JP5362696B2 - Polyfunctional acrylic compound and photosensitive composition containing the same - Google Patents

Abstract

The present invention provides a polyfunctional acrylic compound with a siloxane group, and a colorful or transparent photosensitive composition which comprises the polyfunctional acrylic compound and is used for manufacturing a color filter used for LCD. The polyfunctional acrylic compound of the invention comprises the siloxane group. The photosensitive resin composition which comprises the polyfunctional acrylic compound is advantageous in that: an excellent binding force is provided for the pattern, and fine pattern loss in a developing process is prevented.

Description

  The present invention relates to a polyfunctional acrylic compound and a photosensitive composition containing the same, and more specifically, a polyfunctional acrylic compound containing a siloxane group and the formation of a pattern having excellent adhesive force by containing the same. The present invention relates to a photosensitive composition used for a color filter for a liquid crystal display device.

  The structure of a liquid crystal cell used in a liquid crystal display element is mainly composed of a thin film transistor substrate for driving, a color filter for realizing color, and a liquid crystal formed between two substrates. The color filter uses a color ink having three or more transmission-absorption wavelengths to form a color image after forming a pattern by a photo-etching method using a photosensitive organic material in which a pigment is dispersed. A substrate on which pixels are formed. In addition to the pixels, an overcoat is used on the color filter substrate in some cases to reduce the level difference of the pixels, or column spacers are patterned in order to maintain a constant interval inside the liquid crystal cell.

  The organic material used for manufacturing the color filter is generally a negative composition among the photosensitive resin compositions that can use the photo-etching method, and such a composition has alkali solubility. In order to give, a binder containing a carboxylic acid, a polyfunctional acrylic compound, a photoinitiator that generates radicals upon receiving light, a surfactant, a solvent, and a coupling agent that provides adhesion between the pattern and the glass substrate It consists of a mixture.

  Recently, the resolution of the liquid crystal display element has been gradually improved, and accordingly, the size of the pattern used for the color filter has been reduced. As a result, when patterning pixels using a photosensitive material or patterning smaller column spacers, etc., the pattern was lost due to water pressure during the development process due to its too small size. The probability of doing is high.

  The problem to be solved by the present invention is to solve the problem that a pattern is lost due to water pressure during the development process in forming a fine pattern using a photosensitive material.

  Accordingly, an object of the present invention is to provide a polyfunctional acrylic compound capable of improving the adhesive force of a pattern.

  Another object of the present invention is to provide a photosensitive composition capable of preventing the occurrence of defects due to the loss of a pattern by containing the polyfunctional acrylic compound.

In order to solve the above problem, the polyfunctional acrylic compound according to an embodiment of the present invention may be represented by the following Chemical Formula 1 or Chemical Formula 2.

In Formula 1 and Formula 2, R1 to R10 may be the same as or different from each other, and are independently a hydrogen atom (—H), an acryloyl group (—C (O) —CH═CH ₂ ), a succinic acid group ( -C (O) C 2 H 4 C (O) OH) and are any one selected from the group consisting of substituents of the structure of the following formula 3, the acryloyl group two or more, of the following chemical formula 3 Contains one or more substituents of the structure.

  In Formula 3, R11 to R13 may be the same as or different from each other, and each represents an alkyl group having 1 to 2 carbon atoms.

  The present invention also provides a photosensitive composition comprising the polyfunctional acrylic compound as a polyfunctional monomer.

  The photosensitive composition may further include an alkali-soluble binder resin, a photoinitiator, a solvent, and an additive.

  The photosensitive composition comprises 1 to 35% by weight of the polyfunctional acrylic compound, 1 to 45% by weight of an alkali-soluble binder resin, 0.05 to 10% by weight of a photoinitiator, and 10 to 97.95% by weight of a solvent. Can be included.

  The polyfunctional monomer may further include an acrylic compound that does not include a siloxane group.

