffness and strength of stability - Google Patents

Abstract

PURPOSE: A photo-sensitive resin composition for a column spacer is provided to secure the excellent storage stability and development property, and to obtain a pattern with the wide upper diameter. CONSTITUTION: A photo-sensitive resin composition for a column spacer contains a copolymer A, and a copolymer B. The copolymer A contains 2-tetrahydropyranyl group containing polymerizable monomer marked with chemical formula 1, and an epoxy group-containing polymerizable monomer. In the chemical formula 1, R1 is either a hydrogen atom or an alkyl group with 1~5 carbons. The copolymer B contains a compound marked with chemical formula 2.

Description

Photosensitive resin composition for column spacer having enhanced storage stability, paten stiffness and strength of stability}

The present invention provides a photosensitive resin composition used in the manufacture of a column spacer to maintain a uniform cell gap when the color filter substrate and the TFT (thin film transistor) plate are bonded during a liquid crystal display device manufacturing process, a column spacer pattern manufactured therefrom, A color filter and a liquid crystal element are related.

The photosensitive resin composition is coated on a substrate to form a coating film, and the coating film is entirely exposed to form an insulating film or a protective film, or after exposure by light irradiation using a photomask or the like to a specific portion of the coating film, and then a non-exposed part. Can be used to form a pattern by developing and removing it.

Since the photosensitive resin composition can be irradiated with light to polymerize and harden, photocurable inks, photosensitive printing plates, various photoresists, color filter photoresists for liquid crystal displays (LCD), photoresists for resin black matrices, or transparent photoresists. It is used for ashes.

Among them, the transparent photosensitive resin composition includes a column spacer, an overcoat, and a passivation film, and is usually a liquid containing an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a solvent without using a coloring aid such as a pigment. The composition of the state. As the use of LCD becomes more advanced and diversified, it is manufactured for the purpose of constituting liquid crystal display devices such as TVs and monitors as well as the use of conventional notebooks and mobiles. In other words, photosensitivity is a very important factor. In addition, in the case of forming the pattern, the parts not reacted by the light should be washed away so as not to contaminate the liquid crystal layer or cause problems in the subsequent process.

In particular, in the case of the column spacer, the mechanical properties of the column spacer pattern should be excellent in order to exert the original performance without damaging the liquid crystal display device by the impact applied from the outside. In the case of column spacers, there is generally a deformation of the top shape as well as a reduction in thickness before and after the firing process. If such deformation is large, the area of the portion supporting the thin film transistor substrate is reduced, and the resistance to the external force of the panel is weakened. Therefore, maintaining a large support area by reducing the variation in the firing process is directly related to maintaining the mechanical properties of the column spacer.

In addition, the storage stability of the materials used is important for the stable production of LCD products. In the case of column spacers, the storage stability is particularly important because the same pattern thickness and size are required to maintain a constant distance between the color filter substrate and the TFT plate. . This is due to the increase in viscosity caused by chemical bonding between the polymer resin included in the composition.

Therefore, there is a need for the development of a polymer resin that can minimize the above disadvantages.

In order to solve the problems of the prior art, the present invention is a mixture of an alkali insoluble polymer resin containing an unsaturated carboxylic acid protected carboxyl group and a polymer resin compound containing an alkali-soluble unsaturated carboxylic acid in a predetermined ratio By using as a binder lattice, to provide a column spacer composition with improved storage stability and mechanical strength of the pattern.

The present invention provides a column spacer composition comprising copolymers (A) and (B):

Copolymer (A)

A copolymer containing a 2-tetrahydropyridyl group-containing polymerizable monomer (a-1) and an epoxy group-containing polymerizable monomer (a-2) represented by the following Chemical Formula 1

[Formula 1]

(R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

Copolymer (B)

A copolymer containing a compound represented by formula (2)

[Formula 2]

(m and n are integers from 3 to 40.)

