JP3467488B2 - Resist composition for column spacer of liquid crystal display device - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist composition for a column spacer of a liquid crystal display device, and in particular, it is possible to form a pattern with an appropriate thickness when forming a column spacer of a liquid crystal display device, and to obtain flatness and resolution. The present invention relates to a resist composition having excellent residual film rate and pattern stability.

[0002]

2. Description of the Related Art Normally, a liquid crystal display device (LCD) is composed of two opposed upper and lower panels, a spacer and a liquid crystal inserted between the panels, and the spacer has a thickness of the liquid crystal layer, that is, a space between the panels. It functions to keep a certain cell gap. Only when the cell gap is kept constant, liquid crystal display device performance such as high-speed response, high contrast and wide viewing angle can be realized.

At present, the most widely used spacer forming method is to disperse and coat transparent spherical or cylindrical polymethylmethacrylate or silica particles having a diameter slightly larger than the cell gap. Such a method not only causes a phenomenon in which spherical or cylindrical particles are partially aggregated at the time of injecting liquid crystal, but the particles are moved due to movement, vibration, impact, etc. of the liquid crystal panel to achieve uniform dispersion. Therefore, deviation of the cell gap occurs and it is difficult to maintain a constant cell gap. As a result, the thickness of the liquid crystal layer becomes non-uniform, the hue of the liquid crystal display element changes, and the image is distorted. In addition, scratches may be generated in the alignment film to damage the alignment film, and the electrodes may be damaged when the upper and lower panel substrates are pressure-sealed. These problems are expected to increase due to the trend toward larger liquid crystal display devices such as TFT LCDs, or as applications for information terminals such as mobile phones and pagers, mobile communication devices, and vehicle navigation systems are developed and increased. Get serious.

As a method for solving such a problem, a method of forming a fixed column spacer using a photocurable composition has been proposed. Korean Patent Laid-Open No. 1999-88297 discloses that a composition comprising a copolymer of acrylic acid and acrylate, a polyvalent acrylate cross-linking agent and a photoinitiator is applied, and then ultraviolet rays are irradiated to cure a desired portion. There is disclosed a method of forming a spacer by a method of washing and removing the uncured portion with an aqueous base solution. Such a method can form fixed spacers having a constant thickness and a constant spacing,
A uniform cell gap can be maintained regardless of the external environment.

However, it is difficult for the photocurable composition disclosed in the above-mentioned publication to form a thickness of 3 to 10 μm, which is an appropriate cell gap used in a liquid crystal display device. That is, since it is difficult to achieve a viscosity suitable for producing a film having a thickness of 3 to 10 μm by a spin coating method, it is necessary to spin coat the composition, cure the composition, and develop the composition. There is the inconvenience of having to repeatedly form a spacer having an appropriate thickness. In addition, since the composition uses an acrylic resin as a main component, volume shrinkage occurs after curing and it is difficult to form a spacer having a uniform thickness, and thus heat resistance and pattern stability are also poor.

[0006]

Therefore, a technical problem to be solved by the present invention is that a pattern can be formed to an appropriate thickness when forming a column spacer of a liquid crystal display element, and the heat resistance and the pattern stability can be improved. Another object of the present invention is to provide a resist composition having excellent flatness, resolution and residual film ratio.

[0007]

In order to achieve the above technical object, the present invention provides a compound represented by the general formula (1):

[0008]

[Chemical 6]

(In the general formula (1), X is a hydrogen atom or a methyl group, and Y ¹ is a carbon atom having 2 to 1 carbon atoms.
6 is an alkyl group or a hydroxyalkyl group, and is Y
² is the following chemical formula (I) or chemical formula (XX)

[0010]

[Chemical 7]

[0011]

[Chemical 8]

[0012]

[Chemical 9]

(In the above formulas (I) to (XX), R ₁ is hydrogen or a methyl group, R ₂ is an alkylene group having 1 to 10 carbon atoms, and R ₃ is 1 to 10 carbon atoms. Is a residual group of hydrocarbons of
R ₄ is hydrogen or a methyl group, R ₅ is an alkylene group having 1 to 10 carbon atoms, and k is 0 to 1
It is an integer of 0. ) Is any one selected from the compounds represented by: ) Binder resin represented by the general formula (2)

[0014]

[Chemical 10]