  The acrylic compound not containing the siloxane group is introduced into dipentaerythritol in the form of KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, Aronix M-520, and tetrahydrofurfuryl ( KAYARAD TC-110S introduced into tetrahydrofurfuryl acrylate, KAYARAD HX-220, KAYAARAD HK-620 introduced into neopentyl glycol hydroxypivalate, epoxide acrylate of bisphenol A derivative, novolak-epoxy acrylate U-324A, U15HA, U-4HA, Hanse Chemie as urethane-based polyfunctional acrylate It can be of Nanocryl XP series (0596,1045,21 / 1364) and Nanopox 1 or more compounds selected from the group consisting of XP series (0516,0525).

  In addition, the acrylic compound that does not include the siloxane group may include 1 to 15% by weight of the composition.

  The photosensitive composition may further include one or more selected from the group consisting of a curing colorant, an accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler, and a surfactant. .

  In addition, the photosensitive composition according to one embodiment of the present invention includes substantially no additional coupling agent by including the polyfunctional acrylic compound represented by Chemical Formula 1 or Chemical Formula 2.

  According to the embodiment of the present invention, based on the structural characteristics of the polyfunctional acrylic compound represented by the chemical formula 1 or the chemical formula 2, the photosensitive composition including the polyfunctional acrylic compound does not include a separate coupling agent. It can have excellent adhesion.

  Therefore, if a pattern is formed using the photosensitive resin composition containing a polyfunctional acrylic compound having a siloxane group according to the present invention, it is possible to prevent defects caused by loss of a small pattern during the development process. . Such a resin composition is advantageous when manufacturing color pixels, column spacers, overcoats and the like of high-resolution color filters.

The polyfunctional acrylic compound containing a siloxane group for achieving the object of the present invention as described above is represented by the following chemical formula 1 or chemical formula 2. Here, the polyfunctional acrylic compound refers to a compound containing two or more acrylic groups.

R1 to R10 independently represent a hydrogen atom (—H), an acryloyl group (—C (O) —CH═CH ₂ ), a succinic acid group (—C (O) C ₂ H ₄ C (O) OH) and It is any one selected from the group consisting of substituents having the structure of the following chemical formula 3, including two or more acryloyl groups and one or more substituents having the structure of the following chemical formula 3.

  In Formula 3, R11 to R13 may be the same as or different from each other, and each represents an alkyl group having 1 to 2 carbon atoms. When the number of carbon atoms exceeds 3 or more, the effect of improving the adhesive force pursued by the present invention cannot be expected.

   The polyfunctional acrylic compound represented by the chemical formula 1 or the chemical formula 2 is prepared by diluting an acrylic compound selected from the group consisting of dipentaerythritol pentaacrylate and pentaerythritol triacrylate in an organic solvent, and adding the anhydrous solution to the diluted solution. Succinic acid is added and allowed to react for a predetermined time. Alternatively, 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane can be added and reacted with the mixture, and then the solvent can be removed for production. Reacting dipentaerythritol pentaacrylate or pentaerythritol triacrylate with 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane without a catalyst by adding the succinic anhydride Can do.

  The photosensitive resin composition for achieving the object of the present invention comprises 1 to 35% by weight of the polyfunctional acrylic compound represented by the above chemical formula 1 or 2 and 1 to 45% by weight of the alkali-soluble binder resin. It contains 0.05 to 10% by weight of an agent and 10 to 97.95% by weight of a solvent, and if necessary, a colorant, a curing accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler or an interface. One or more additives such as an activator may be further included.

  The polyfunctional acrylic compound represented by Chemical Formula 1 or Chemical Formula 2 has a function of improving the adhesive strength of the photosensitive composition by including a siloxane group. Therefore, the present invention can provide a photosensitive composition that is preferable in terms of adhesive strength with only an acrylic compound, even if it does not contain a separate coupling agent. Such an acrylic compound may be included in an amount of 1 to 35% by weight, preferably 1 to 15% by weight. If less than 1% by weight is included, it is difficult to obtain an effect in terms of adhesive strength, and if it exceeds 35% by weight, the adhesive force becomes excessive, and the photosensitive composition is not removed cleanly after the development step. Residue phenomenon occurs on the substrate.