The copolymers (A), (B) or (A) and (B) are aliphatic or aromatic (meth) acrylates, caprolactone-modified (meth) acrylates, acrylate monomers having hydroxyl groups, styrene-based monomers, silicone-based ( It may include at least one polymerizable monomer (a-3) selected from the group consisting of a meta) acrylate monomer, 1,3-butadiene and isoprene.

The present invention also provides a column spacer pattern, a color filter for a liquid crystal display device, and a liquid crystal display device formed from the composition.

The photosensitive composition for column spacers provided by the present invention has excellent storage stability and developability, a pattern having a large upper diameter when forming a pattern, and has excellent pattern toughness and compression recovery rate.

The composition of the present invention is described in detail below.

<Copolymer (A)>

Copolymer (A) is a copolymer containing monomer (a-1), (a-2) and monomer (a-3) as needed.

(a-1) 2-tetrahydropyranyl group-containing polymerizable monomer represented by the following formula (1)

[Formula 1]

R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. This alkyl group can be either straight or branched. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group and n-pentyl group.

The monomer of Formula 1 is pyrolyzed in the present firing to generate an acid, and the generated acid reacts with an adjacent epoxy group to cure. Since the monomer of Formula 1 is a kind of latent curing agent, it shows a very good storage stability compared to conventional thermosetting compositions containing carboxylic acid or carboxylic anhydride. The content of monomer (a-1) represented by the general formula (1) is 5 to 50% by weight of the copolymer (A), particularly preferably 10 to 40% by weight.

(a-2) Epoxy Group-Containing Polymerizable Monomer

The polymerizable monomer (a-2) is, for example, glycidyl (meth) acrylate, glycidyl-ethyl (meth) acrylate, glycidyl-n-propyl (meth) acrylate, glycidyl-n -Butyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 5,6-epoxyheptyl (meth) acrylate, 6,7-epoxyheptyl -Aliphatic epoxy compounds, such as ethyl acrylate and methylglycidyl (meth) acrylate. The content of the polymerizable monomer (a-2) is in the range of 5 to 70% by weight in the copolymer (A), preferably 10 to 50% by weight. When the content of the monomer (a-2) is less than 5% by weight, hardening does not occur sufficiently and defects in mechanical strength, chemical resistance and heat resistance are likely to occur.

(a-3) Other polymerizable monomer

The polymerizable monomer added as needed other than the monomers (a-1) and (a-2) is not particularly limited. For example, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) Aliphatic or aromatic such as acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate ( Meta) acrylate; Caprolactone modified (meth) acrylates such as TONE M-100, TONE M-101, TONE M-201 (above DOW Chemical) and FM-1, FM-2, FM-3 (above Daicel UCB); Acrylate monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, M-20G, M-40G, and M-90G (above manufactured by Shin-Nakamura); Styrene monomers such as styrene, 4-methoxystyrene, and 4-methylstyrene; Silicone-based (meth) acrylate monomers such as KBM-503 and KBM-5103 (from ShinEtsu Chemical Co., Ltd.); 1, 3- butadiene, isoprene, etc. are mentioned. Monomer (a-3) can be used in order to adjust suitably the physical property of a cured coating film obtained from a thermosetting resin composition, for example, mechanical strength, adhesiveness, flatness, etc. Monomer (a-3) may be included in the range of 0 to 80% by weight of the copolymer (A).

<Copolymer (B)>

Copolymer (B) is a copolymer which essentially contains the compound (b-1) represented by following formula (2), and contains a polymeric monomer (a-3) as needed.

[Formula 2]

(m and n are integers from 3 to 40.)

The polymerizable monomer (a-3) may be included in the range of 0 to 80% by weight of the copolymer (B).

The copolymers (A) and (B) can be any of random copolymers, block copolymers, and the like, and the copolymer production method is not particularly limited, such as a solution polymerization method or an emulsion polymerization method.

The molecular weight of the copolymer (A) is not particularly limited as long as it can realize a flat film. It is appropriately selected depending on the thickness of the film to be formed, the equipment to be applied, and the conditions and purposes for forming the film. Usually, the range of about 2,000-100,000 polystyrene conversion weight average molecular weight is appropriate, and it is more preferable to exist in the range 3,000-50,000. When the molecular weight is 2,000 or less, the film forming performance of the composition tends to be lowered, and when the molecular weight is 100,000 or more, there is a problem in that the polymer is not easy to handle.