(In the above general formula (2), the polymerized unit A is
Is benzyl methacrylate, styrene, α-methylstyrene, isobornyl acrylate, isobonyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl ethyl Is any one selected from the group consisting of oxyacrylate, dicyclopentanylethyloxymethacrylate, dicyclopentenylethyloxyacrylate, dicyclopentenylethyloxymethacrylate, B is acrylic acid or methacrylic acid , C is any one selected from the group consisting of glycidyl methacrylate, hydroxyethyl methacrylate, dimethylamino methacrylate, acrylamide, and The binder resin of the general formula (2) is a random copolymer which is not bound to the arrangement order of the polymerized units A, B and C. ) A binder resin represented by (4), and 10 to 40 parts by weight of a binder resin selected from the group consisting of a mixture thereof, 1 to 20 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond, and photoinitiating. A resist composition for a column spacer of a liquid crystal display device, comprising 1 to 10 parts by weight of an agent and 0.001 to 0.1 part by weight of a silicon compound containing an epoxy group.

The binder resin represented by the general formula (1) is a copolymer of a monomer containing a carboxylic acid and a monomer having a double bond, and a binder resin of the present invention containing such a copolymer. If a pattern is formed after applying the composition, there is no defect such as a residue after development and the flattening rate is very excellent. That is, Y ^{1 in the} general formula (1) is an alkyl group or a hydroxyalkyl group having 2 to 16 carbon atoms, which contributes to the improvement of the adhesive force, and Y ² contains an acrylic copolymer resin containing an aromatic group. Unlike the conventional binder resin, which contains a bulky ring structure, it not only enhances the residual film ratio, but also has a high glass transition temperature, and therefore has excellent heat resistance.

The average molecular weight of the binder resin represented by the general formula (1) is 2,000 to 50,000, the dispersity is 1.0 to 5.0, and the acidity is 30 to 400 KOHmg / g.
It is desirable to use the average molecular weight of 5,
000 to 40,000, dispersity is 1.6 to 3.
It is more desirable to use those having an acidity of 0 and an acidity of 50 to 150 KOHmg / g.

Further, when the binder resin represented by the general formula (2) is used, the same effect is obtained as when the binder resin represented by the general formula (1) is used. In the binder resin represented by the general formula (2), it is possible to introduce other types of polymerized units within a range that does not impair the object of the present invention.

[0019]

[Chemical 11]

The number of alkyl groups is 2 to 1 as in D of
Further alkyl acrylates or alkyl methacrylates of 6 can be introduced. As such a repeating unit,
More specifically, methyl methacrylate, butyl methacrylate, lauryl methacrylate, methyl acrylate, butyl acrylate, lauryl acrylate, styrene and the like can be mentioned.

The binder resin represented by the general formula (2) preferably has an average molecular weight of 2,000 to 100,000, a dispersity of 1.0 to 5.0, and an acidity of 30 to 400 KOHmg / g. Average molecular weight is 5,000 to 6
More preferably, the dispersity is 2,000, the dispersity is 1.6 to 3.0, and the acidity is 50 to 150 KOHmg / g.

In particular, when the binder resin represented by the general formula (1) and the binder resin represented by the general formula (2) are mixed and used, the polyfunctional monomer and the binder resin in the composition are mixed. In addition to improving the crack resistance of the pattern, the whitening phenomenon disappears.

1 to 20 parts by weight of an elastomer having an ethylenically unsaturated bond may be further added to the resist composition for a column spacer of a liquid crystal display device according to the present invention.
As such an elastomer, it is desirable to use one having an ethylenically unsaturated bond number of 2 to 15 in the side chain, but for example, a urethane acrylic resin having an ethylenically unsaturated bond in the side chain can be used. Examples of such urethane acrylic resin include U series and UA series of Shin-Nakamura, Japan. Other elastomers that can be used include thermoplastic elastomers obtained by modifying SBS, SIS, SIBS, EPDM, EP rubber, butadiene rubber, isoprene rubber and the like, and these may be used alone or in combination of two or more. . Since the column spacer formed as a resist composition to which an elastomer having such an ethylenically unsaturated bond is added has an extremely improved elasticity, a lower overcoat or a black matrix by a pressure applied from the outside to the panel after forming the panel, The possibility that a color filter pixel or the like is broken can be eliminated.