  The alkali-soluble binder resin is a polymer resin containing an acid functional group and is not limited to a specific structure as long as it is generally used in the industry, and may be used alone or in combination of two or more. Can be used as a mixture. However, the acid value is preferably in the range of 30 to 300 mgKOH / g, and the weight average molecular weight is preferably in the range of 1,000 to 200,000. When the acid value is less than 30 mgKOH / g, the solubility in an alkali developer may be poor, and when it exceeds 300 mgKOH / g, an undercut phenomenon may occur in the pattern. If the molecular weight is less than 1,000, there is no difference in developability due to exposure, which may make it impossible to form a pattern by a photoetching method. If the molecular weight exceeds 200,000, the viscosity of the solution is high. As a result, the coating may not be performed smoothly.

  Further, the composition of the present invention may contain 1 to 15% by weight of a polyfunctional acrylic compound containing no siloxane group in addition to the compound represented by Chemical Formula 1 or Chemical Formula 2.

  The other polyfunctional acrylic compound not containing a siloxane group is not limited to a specific structure as long as it is a compound having two or more acrylic groups in one molecule, and is known in the art. It can be used, and can be used individually or in mixture of 2 or more. Specific examples of such compounds include KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and Aronix M-520 as forms introduced into dipentaerythritol. KAYARAD TC-110S introduced into furyl acrylate, KAYARAD HX-220, KAYARAD HK-620 introduced into neopentyl glycol hydroxypivalate, and the like.

  Moreover, there are U-324A, U15HA, U-4HA and the like as bisphenol A derivative epoxy acrylate, novolak-epoxy acrylate, and urethane-based polyfunctional acrylate.

  In some cases, a colloidal solution in which a very small pulverized silica dispersion is dispersed in a polyfunctional acrylic compound can be used. When these are used, the basic function is the polyfunctional acrylic compound. However, the effect of increasing the strength and hardness of the thin film can be obtained by silica as dispersed particles. For example, there are Nanocryl XP series (0596, 1045, 21/1364) and Nanopox XP series (0516, 0525) manufactured by Hanse Chemie.

  In the photosensitive resin composition according to the present invention, the photoinitiator may be used alone or in combination of two or more, and examples thereof include 2,4-trichloromethyl- (4′-methoxyphenyl). ) -6-triazine compounds such as triazine; biimidazole compounds such as 2,2′-bis (2-chlorophenyl) -4,4′-5,5′-tetraphenylbiimidazole; 2-hydroxy-2 An acetophenone compound such as methyl-1-phenylpropan-1-one; a benzophenone compound such as 4,4′-bis (dimethylamino-) benzophenone; a thioxanthone compound such as 2,4-diethylthioxanthone; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; , 3′-carbonylbis-7- (diethylamino-) coumarin, such as Irgacure OXE-01 and Oxyloxime compounds such as OXE-02 from Ciba Geigy. It is not limited to these, What is known in this industry can be used.

  In the photosensitive resin composition according to the present invention, the solvent may be one or a mixture of two or more. Examples thereof include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, propyl cellosolve, ethylene glycol dimethyl ether, ethylene. Glycol diethyl ether, ethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propyl glycol diethyl ether, propylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclopentanone, cyclohexanone, propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethyl acetate It is selected from the group consisting of xylpropionic acid, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, and dipropylene glycol monomethyl ether, but is not necessarily limited thereto and is known in the art Things can be used.

  If necessary, the photosensitive resin composition of the present invention may further contain one or more additives such as a colorant, a curing accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler, or a surfactant. it can.