The column spacer composition of the present invention, in addition to the copolymers (A) and (B), additives necessary for other purposes such as film forming performance, photocuring performance, alkali solubility, chemical stability, and the like, for example, radical initiators having a photoactivity, and multi-tubes Functional monomers, adhesion aids, surfactants, solvents and the like.

<Photoactive radical initiator>

Non-limiting examples of photoactive radical initiators for imparting curing properties by light irradiation of the composition include 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloro methyl -(4'-methoxystyryl) -6-triazine, 2,4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4'- Dimethoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methylbiphenyl) -6-triazine, 2,4-trichloromethyl- (4'-ethylbiphenyl) -6 Triazine compounds such as -triazine and 3- {4- [2,4-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-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-mol Acetope such as polyno-1-propane-1-one (Irgacure-907) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure-369) Non-based compounds; O-acyl oxime compounds such as Irgacure OXE 01 and Irgacure OXE 02 from Ciba Geigy; Benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone; Thioxanthone-based compounds such as 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone; 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; 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] -quinolizine-11-one, and the like, and may be used by one or more thereof, but are not limited thereto. Known ones can be used.

The use ratio of the photoactive radical initiator can be 0.1 to 30 parts by weight per 100 parts by weight of the total amount of the copolymers (A) and (B), more preferably 1 to 15 parts by weight.

<Polyfunctional monomer>

The polyfunctional monomer has one or more ethylenically unsaturated bonds and is preferably a compound having 2 to 6 unsaturated functional groups. For example, polyethyleneglycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Compounds selected from the group of polyfunctional (meth) acrylates such as acrylate and dipentaerythritol hexa (meth) acrylate can be used alone or in combination of two or more thereof. It is more preferable to use dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate among them.

The use ratio of the polyfunctional monomer is 1 to 300 parts by weight per 100 parts by weight of the total amount of the copolymers (A) and (B), more preferably 100 to 200 parts by weight. The polyfunctional monomer is a crosslinking compound and is a lower molecular weight than the copolymers (A) and (B), and forms chemical bonds by radicals generated by light irradiation.

<Adhesive preparation>

The adhesion aid is a compound that serves to enhance adhesion to the substrate, and the silane-based compound is generally limited, but is not particularly limited as long as it satisfies the above object. For example, methacryloxypropyl trimethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, (gamma)-mercaptopropyl trimethoxysilane, Vinyltriacetoxysilane, vinyltrimethoxysilane, and the like.

The use ratio of the adhesion aid may be 30 parts by weight or less per 100 parts by weight of the total amount of the copolymers (A) and (B), more preferably 20 parts by weight or less. When the adhesive aid is used in excess of 30 parts by weight, the coating properties and storage stability may deteriorate.

<Other additives>

Other additives include surfactants. Surfactant is fluorine-type or silicone type surfactant. Examples of the fluorine-based surfactants include 3-4 FC-4430, and the silicone-based surfactants include BYK-306, BYK-307, BYK-310, BYK-331 (above BYK-Chemie), and SH-. 8400, SF-8419 (above Toray-Silicon), etc. are mentioned. Other additives are preferably used in an amount of 2 parts by weight or less per 100 parts by weight of the total amount of the copolymers (A) and (B). In the case of surfactants, the use of more than 2 parts by weight tends to cause excessive foaming.

<Solvent>

The solvent used for preparing the composition solution of the present invention is not particularly limited as long as it is capable of dissolving each component uniformly and at the same time chemically stable and not reactive with the components of the composition. Alkyl ketones such as methyl ethyl ketone and cyclohexanone; Ethers such as tetrahydrofuran; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and ethylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate; Ethylene glycols such as butyl cellosolve, 2-methoxyethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol diethyl ether; Compounds selected from the group consisting of esters such as ethyl acetate, ethyl lactate and ethyl 3-ethoxypropionate are used alone or in combination of two or more thereof.

