JP2011132232A - Crosslinking compound and photosensitive composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crosslinking compound containing a cinnamic acid group, a method for producing the compound and a photosensitive composition containing the compound. <P>SOLUTION: The crosslinking compound containing a cinnamic acid group is used in the photosensitive composition such as a color filter composition for LCD to improve photosensitivity and membrane strength compared with conventional case to use an acrylate compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a crosslinkable compound contained in a photosensitive composition, in particular, a crosslinkable compound containing a cinnamic acid group, a method for producing the same, and a photosensitive composition containing the same.

  In the production of a color filter for a liquid crystal display element, a photosensitive composition is produced in the form of a solution based on a crosslinkable compound, a binder polymer, and a photopolymerization initiator as essential materials. Therefore, since the manufactured thin film also has a polymer as a main component, the overall physical properties are greatly influenced by the crosslinkable compound and the binder polymer. In particular, the photosensitivity and the mechanical strength of the thin film vary greatly depending on the type of the crosslinkable compound.

Typical examples of the crosslinkable compound include pentaerythritol triacrylate represented by the following general formula 4 and dipentaerythritol hexaacrylate represented by the general formula 5.
The two acrylates are the most widely used, and are relatively excellent in photosensitivity and mechanical strength of the thin film. It is becoming necessary to develop new materials that exceed this.

  An object of the present invention is to provide a crosslinkable compound capable of forming a thin film having superior photosensitivity and mechanical strength, which is differentiated from conventional materials.

  Another object of the present invention is to provide a method for producing the crosslinkable compound.

  Another object of the present invention is to provide a photosensitive composition using the crosslinkable compound.

A crosslinkable compound according to an embodiment of the present invention for solving the above-described problems is represented by the following general formula 1.

In the formula, R is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a halogen element.
A crosslinkable compound according to an embodiment for solving another problem of the present invention is represented by the following general formula 2.

  In the formula, R is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a halogen element.

According to another embodiment for solving the problems of the present invention, the method for producing the crosslinkable compound represented by the general formula 1 includes pentaerythritol triacrylate and cinnamic acid represented by the following general formula 3. Reacting with the anhydrous chloride of the derivative can be included.

In the formula, R is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a halogen element.
According to another embodiment for solving the problems of the present invention, the method for producing the crosslinkable compound represented by the general formula 2 includes dipentaerythritol pentaacrylate and cinnamon represented by the following general formula 3. Reacting with the anhydrous chloride of the acid derivative may be included.

  In the formula, R is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a halogen element.

In addition, the photosensitive composition which concerns on the other Example for solving the subject of this invention contains the crosslinkable compound, binder resin, photoinitiator, and solvent which are represented by the said General formula 1 or General formula 2. Can be included.
According to another embodiment of the present invention, the crosslinkable compound is obtained by, for example, esterifying a polyhydric alcohol with an α, β-unsaturated carboxylic acid into the compound represented by the general formula 1 or the general formula 2. Compound obtained, compound obtained by adding (meth) acrylic acid to compound containing glycidyl group, ester compound of hydroxyl group or compound having ethylenically unsaturated bond and polyvalent carboxylic acid, hydroxyl group or ethylenically unsaturated One or more selected from the adduct of a compound having a bond and a polyisocyanate, (meth) acrylic acid alkyl ester, and 9,9′-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene are mixed. It is what is done.
The crosslinkable compound may be included in an amount of 5 to 70% by weight based on the total solid content of the photosensitive composition.
The binder resin is alkali-soluble and is, for example, an acrylic binder resin containing a carboxyl group.
The photopolymerization initiator is selected from, for example, triazine compounds, biimidazole compounds, acetophenone compounds, O-acyloxime compounds, benzophenone compounds, thioxanthone compounds, phosphine oxide compounds, and coumarin compounds. One or more.
Examples of the solvent include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2 -Methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl Seteto, and it is at least one selected from the group consisting of dipropylene glycol monomethyl ether.
In addition, according to an embodiment of the present invention, the photosensitive composition includes, for example, a colorant, a curing accelerator, a thermal polymerization inhibitor, a surfactant, a photosensitizer, a plasticizer, an adhesion promoter, and a filler. 1 or more types of additives chosen from among these can further be included.
The colorant is, for example, a pigment, a dye or a mixture thereof.
Examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, and 2-mercapto-4,6-dimethylamino. Pyridine, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethanetris (2-mercaptoacetate), and trimethylolethanetris (3-mercaptopropionate) One or more selected.
The thermal polymerization inhibitor is, for example, one selected from the group consisting of p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine aluminum salt, and phenothiazine. That's it.
The photosensitive composition is 1 to 30 parts by weight of a crosslinkable compound represented by the general formula 1 or 2 with respect to 100 parts by weight of the photosensitive composition, 1 to 20 parts by weight of a binder resin, and 0. 1 to 5 parts by weight, and 45 to 95 parts by weight of solvent can be included.