  As examples of the colorant, one or more pigments, dyes, or a mixture thereof can be used. For example, the black pigment may be a metal oxide such as carbon black, black smoke, or titanium black. Examples of carbon black include cyst 5HIISAF-HS, cyst KH, cyst 3HHAF-HS, cyst NH, cyst 3M, cyst 300HAF-LS, cyst 116HMMAF-HS, cyst 116MAF, cyst FMFEF-HS, cyst SOFEF, cyst VGPF, Cyst SVHSRF-HS and cyst SSRF (Tokai Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G , Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 230 , # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, # 25, # CF9, # 95, # 3030, # 3050, MA7, MA77, MA8 , MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75 , PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINT X-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (Degussa Corporation); RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA-10, RAVEN-10, RAVEN-10 , RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, VAVE -520, Raven-500, RAVE -460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, RAVEN-1170 (Columbia Carbon Co., Ltd.) or a mixture of these.

  Examples of colorants that are colored include carmine 6B (C.I. 12490), phthalocyanine green (C.I. 74260), phthalocyanine blue (C.I. 74160), and perylene black (BASF K0084.K0086). , Cyanine black, linole yellow (CI 21090), linole yellow GRO (CI 21090), benzidine yellow 4T-564D, Victoria pure blue (CI 42595), C.I. I. PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 202, 214, 215, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; I. PIGMENT GREEN 7, 36; C.I. I. PIGMENT blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 28, 36, 60, 64; C.I. I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; I. PIGMENT VIOLET 15, 19, 23, 29, 32, 37, etc. Other than these, white pigments, fluorescent pigments and the like can also be used. As a phthalocyanine complex compound used as a pigment, a substance having zinc as a central metal can be used in addition to copper. However, it is not necessarily limited thereto, and those known in the art can be used.

  Examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, and 2-mercapto-4,6- Although it is selected from the group consisting of dimethylamino-pyridine, it is not necessarily limited thereto, and those known in the art can be used.

  Examples of the thermal polymerization inhibitor include p-anisole and hydroquinone, but are not necessarily limited thereto, and those known in the art can be used.

  As the plasticizer, an adhesion promoter, a filler, a surfactant, and the like, any compound that can be included in the conventional photosensitive resin composition can be used.

  The photosensitive resin composition according to the present invention is applied to a support such as a metal, paper, glass, or plastic substrate by using a roll coater, a curtain coater, a spin coater, a slot die coater, or various printing and deposition methods. Can.

  Further, after being applied on the support, it is transferred onto another support, applied onto the first support, transferred onto a blanket, etc., and further transferred onto the second support. The application method is not particularly limited.

  Examples of the light source for curing the photosensitive resin composition according to the present invention include a mercury vapor arc, a carbon arc, a xenon arc, and a halogen arc that emit light having a wavelength of 250 to 450 μm. However, it is not particularly limited thereto, and those known in the art can be used.

  The photosensitive resin composition according to the present invention is a photocurable paint, a photocurable ink, a transparent photosensitive composition for producing an LCD color filter, a pigment-dispersed photosensitive resin composition, a light-shielding film for an LCD or an organic light-emitting diode. It can be used for the production of photosensitive resin compositions for use, and its use is not particularly limited.

  Moreover, this invention provides the transparent thin film layer for liquid crystal display devices manufactured using the photosensitive resin composition by this invention. The transparent thin film layer for the liquid crystal display device can be manufactured by a general manufacturing method known in the art except that the photosensitive resin composition according to the present invention is used.

  The present invention also provides a liquid crystal display device comprising the transparent thin film layer for the liquid crystal display device. The liquid crystal display device is manufactured by a general manufacturing method known in the art except that it includes a transparent thin film layer for a liquid crystal display device manufactured using the photosensitive resin composition according to the present invention. be able to.

  Hereinafter, the present invention will be described in more detail through examples. However, the following examples are merely for illustrating the present invention and are not intended to limit the scope of the present invention.