The polyfunctional monomer having an ethylenically unsaturated bond contained in the resist composition for a column spacer of a liquid crystal display device according to the present invention may be an ethylenically unsaturated bond used in a conventional photosensitive composition. The polymerizable compound having the above can be used, for example, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups,
Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propylene glycol di (meth) having 2 to 14 propylene oxide groups. ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other compounds obtained by esterification of α, β-unsaturated carboxylic acid, and trimethylolpropane triglycidyl ether acrylic Compounds obtained by adding (meth) acrylic acid to glycidyl group-containing compounds such as acid adducts, bisphenol A diglycidyl ether acrylic acid adducts, and phthalic acid of β-hydroxyethyl (meth) acrylate Esters, and adducts of β- hydroxyethyl (meth) compound having a hydroxyl group and an ethylenically unsaturated bond such as toluene diisocyanate adduct acrylate ester compound with a polyvalent carboxyl acid or polyisocyanate, methyl (meth)
Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid alkyl ester such as 2-ethylhexyl (meth) acrylate, etc. may be used alone or in admixture of two or more.

As described above, the composition of the polyfunctional monomer of the polymerizable compound having an ethylenically unsaturated bond, the elastomer having an ethylenically unsaturated bond, and the binder resin is appropriately adjusted according to the present invention to provide elasticity, high heat resistance, A resist composition for a column spacer that can maintain high transparency, a high flattening rate and pattern stability can be manufactured.

As the photoinitiator contained in the resist composition of the present invention, an acetophenone type or a benzophenone type is used alone or in a mixture thereof in order to enhance the transparency and minimize the dose amount. Is desirable. If the photoinitiator itself has a color, it acts to reduce transparency, so it has appropriate sensitivity in the wavelength band used during exposure, and high transparency can be achieved by using a colorless photoinitiator. . Generally, the photoinitiator is used according to the wavelength of the ultraviolet ray used in the temporary bridge reaction using the acrylic multifunctional monomer, but the mercury lamp, which is the most widely used ultraviolet wavelength, has a wavelength in the range of 310 to 420 nm. It is desirable to use a photoinitiator that generates radicals in this wavelength range.

As such a photoinitiator, Irgacure 3
69, Irgacure 907, EPD / BMS mixed system, and other benzophenone-based and triazine-based photoinitiators. Examples include benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzyl, benzyldimethylketal, and 1-benzyl-1. -Dimethylamino-1-
(4-morpholino-benzoyl) propane, 2-morpholyl-
2- (4-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-proxythioxanthone, isopropylthioxanthone, diethylthioxanthone,
Ethylanthraquinone, 4-benzoyl-4-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-
(4-Isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis
(9-Acridinyl) heptane, 9-n-butyl-3,6-bis
(2-morpholino-isobutyroyl) carbazole, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2
Examples include -phenyl-4,6-bis (trichloromethyl) -s-triazine and 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine.

The epoxy group-containing silicon-based additive contained in the resist composition of the present invention improves the adhesive strength between the ITO electrode and the composition and, after curing, improves the heat resistance. Examples of such silicon compounds include (3-glycidoxypropyl) trimethoxy (ethoxy) silane.
(3-glycidoxypropyl) methyldimethoxy (ethoxy) silane, (3-glycidoxypropyl) dimethylmethoxy (ethoxy) silane, 3,4-epoxybutyltrimethoxy (ethoxy) silane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxy (ethoxy) silane and the like, which may be used alone or as a mixture thereof.

If necessary, compatible additives such as a photosensitizer, a thermal polymerization inhibitor, a defoaming agent and a leveling agent may be added to the resist composition for column spacers of the present invention.

The resist composition for column spacers of the present invention is prepared by spin coating a substrate by adding a solvent, irradiating ultraviolet rays with a mask and developing with an alkali developing solution to form column spacers. 1
Addition of solvent in the range of 0 to 35 cps is desirable for producing a coating layer capable of keeping the cell gap at a thickness of 3 to 10 μm. More desirably, adjusting the viscosity to 15 to 30 cps has no pinholes in the thin film after coating, and it is more advantageous to adjust the thickness of the thin film. As such a solvent, when considering the transparency of the thin film obtained in addition to the coating property of the composition, the binder resin, the compatibility with the multifunctional monomer and other compounds, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, Diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EE
P), ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether,
Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl (or ethyl) acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) ,
γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl (or ethyl) cellosolve,
Diethylene glycol methyl (or ethyl) ether,
A solvent selected from dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, and octane may be used alone or in combination with one or more.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The examples of the present invention are provided to those skilled in the art to more fully describe the present invention.

Example 1 A binder resin, a polyfunctional monomer, a photoinitiator, and a silane-based epoxy compound were mixed according to the composition and content shown in Table 1 below in a reaction mixing tank equipped with an ultraviolet blocking film and a stirrer. A predetermined light increasing / decreasing agent, a thermal polymerization inhibitor, a defoaming agent, and a leveling agent were sequentially added to prepare a resist composition for a column spacer, and then the mixture was stirred at room temperature. Then, a solvent was added to the composition to adjust the viscosity of the resist composition to 25 cps.