The present invention also provides a method for producing a transparent thin film layer for a liquid crystal display device, which is produced using the photosensitive resin composition according to the present invention.

The transparent thin film layer for the liquid crystal display device may be manufactured through a general manufacturing method known in the art, except for using the photosensitive resin composition according to the present invention. For example, it can be used in slit coaters, roll coaters, curtain coaters, spin coaters, spin coaters, and various printing, deposition, etc., and is applied on supports such as metal, paper, glass, and plastic substrates. Can be. Moreover, after apply | coating on support bodies, such as a film, it is also possible to transfer on other support bodies, The application method is not specifically limited.

As a light source for hardening the photosensitive resin composition of this invention, mercury vapor arc (arc), carbon arc, Xe arc etc. which emit light of 250-450 nm in wavelength, for example are mentioned.

The present invention will be described in more detail with reference to the following examples. However, the Examples are provided to illustrate the present invention and the scope of the present invention is not limited thereto.

<Examples>

In the following Examples, the present invention will be described in more detail, but the present invention is not limited to these Examples.

Synthesis Example 1

30 parts by weight of a mixture of 2-tetrahydropyranyl methacrylate, glycidyl methacrylate, styrene and benzyl methacrylate in a molar content of 10%, 30%, 20% and 40%, respectively, as a thermal initiator 3 parts by weight of V-65 and 70 parts by weight of propylene glycol methyl ether acetate were added to a reaction vessel, and the reaction was carried out for 12 hours while maintaining at 60 ° C. in a nitrogen atmosphere. The molecular weight of the obtained reactive binder was Mw = 16000.

Synthesis Example 2

As in Synthesis Example 1, 2-tetrahydropyranyl methacrylate, glycidyl methacrylate, styrene and benzyl methacrylate were used as molar ratios of 30%, 30%, 10%, and 30%, respectively. . The molecular weight of the obtained reactive binder was Mw = 17000.

&Lt; Synthesis Example 3 &

30 parts by weight of a mixture of methacrylic acid, styrene and benzyl methacrylate in a molar content of 60%, 10% and 30%, respectively, 3 parts by weight of V-65 as a thermal initiator and 70 parts by weight of propylene glycol methylether acetate After the addition, the reaction was carried out for 12 hours while maintaining at 60 ° C. in a nitrogen atmosphere. The copolymer solution was poured into a flask with a stirrer, the temperature was raised to 110 ° C, and glycidyl methacrylate was added to react until the epoxy group disappeared completely, thereby bringing the copolymer to a molar content of 20% methacrylic acid. Was synthesized. The acid value of the obtained copolymer was 105 KOH mg / g, and the molecular weight was Mw = 15000.

Comparative Synthesis Example 1

30 parts by weight of a mixture of methacrylic acid, glycidyl methacrylate, styrene and benzyl methacrylate in a molar content of 10%, 30%, 20% and 40%, respectively, 3 parts by weight of V-65 as a thermal initiator and 70 parts by weight of propylene glycol methyl ether acetate was placed in a reaction vessel, and the reaction was continued for 12 hours while maintaining at 60 ° C. in a nitrogen atmosphere. The molecular weight of the obtained reactive binder was Mw = 19000.

&Lt; Example 1 >

Using a mixture of the copolymer prepared in Synthesis Example 1 and Synthesis Example 3 in a weight ratio of 3: 7 as a binder polymer, 8 parts by weight of the binder polymer, 12 parts by weight of hexaacrylate, 1- [9- as a photopolymerization initiator Ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-0-acetate (trade name Irgacure OXE 02, manufactured by Ciba Specialty Chemicals, Inc.) 1 weight Part and 79 parts by weight of an organic solvent PGMEA were mixed using a shaker for 3 hours. This mixed photosensitive solution is filtered using a 5 micron filter to obtain a photosensitive composition for column spacers.