Synthesis example 1
Dipentaerythritol pentaacrylate is diluted to 50% by weight in propylene glycol methyl ether acetate. After adding succinic anhydride to the diluted solution at a molar ratio of 1: 1, the mixture was stirred at 80 ° C. for 12 hours, and the succinic anhydride added at a molar ratio of 1: 1 to 3-glycidide. After introducing oxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane), the mixture is further stirred for 12 hours and then cooled. Then, the compound obtained by removing the solvent using vacuum was dissolved in d6-DMSO, and analyzed using 500 MHz ¹ H-NMR. .

5.8 to 6.5 (9H, d, —CH═CH ₂ ), 2.5 to 2.7 (4H, t, —OC (O) —CH ₂ —CH ₂ —C (O) O—) _{, 4.1~4.5 (5H, m, -O} -CH 2 -CH (OH) -CH 2 -O-).

Synthesis example 2
The procedure was the same as in Synthesis Example except that dipentaerythritol pentaacrylate was used as pentaerythritol triacrylate in Synthesis Example 1. The compound obtained from the result of Synthesis Example 2 was dissolved in d6-DMSO and analyzed using 500 MHz ¹ H-NMR. The result is the same as in Chemical Formula 5.

5.8 to 6.5 (15H, d, —CH═CH ₂ ), 2.5 to 2.7 (4H, t, —OC (O) —CH ₂ —CH ₂ —C (O) O—) _{, 4.1~4.5 (5H, m, -O} -CH 2 -CH (OH) -CH 2 -O-).

Synthesis example 3
The same as Synthesis Example 1 except that glycidoxypropyltriethoxysilane was used instead of glycidoxypropyltrimethoxysilane in Synthesis Example 1. The compound obtained from the result of Synthesis Example 3 was dissolved in d6-DMSO and analyzed using 500 MHz ¹ H-NMR. The result is the same as in Chemical Formula 6.

5.8 to 6.5 (15H, d, —CH═CH ₂ ), 2.5 to 2.7 (4H, t, —OC (O) —CH ₂ —CH ₂ —C (O) O—) _{, 4.1~4.5 (5H, m, -O} -CH 2 -CH (OH) -CH 2 -O-).

Synthesis example 4
The same as Synthesis Example 2 except that glycidoxypropyltriethoxysilane was used instead of glycidoxypropyltrimethoxysilane in Synthesis Example 2. The compound obtained from the result of Synthesis Example 4 was dissolved in d6-DMSO and analyzed using 500 MHz ¹ H-NMR. The result is the same as in Chemical Formula 7.

5.8 to 6.5 (15H, d, —CH═CH ₂ ), 2.5 to 2.7 (4H, t, —OC (O) —CH ₂ —CH ₂ —C (O) O—) _{, 4.1~4.5 (5H, m, -O} -CH 2 -CH (OH) -CH 2 -O-).

Example 1
8 parts by weight of a binder resin (benzyl methacrylate and methacrylic acid are copolymerized at a molar ratio of 70:30, molecular weight is about 20,000), 8 parts by weight of the compound of Formula 4 obtained by Synthesis Example 1, as a photoinitiator 1 part by weight of Irgacure 907 manufactured by Ciba Geigy and 83 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed with stirring for 3 hours. The solution thus obtained is filtered through a 5 micron filter to prepare a photosensitive composition solution, spin-coated on glass, preheated at about 100 ° C. for 2 minutes, and has a thickness of about 2.5 μm. A uniform film was formed.

  After the film was exposed under a high-pressure mercury lamp using an independent pattern type photomask having a diameter of 5 to 20 microns and spaced at 1 micron intervals, the pattern was subjected to a KOH alkaline aqueous solution having a pH of 11.3 to 11.7. And developed with deionized water. After observing the state of the pattern with an optical microscope, the size of the remaining minimum pattern was determined based on the diameter of the photomask. As a result of the discrimination, all 5 micron patterns remained.