In the examples, the binder resin is the above-mentioned general formula (1) (in the general formula (1), X is a methyl group, and Y ¹
Is a methyl group) Y ² is represented by the chemical formula (I) to the chemical formula (XX) is represented by the chemical formula (1-I) to the chemical formula (1-XX),
In this case, R ₁ , R ₂ , R ₃ and R ₄ are each methyl, methyl, ethyl and methyl, and k is 1.

<Examples 2 to 32> A resist for a column spacer was prepared in the same manner except that the components and contents of the composition of Example 1 were changed according to the compositions shown in Tables 1 to 3 below. A composition was produced.

<Comparative Examples 1 to 8> Instead of the binder resin of Example 1, the following general formula (4) was used.

[0036]

[Chemical 12]

(In the general formula (4), p is 0.3.
Where q is 0.2 and r is 0.5. Column) in the same manner except that a binder resin (average molecular weight 30,000) represented by the formula (1) was used and the composition and content of the composition were changed according to the compositions shown in Tables 2 and 3 below. A resist composition for spacers was manufactured.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

<Examples 33 to 51> The same method as in Example 1 was repeated except that urethane acrylate was added to the composition of Example 1 and the components and contents were changed according to the compositions shown in Table 4 below. A resist composition for column spacer was manufactured. In Table 4, the number of unsaturated double bonds in the side chain of urethane acrylate (product of Shin-Nakamura, Japan) is 1 to 1.
5 is represented by UA1 to UA15, respectively.

[0042]

[Table 4]

<Comparative Examples 9 to 12> Binder resins represented by the general formula (4) of Comparative Examples 1 to 8 were used in place of the binder resins of Examples 33 to 51, and the components and contents of the compositions were changed. A resist composition for a column spacer was manufactured by the same method except that the composition was changed according to the composition shown in Table 5 below.

[0044]

[Table 5]

Evaluation of the resist compositions according to the above-mentioned Examples and Comparative Examples was carried out on a substrate such as a silicon wafer or a glass plate, and thermal characteristics investigation, flatness,
Performance evaluations such as residual film rate and pattern formation were performed. In particular, compositions containing urethane acrylate were further evaluated for compression recovery and the results are shown in Tables 6 and 7 below.

(1) Investigation of Thermal Properties In order to evaluate the thermal properties of the resist composition for column spacers, a thermogravimetric analysis (TGA)
Was used to measure the thermal decomposition temperature, and the temperature at which 5% of the initial weight decreased was compared as the initial decomposition temperature.

(2) The flatness resist composition was applied onto a substrate by a spin coater at 600
After applying for 13 seconds at a speed of rpm, pre-bake at 90 ° C. for 3 minutes, cure at 365 nm for 15 seconds, and then 220 ° C.
Then, post-baking was performed for 30 seconds to form a resist film. The thickness of the resist film formed on the silicon wafer or the glass plate was measured at 25 different points by using a thickness measuring instrument to obtain the difference between the maximum thickness and the minimum thickness.

(3) Residual film ratio The ratio of the thickness of a film formed after spin-coating a substrate spacer resist composition on a substrate and performing pre-baking and post-baking to remove the solvent. (%) Was measured.

(4) Pattern formation A silicon wafer on which a resist pattern was formed was cut from the direction perpendicular to the line pattern, and the result was observed by an electron microscope from the cross-sectional direction of the pattern. The pattern side wall is erected at an angle of 80 ° or more with respect to the substrate,
The case where the film was not reduced was judged as "good", and the case where the film was observed was judged as "film reduced".

(5) Investigation of compression recovery rate In order to evaluate the compression recovery rate of the resist composition for column spacers, a nano indenter II (Nanoindent II) manufactured by MTS Co., Ltd. in the United States was manufactured.
er II), an indentation experiment was carried out. The indenter uses a flat punch tip,
After applying a load of 10 mN and stopping for 5 seconds, the load was removed to 0.98 mN and the restored distances were compared.

[0051]

[Table 6]

[0052]

[Table 7]

As can be seen from Tables 6 and 7, the resist composition for column spacers of the present invention is not only superior in heat resistance unlike conventional resist compositions, but also has a residual film ratio and a flatness during film formation. It can be seen that the property and the pattern stability are also very excellent. In particular, the liquid crystal display device employing the column spacer made of the resist composition of Examples 33 to 51, which further contains an elastomer having an ethylenic unsaturated bond such as urethane acrylate, has a significantly increased elasticity. There is no risk of cracking the lower overcoat, black matrix, color filter pixels, etc. due to the pressure applied to.