Spin coating of this composition on glass and electrothermally treating at about 100 [deg.] C. for 2 minutes yields an even film having a thickness of about 2.5 [mu] m. After the film was exposed under a high pressure mercury lamp using a circular isolated pattern photomask having a diameter of 15 μm, the pattern was developed for 60 seconds with an aqueous KOH alkali solution having a pH of 11.3 to 11.7 and washed with deionized water. After post-treatment at 200 ° C. for about 30 minutes, the state of the pattern was observed with a pattern profiler, and the pattern toughness and compression recovery rate were measured with a micro compression tester.

<Example 2>

It is the same as that of Example 1 except for using the mixture of the copolymer prepared in Synthesis Example 1 and Synthesis Example 3 in a weight ratio of 5: 5 as the binder polymer.

<Example 3>

It is the same as that of Example 1 except for using a mixture of the copolymer prepared in Synthesis Example 2 and Synthesis Example 3 in a weight ratio of 3: 7 as the binder polymer.

<Example 4>

It is the same as that of Example 1 except for using a mixture of the copolymer prepared in Synthesis Example 2 and Synthesis Example 3 in a weight ratio of 5: 5 as the binder polymer.

Comparative Example 1

Except that the copolymer prepared in Synthesis Example 1 was used alone as a binder polymer is the same as in Example 1.

Comparative Example 2

Except that the copolymer prepared in Synthesis Example 2 was used alone as a binder polymer is the same as in Example 1.

Comparative Example 3

Except that the copolymer prepared in Synthesis Example 3 was used alone as a binder polymer is the same as in Example 1.

<Comparative Example 4>

Except for using the copolymer prepared in Comparative Synthesis Example 1 alone as a binder polymer is the same as in Example 1.

Comparative Example 5

Except that the copolymer prepared in Comparative Synthesis Example 1 and Synthesis Example 3 in a weight ratio of 3: 7 was used as the binder polymer as in Example 1.

Comparative Example 6

It is the same as that of Example 1 except for using a mixture of the copolymer prepared in Comparative Synthesis Example 1 and Synthesis Example 3 in a weight ratio of 5: 5 as the binder polymer.

<Evaluation of Physical Properties of Photosensitive Compositions for Column Spacers>

The physical properties of the photosensitive compositions for column spacers prepared in Examples and Comparative Examples were measured by the following methods, and the results are summarized in the following [Table 1].

Storage stability

The curable composition (P1) was stored at room temperature for 2 weeks, and then the rate of change relative to the initial viscosity was measured.

Developability

The KOH alkali aqueous solution of 11.3-11.7 was used as a developing solution, and it confirmed whether the unexposed part remained after developing for 60 second. If the glass surface of the remaining part except the pattern after the development was seen, it was marked as good (O), and not visible as bad (X).

Pattern top diameter

The upper diameter corresponding to 95% of the total thickness of the pattern obtained through the Examples and Comparative Examples was measured by a pattern profiler.

Pattern toughness

The pattern formed by the circular independent patterned photomask having a diameter of 15 μm was applied by a micro-compression tester for 20 seconds with a 100mN load, and the thickness change was measured by 10% by removing the same force for the same time. If less, it was marked as good (O) and if it was 10% or more, poor (X).

Compression Recovery Rate

The pattern formed by the circular independent patterned photomask having a diameter of 15 μm was applied with a micro-compression tester for 20 seconds with a load of 100 mN, and then the thickness of the pattern was measured while removing the same force for the same time, thereby measuring the pattern thickness of the initial state. The ratio of the thickness change in the state where all the forces were removed from the thickness change when the pattern thickness was the lowest was shown.

Storage stability Developability Pattern top diameter Pattern toughness Compression Recovery Rate Example 1 0.12% O 22.2 μm O 97.1% Example 2 0.14% O 23.4 ㎛ O 98.3% Example 3 0.14% O 21.9㎛ O 96.5% Example 4 0.16% O 22.7 ㎛ O 97.9% Comparative Example 1 0.13% X - - - Comparative Example 2 0.11% X - - - Comparative Example 3 0.09% O 17.5㎛ X 89.5% Comparative Example 4 2.89% O 19.3 μm X 91.6% Comparative Example 5 1.92% O 18.6 μm X 90.6% Comparative Example 6 2.42% O 19.9㎛ X 92.4%

The photosensitive compositions of Comparative Example 1 and Comparative Example 2, which did not contain a copolymer (B) as one component of the composition of the present invention, had poor development characteristics and could not obtain a pattern.