Example 2
The compound of Formula 4 obtained in Synthesis Example 1 in Example 1 is 4 parts by weight instead of 8 parts by weight, and dipentaerythritol hexaacrylate (when R1 to R6 are all substituted with acryloyl groups in Formula 1) The same as Example 1 except that 4 parts by weight were mixed. As a result of discrimination after the experiment, all 5 micron patterns remained.

Example 3
Example 1 was the same as Example 1 except that 8 parts by weight of the compound of Formula 5 obtained in Synthesis Example 2 was mixed in place of 8 parts by weight of the compound of Formula 4 obtained in Synthesis Example 1. is there. As a result of discrimination after the experiment, all 6-micron patterns remained.

Example 4
Instead of 8 parts by weight of the compound of Formula 4 obtained in Synthesis Example 1 in Example 1, 4 parts by weight of the compound of Formula 5 obtained in Synthesis Example 2 and 4 parts by weight of pentaerythritol triacrylate were mixed. Is the same as in Example 1. As a result of discrimination after the experiment, all 6-micron patterns remained.

Example 5
Example 1 is the same as Example 1 except that the compound of Formula 6 obtained in Synthesis Example 3 was used instead of the compound of Formula 4 obtained in Synthesis Example 1.

Example 6
Example 2 is the same as Example 2 except that the compound of Formula 6 obtained in Synthesis Example 3 was used instead of the compound of Formula 4 obtained in Synthesis Example 1.

Example 7
Example 1 is the same as Example 1 except that the compound of Formula 7 obtained in Synthesis Example 4 was used instead of the compound of Formula 4 obtained in Synthesis Example 1 in Example 1.

Example 8
Example 2 is the same as Example 2 except that the compound of Formula 7 obtained by Synthesis Example 4 was used instead of the compound of Formula 4 obtained by Synthesis Example 1 in Example 2.

Comparative Example 1
Example 8 is the same as Example 1 except that 8 parts by weight of dipentaerythritol hexaacrylate is mixed in place of 8 parts by weight of the compound of Formula 4 obtained in Synthesis Example 1 in Example 1. As a result of discrimination after the experiment, all 7-micron patterns remained.

Comparative Example 2
In place of 8 parts by weight of the compound of Formula 4 obtained in Synthesis Example 1 in Example 1, 8 parts by weight of dipentaerythritol hexaacrylate and 1 part by weight of 3-methacryloxypropylmethyldimethoxysilane as a coupling agent were mixed. This was the same as Example 1 except that 82 parts by weight of the solvent was mixed instead of 83 parts by weight. As a result of discrimination after the experiment, all 5 micron patterns remained.

Comparative Example 3
Example 8 is the same as Example 1 except that 8 parts by weight of pentaerythritol triacrylate was mixed in place of 8 parts by weight of the compound of Formula 4 obtained in Synthesis Example 1 in Example 1. As a result of discrimination after the experiment, all 8 micron patterns remained.

Comparative Example 4
Instead of 8 parts by weight of the compound of Formula 4 obtained in Synthesis Example 1 in Example 1, 8 parts by weight of pentaerythritol triacrylate and 1 part by weight of 3-methacryloxypropylmethyldimethoxysilane as a coupling agent were mixed. This was the same as Example 1 except that 82 parts by weight of the solvent was mixed instead of 83 parts by weight. As a result of discrimination after the experiment, all 6-micron patterns remained.

The results obtained by the examples and comparative examples are summarized in Table 1 and FIG.

  From the results of this experiment, it can be said that the photosensitive resin composition having excellent adhesive force is left so that the pattern produced from the photomask having a smaller pattern is not lost, compared to the films according to the examples and comparative examples. The results of observing the size of the remaining pattern without being lost due to water pressure during the development process are as shown in Table 1 above.