According to the present invention, a thin film made using such a photosensitive composition by using, as a monomer of the photosensitive composition, a compound having a cinnamic acid group as a crosslinkable compound having two or more unsaturated acrylic bonds. Has very good photosensitivity and film strength.
Therefore, by using the photosensitive composition according to the present invention, it is possible to provide a thin film that meets the requirements for an increase in the size of a liquid crystal display element and has excellent physical properties.
Thus, the photosensitive composition according to the present invention is a pigment dispersion type photosensitive material for manufacturing TFT LCD color filters, a black matrix forming photosensitive material for TFT LCD or organic light emitting diode, an overcoat layer forming photosensitive material, a column spacer photosensitive material. It is desirable to be used for materials, but it is also used for the production of photo-curable paints, photo-curable inks, photo-curable adhesives, photosensitive materials for printed boards, printed wiring boards, other transparent photosensitive materials, and PDPs. There are no particular restrictions on its use.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

The crosslinkable compound represented by the general formula 1 according to the present invention can be produced by reacting the pentaerythritol triacrylate represented by the general formula 4 with the anhydrous cinnamic acid derivative represented by the general formula 3, This is as represented by the following reaction formula 1.

Specifically, it can be produced by stirring and reacting a solution obtained by dissolving pentaerythritol triacrylate in propylene glycol methyl ether acetate and an anhydrous chloride of cinnamic acid derivative.
In one example of this, first, 50 g of pentaerythritol triacrylate is dissolved in 50 g of propylene glycol methyl ether acetate using a 500 mL round bottom flask. The mixture is then stirred using a magnetic stirrer and the temperature is raised to 70 ° C. and maintained until the reaction is complete. Next, 24 g of anhydrous cinnamic acid derivative was slowly mixed with a solution prepared by dissolving 50 g of propylene glycol methyl ether acetate to 0.6 mL per minute. After all the prepared solutions were mixed, about 2 hours Further agitation is performed to complete the reaction. Thereafter, the temperature is lowered to room temperature and the solution is taken. When the obtained solution is dried in a vacuum dryer, a crosslinkable compound of formula 1 and HCl are obtained.
Further, the crosslinkable compound represented by the general formula 2 according to another embodiment of the present invention is dipentaerythritol pentaacrylate represented by the general formula 5 and an anhydrous chloride of cinnamic acid derivative represented by the general formula 3. These can be produced by reacting with the following reaction formula 2.

Specifically, it can be produced by stirring and reacting a solution obtained by dissolving dipentaerythritol pentaacrylate in propylene glycol methyl ether acetate and anhydrous chloride of cinnamic acid derivative.
In one example of this, first, 50 g of dipentaerythritol pentaacrylate is dissolved in 50 g of propylene glycol methyl ether acetate using a 500 mL round bottom flask. The mixture is then stirred using a magnetic stirrer and the temperature is raised to 70 ° C. and maintained until the reaction is complete. Next, a solution prepared by dissolving 50 g of propylene glycol methyl ether acetate in 16.2 g of anhydrous cinnamic acid derivative was slowly mixed to about 0.6 mL per minute. After all the prepared solutions were mixed, about The reaction is completed by further stirring for about 2 hours. Thereafter, the temperature is lowered to room temperature and the solution is taken. When the obtained solution is dried in a vacuum dryer, a crosslinkable compound of formula 2 and HCl are obtained.
The cinnamic acid derivative represented by the general formula 3 according to the present invention can include both cis type and trans type, and is not particularly limited.