The photosensitive composition of Comparative Example 3, which does not include a copolymer (A) as one component of the composition of the present invention, was superior to Examples and other comparative examples in terms of storage stability, but a pattern having a large upper diameter was not obtained. In terms of pattern toughness and compressive resilience, the results were poor compared to the compositions of the present invention.

The photosensitive compositions of Comparative Examples 4, 5, and 6, which include a copolymer prepared from Comparative Synthesis Example 1 in which a carboxyl group is not protected instead of copolymer (A) which is one component of the composition of the present invention, are particularly poor in storage stability and have a pattern toughness. Showed poor results.

In the case of poor storage stability, the viscosity increases when stored at room temperature for a long time, and as a result, the pattern thickness, pattern size, developability, etc. when forming the column spacer pattern show a lot of difference from the initial manufacturing state. It becomes difficult to do it. The viscosity increase is mainly caused by a chemical reaction in the composition solution, the most influential reaction is the reaction of the functional groups in the binder polymer slowly at room temperature. Representative examples of such a reaction include the case where methacrylic acid and glycidyl methacrylate are present in one copolymer, which is the case of Comparative Example 4,5,6.

On the other hand, in Comparative Example 3 in which the binder matrix was formed using only the copolymer B obtained in Synthesis Example 3 alone, the composition was reacted after glycidyl methacrylate and methacrylic acid were already reacted at a high temperature during copolymerization. Since it was formed, the viscosity was found to be very small at room temperature storage in the future. However, since there is no functional group that can react by heat, the bonding strength between molecules is relatively weak in the heating process (pre-bake & post-bake) applied during pattern formation, which causes the pattern toughness or compression recovery rate to be lower than that of other examples. appear.

Claims (10)

A column spacer composition comprising copolymers (A) and (B): Copolymer (A) A copolymer containing a 2-tetrahydropyridyl group-containing polymerizable monomer (a-1) and an epoxy group-containing polymerizable monomer (a-2) represented by the following Chemical Formula 1 [Formula 1]

(R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) Copolymer (B) A copolymer containing a compound represented by formula (2) [Formula 2]

(m and n are integers from 3 to 40.) The method of claim 1, wherein the copolymers (A), (B) or (A) and (B) are aliphatic or aromatic (meth) acrylates, caprolactone-modified (meth) acrylates, acrylate monomers having a hydroxyl group, A column spacer composition comprising at least one polymerizable monomer (a-3) selected from the group consisting of styrene monomers, silicone (meth) acrylate monomers, 1,3-butadiene and isoprene. The column spacer composition of claim 1, wherein the monomer (a-1) represented by Formula 1 is 2-tetrahydropyranyl methacrylate or 2-tetrahydropyranyl acrylate. The column spacer composition of claim 1, wherein the monomer (a-2) is glycidyl methacrylate or 3,4-epoxycyclohexyl methacrylate. The column spacer composition according to claim 1, wherein the mixing ratio of the copolymers (A) and (B) is from 1: 9 to 5: 5. The copolymer (A) according to claim 2, wherein the copolymer (A) is 5 to 50% by weight of the monomer (a-1), 5 to 70% by weight of the monomer (a-2) and 0 to the polymerizable monomer (a-3). Column spacer composition, characterized in that it comprises ~ 80% by weight. 3. The column spacer composition of claim 2, wherein the copolymer (B) comprises 0 to 80 wt% of the polymerizable monomer (a-3). A column spacer pattern formed from the composition of claim 1. The color filter for liquid crystal display elements manufactured using the composition of any one of Claims 1-7. The liquid crystal display device manufactured using the composition of any one of Claims 1-7.