  From the results of Table 1, the results of Example 1 and Example 2 were compared with the results of Comparative Example 1 and Comparative Example 2, as in Example 1 and Example 2, according to Synthesis Example 1 according to the present invention. When the resulting compound of Formula 4 was used in full (Example 1) or partially (Example 2) with a polyfunctional acrylic compound, the minimum pattern size was observed to be 5 microns, which was less than 7 microns in size. It can be said that the pattern is a result showing that the adhesive strength is superior to Comparative Example 1 which is lost and not observed. In addition, in Examples 1 and 2, the same adhesive strength as that in the case of using the coupling agent was realized as in Comparative Example 2, although the coupling agent was not used. You can see that

  Similarly, when the results of Example 3 and Example 4 are compared with those of Comparative Example 3 and Comparative Example 4, the compound of Chemical Formula 5 obtained by Synthesis Example 2 is fully (Example 3) or a part of the polyfunctional acrylic compound. (Example 4) When used, the size of the smallest remaining pattern was 6 microns, and any pattern with a size of less than 8 microns had better adhesion than the lost Comparative Example 3. It can be seen that it implements the same degree of adhesion as when using the coupling agent of Comparative Example 4.

  Therefore, the photosensitive resin composition containing the polyfunctional acrylic compound having a siloxane group according to the present invention has superior adhesive strength as compared with the existing technology. It is possible to prevent defects caused by the loss of the small pattern.

It is the photograph which image | photographed the shape of the pattern manufactured by the Example and the comparative example.

Claims (6)

1 to 35% by weight of a polyfunctional acrylic compound represented by the following chemical formula 1 or a polyfunctional acrylic compound represented by the following chemical formula 2 ;
1 to 45% by weight of an alkali-soluble binder resin,
0.05 to 10% by weight of photoinitiator,
A negative photosensitive composition comprising 10 to 97.95% by weight of a solvent.
[In Formula 1 above,
R1 to R6 may be the same as or different from each other, and are independently a hydrogen atom (—H), an acryloyl group (—C (O) —CH═CH ₂ ), a succinic acid group (—C (O) C ₂ H ₄ C (O) OH) and any one selected from the group consisting of substituents having the structure of the following chemical formula 3, wherein at least two acryloyl groups and at least one substituent having the structure of the following chemical formula 3 are used. Is included. ]
[In Formula 3,
R11 to R13 may be the same as or different from each other, and each represents an alkyl group having 1 to 2 carbon atoms. ]
[In Formula 2 above
R7 to R10 may be the same or different from each other, and are independently a hydrogen atom (—H), an acryloyl group (—C (O) —CH═CH ₂ ), a succinic acid group (—C (O) C ₂ H ₄ C (O) OH) and any one selected from the group consisting of substituents having the structure of the following chemical formula 3, wherein at least two acryloyl groups and at least one substituent having the structure of the following chemical formula 3 are used. Is included. ]
[In Formula 3,
R11 to R13 may be the same as or different from each other, and each represents an alkyl group having 1 to 2 carbon atoms. ] The polyfunctional acrylic compound is included as a polyfunctional monomer,
The negative photosensitive composition according to claim 1, wherein the polyfunctional monomer further comprises an acrylic compound not containing a siloxane group. The negative photosensitive composition according to claim 2, wherein the acrylic compound containing no siloxane group is contained in an amount of 1 to 15% by weight of the total composition. The composition according to claim 1, further comprising at least one selected from the group consisting of a curing colorant, an accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler, and a surfactant. The negative photosensitive composition as described in any one of Claims. The negative photosensitive composition as described in any one of Claims 1-4 whose photosensitive composition containing the said polyfunctional acrylic compound is a thing which does not contain a coupling agent. The polyfunctional acrylic compound represented by the chemical formula 1 or the polyfunctional acrylic compound represented by the chemical formula 2 is selected from the group consisting of compounds represented by the following chemical formulas 4 to 7, The negative photosensitive composition as described in any one of 5 .