Meanwhile, according to an embodiment of the present invention, the present invention is characterized in that it provides a photosensitive composition comprising a crosslinkable compound represented by the general formula 1 or the general formula 2, a binder resin, a photopolymerization initiator, and a solvent. is there.
That is, by using a crosslinkable compound containing a cinnamic acid group in the photosensitive composition, the photosensitivity of the thin film and the strength of the film are improved. The existing acrylate-based crosslinkable compound undergoes a polymerization reaction only by radicals, but the cinnamic acid group itself undergoes a photoreaction, so when using a crosslinkable compound containing a cinnamic acid group, the two reactions are both The effect of being performed improves the photosensitivity and the strength of the film.

  The crosslinkable compound contains two or more unsaturated acrylic bonds, and a compound represented by the general formula 1 or the general formula 2 is used.

  In addition, the compound represented by the general formula 1 or the general formula 2 may be used by mixing other crosslinkable compounds containing two or more unsaturated groups.

  Examples of the crosslinkable compound that can be mixed include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyloxymethylethylphthalic acid, propylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol A mixture of an acid variant of penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate (trade name; Nippon Tojo) Compound obtained by esterifying polyhydric alcohols such as TO-2348 and TO-2349 manufactured by Synthetic Co., Ltd. with α, β-unsaturated carboxylic acid; trimethylolpropane triglycidyl ether acrylic acid adduct, bisphenol A diester Compound obtained by adding (meth) acrylic acid to a compound containing glycidyl group such as glycidyl ether acrylic acid adduct; phthalic acid diester of β-hydroxyethyl (meth) acrylate, β-hydroxyethyl (meth) acrylate An ester compound of a compound having a hydroxyl group or an ethylenically unsaturated bond such as toluene diisocyanate adduct and a polycarboxylic acid, or an adduct of polyisocyanate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, etc. ) An acrylic acid alkyl ester; and 9,9′-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, including, but not limited to, A known general one can be used. In some cases, silica dispersions can be used for these compounds, and examples thereof include Nanocry XP series (0596, 1045, 21/1364) and Nanopox XP series (0516, 0525) manufactured by Hanse Chemie.

  And the said crosslinkable compound is 5-70weight% with respect to the whole solid content of the photosensitive composition. When the crosslinkable compound is less than 5% by weight, the effect to be obtained in the present invention cannot be ensured, and considering the viscosity problem of the photosensitive composition, it is desirable that the content is 70% by weight or less.

  Examples of the binder resin include those commonly used in the art such as an alkali-soluble binder resin. Specifically, an acrylic binder resin that is soluble in alkali and contains a carboxyl group, desirably having a weight average molecular weight of 3,000 to 150,000 can be used.

  Examples of the photopolymerization initiator include 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine, 2, 4-trichloromethyl- (fipronyl) -6-triazine, 2,4-trichloromethyl- (3 ′, 4′-dimethoxyphenyl) -6-triazine, 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid, 2,4-trichloromethyl- (4'-ethylbiphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methylbiphenyl) -6- Triazine compounds such as triatin; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4, Biimidazole compounds such as 4 ', 5,5'-tetraphenylbiimidazole; 2-hydroxy- -Methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy) propyl Ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one (Irgacure-907), 2- Acetophenone compounds such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure-369); O-acyloxy such as Irgacure OXE 01 and Irgacure OXE 02 manufactured by Ciba Geigy Compounds such as 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone Phenone compounds; thioxanthone compounds such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, diisopropylthioxanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 Phosphine oxide compounds such as 3,4,4-trimethylpentylphosphine oxide and bis (2,6-dichlorobenzoyl) propylphosphine oxide; 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] -benzopyrano [6, A coumarin compound such as 7,8-ij] -quinolizin-11-one may be used alone or in admixture of two or more.

  Examples of the solvent include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2 -Methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl Seteto, and can include one or more members selected from the group consisting of dipropylene glycol monomethyl ether, it not necessarily limited thereto.

  On the other hand, the photosensitive composition of the present invention includes one additive such as a colorant, a curing accelerator, a thermal polymerization inhibitor, a surfactant, a photosensitizer, a plasticizer, an adhesion promoter, and a filler depending on the application. The above can be further included.