[0054]

As described above, the above-mentioned resist composition according to the present invention is not only excellent in heat resistance, but also capable of forming a pattern with a uniform and appropriate thickness, and having a high resolution, a residual film ratio and a stable pattern. Good property. Therefore, if a column spacer is formed using the resist composition of the present invention, a uniform cell gap can be maintained regardless of the size of the display element, and the cell gap can be prevented from changing due to movement, vibration, or impact of the liquid crystal panel. sell. In particular, since the column spacer made of a resist composition further containing an elastomer having an ethylenic unsaturated bond has a very high elasticity, a liquid crystal display device adopting this has a lower overcoat or a black matrix due to the pressure applied to the panel from the outside. , The color filter pixel is not broken.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hyuk Jin, Cha Korea, 302-222, Daejeon, Sog, Samcheong-dong (No street number) Garam Apartment No. 2-1502 (72) Inventor Jae Hun, Lee Korea, 305-761, Daejeong, Yousung-gu, Jongmin-dong # 464-1, Expo Apartment No. 108-1604 (72) Inventor Sung-jae, Hong Korea, 300-200, Daejeon, Dong-gu , Young Jung-Dong # 135-5, Woo Jung Villa No. 403 (72) Inventor Kung Joo, Lee South Korea, 402-200, Incheon, Nam-Gu, Juan-Dong # 52-17 (72) Inventor Young Man, John, 139-052, Seoul, Nowon-gu, Olgae 2-Don (No house number), Chongbek Apartment No. 106-610 (72) Inventor Soo Young, Choi Republic of Korea, 305-755, Daejeong, Yousung-Gu, Oung-Don (No house number), Hanbit Apartment No. 127-1104 (72) Inventor Myson, Liu South Korea, 302-170, Daejeon, Sorgh, Garhma Dong # 732 Number 305 (72) Inventor Young-Kun, Kim South Korea, 330-810, Chun-Chonnam -Do, Cheonan-si, Jiksan-myon, Panjeongri 1-gu # 223-43 (72) Inventor Taeyeon, Kim South Korea, 430-014, Kyonguido, Anyang-si, Manangu, Bakdal -Dong # 9-7 (72) Inventor Eun, Kim, Republic of Korea, 302-723, Dejeong, Sog, Gwangjo Dong (no address), Goo Bon Village Apartment No. 802-80 2 (72) Inventor Chun Woo, Yoo Republic of Korea, 570-100, Jollabukdo, Iksan-si, Namjeong-Dong (no street number), Songho Apartment No. 205 (72) Inventor Deo Woo, Lee South Korea, 420 -010, Kyung-gide, Buchon-si, Won-mig, Simguk-dong, # 346-10, Sinhwa Villa No. 402 (72) Inventor, Dong Kong, Ko, Republic of Korea, 704-400, Daegu, Darsog, Wolson-Don (No house number), Wolson Djugon Apartment No. 303-1405 (72) Inventor Mu-Hyun, Kwon Korea, 143-302, Seoul, Gwangjin-gu, Noyu 2-Don # 829, Hankhang Hyundai Apartment Number 101-1504 (72) Inventor Chul Woo, Lee Korea, 302-120, Daejeon, Sog, Dunsung-dong (No address), Semmoria Part No. 108-201 (72) Inventor Sun-il, Yun Republic of Korea, 301-754, Daejeong, Jun-gu, Munhwa-dong (no address), San-apartment No. 3-209 (56) References 2000-154207 (JP, A) JP 2000-256428 (JP, A) JP 2000-292615 (JP, A) JP 6-331968 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42 G02F 1/1339 500

Claims (11)

(57) [Claims] 1. A general formula (1): (In the general formula (1), X is a hydrogen atom or a methyl group, Y ¹ is an alkyl group or a hydroxyalkyl group having 2 to 16 carbon atoms, and Y ² is a chemical formula (I) to a chemical formula (XX ) [Chemical 2] [Chemical 3] [Chemical 4] (In the above chemical formulas (I) to (XX), R ₁ is hydrogen or a methyl group, R ₂ is an alkylene group having 1 to 10 carbon atoms, R ₃ is a residual group of a hydrocarbon having 1 to 10 carbon atoms, R ₄ is hydrogen or a methyl group, R ₅ is an alkylene group having 1 to 10 carbon atoms,
k is an integer of 0 to 10. ) Is any one selected from the compounds represented by: ) A binder resin represented by the general formula (2): (In the general formula (2), the polymer unit A is benzyl methacrylate, styrene, α-methylstyrene, isobornyl acrylate, isobonyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyl acrylate, Any one selected from the group consisting of dicyclopentanyl methacrylate, dicyclopentanyl ethyloxy acrylate, dicyclopentanyl ethyloxy methacrylate, dicyclopentenyl ethyloxy acrylate, dicyclopentenyl ethyloxy methacrylate. Yes, B is acrylic acid or methacrylic acid,
C is any one selected from the group consisting of glycidyl methacrylate, hydroxyethyl methacrylate, dimethylaminomethacrylate, and acrylamide, and the binder resin of the general formula (2) is a polymerized unit A,
It is a random copolymer that is not restricted by the arrangement order of B and C. 10 to 40 parts by weight of a binder resin selected from the group consisting of a binder resin represented by the formula (1) and a mixture thereof, 1 to 20 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond, and a photoinitiator 1 to 1 10 parts by weight and an epoxy group-containing silicon compound from 0.001 to 0.001.
1 part by weight of the resist composition for a column spacer of a liquid crystal display device. 2. The binder resin represented by the general formula (1) has an average molecular weight of 5,000 to 40,000, a dispersity of 1.6 to 3.0, and an acidity of 50 to 150.
KOH mg / g, The resist composition for column spacers of the liquid crystal display element of Claim 1 characterized by the above-mentioned. 3. The binder resin represented by the general formula (2) has an average molecular weight of 5,000 to 60,000, a dispersity of 1.6 to 3.0 and an acidity of 50 to 150.
KOH mg / g, The resist composition for column spacers of the liquid crystal display element of Claim 1 characterized by the above-mentioned. 4. The binder resin represented by the general formula (2) has 2 to 16 alkyl groups as polymerized units.
The alkyl acrylate or the alkyl methacrylate, which is, is further copolymerized.
A resist composition for a column spacer of a liquid crystal display device described in 1. 5. The polyfunctional monomer having an ethylenically unsaturated bond is ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, and trimethylolpropane di (meth) acrylate. ) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra
(Meth) acrylate, a polyvalent selected from the group consisting of propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. A compound obtained by esterifying an alcohol and α, β-unsaturated carboxylic acid, a compound obtained by adding (meth) acrylic acid to a glycidyl group-containing compound, and a compound having a hydroxyl group and an ethylenically unsaturated bond and polyvalent The liquid crystal display device according to claim 1, comprising at least one selected from the group consisting of (meth) acrylic acid alkyl esters and an adduct of an ester compound with a carboxylic acid or a polyisocyanate. A resist composition for column spacers. 6. The resist composition for a column spacer of a liquid crystal display device according to claim 1, wherein the photoinitiator contains a benzophenone-based or triazine-based photoinitiator. 7. The silicon compound containing an epoxy group is (3-glycidoxypropyl) trimethoxy (ethoxy) silane, (3-glycidoxypropyl) methyldimethoxy (ethoxy) silane, (3-glycidoxy) silane. Propyl)
At least one selected from the group consisting of dimethylmethoxy (ethoxy) silane, 3,4-epoxybutyltrimethoxy (ethoxy) silane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy (ethoxy) silane. The resist composition for a column spacer of a liquid crystal display device according to claim 1, which comprises: 8. The resist composition for a column spacer of a liquid crystal display device according to claim 1, wherein a solvent is further added so that the viscosity becomes 10 to 35 cps. 9. The solvent is ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethyl lactate, propylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl. Cellosolve acetate, diethylene glycol methyl (or ethyl) acetate, acetone, methyl isobutyl ketone,
Cyclohexanone, dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran, methanol, ethanol, propanol, iso-propanol, methyl (or ethyl) 9. The composition according to claim 8, comprising at least one selected from the group consisting of cellosolve, diethylene glycol methyl (or ethyl) ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane and octane. A resist composition for a column spacer of a liquid crystal display device. 10. The resist composition for a column spacer of a liquid crystal display device according to claim 1, further comprising 1 to 20 parts by weight of an elastomer having an ethylenically unsaturated bond. 11. The column spacer of a liquid crystal display device according to claim 10, wherein the elastomer having an ethylenically unsaturated bond is a urethane acrylic resin having 2 to 15 side chain ethylenically unsaturated bonds. Resist composition.