  As the colorant, one or more pigments, dyes, or a mixture thereof can be used. Specifically, as the black pigment, a metal oxide such as carbon black, graphite, or titanium black can be used. Examples of carbon black include SEAST 5HIISAF-HS, SEAST KH, SEAST 3HHAF-HS, SEAST NH, SEAST 3M, SEAST 300HAF-LS, SEAST 116HMMAF-HS, SEAST 116MFF, SEAST FMFE, SEAST VGPF, SEAST SVHSRF-HS and SEAST 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 N550M E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 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, PRINTERX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, RINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (Degussa Corp.); RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1060ULTRA 1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-780ULTRA, RAVEN-780ULTRA RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-4 0, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, RAVEN-1170 (Columbia Carbon Corporation )) Or a mixture thereof. Examples of the colorant include carmine 6B (C.I. 12490), phthalocyanine green (C.I. 74260), phthalocyanine blue (C.I. 74160), perylene black (BASF K0084.K0086), cyanine Black, Linole Yellow (C.I. 21090), Linol Yellow GRO (C.I. 21090), Benzidine Yellow 4T-564D, Victoria Pure Blue (C.I. 42595), CI 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; C. PIGMENT GREEN 7, 36; C.I. PIGMENT blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14 , 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; C.I. PIGMENT VIOLET 15, 19, 23, 29 , 32, 37, etc. In addition, white pigments, fluorescent pigments, and the like can also be used. As the phthalocyanine complex compound used as a pigment, a substance having zinc as a central metal in addition to copper can also 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-dimethyl. Aminopyridine, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane Tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), and trimethylolethanetris (3-mercaptopropionate). 1 type or more selected from these groups can be included, but is not limited thereto, and those generally known in the art can be used.

  Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, N-nitrosophenylhydroxyamine ammonium salt, and N-nitrosophenylhydroxyamine aluminum salt. And one or more selected from the group consisting of phenothiazine, but is not limited thereto, and those generally known in the art can be used.

  Of the substances used as additives, all compounds contained in conventional photosensitive resin compositions can be used for surfactants, photosensitizers, plasticizers, adhesion promoters, fillers, and the like.

  On the other hand, the transparent photosensitive composition according to the present invention is used for a roll coater, a curtain coater, a spin coater, a spin die coater, a slot die coater, various printing, deposition, etc. It can be applied on a support such as paper or glass plastic substrate. In addition, after coating on a support such as a film, it can be transferred onto another support, or after being applied to the first support, transferred to a blanket or the like, and further transferred to a second support. The application method is not particularly limited.

  Examples of the light source for curing the transparent photosensitive composition of the present invention include mercury vapor arc (arc), carbon arc, and Xe arc that emit light having a wavelength of 250 to 450 nm. It is not limited.

  The component content of the photosensitive composition is such that the crosslinkable compound is 1 to 30 parts by weight, the binder resin is 1 to 20 parts by weight, and the photopolymerization initiator is 0.1 to 100 parts by weight of the photosensitive composition. It is desirable that 5 parts by weight and the solvent be 45 to 95 parts by weight. When other components that can be added are added, it is desirable to contain 1 to 20 parts by weight of the colorant and 0.01 to 5 parts by weight of the other additives.

  The photosensitive composition according to the present invention is used for a pigment dispersion type photosensitive material for producing TFT LCD color filters, a black matrix forming photosensitive material for TFT LCD or organic light emitting diode, an overcoat layer forming photosensitive material, and a column spacer photosensitive material. However, it can also be used for the production of photo-curable paints, photo-curable inks, photo-curable adhesives, printing plates, photosensitive materials for printed wiring boards, other transparent photosensitive materials, and PDPs. There are no particular restrictions.

(Example 1)
In order to confirm the effect of the present invention, the following photosensitive composition was produced.
8 parts by weight of benzyl methacrylate / methyl methacrylate (MAA) (molar ratio: 70/30, Mw: 24,000) as an alkali-soluble binder resin, 8 parts by weight of the compound of general formula 1 as a crosslinkable compound, as a photopolymerization initiator A solution prepared by mixing 1 part by weight of Irgacure-369 manufactured by Ciba-Geigy and 83 parts by weight of propylene glycol methyl ether acetate (PGMEA) as an organic solvent using a shaker for 3 hours was collected with a 5-micron filter. Used.

The photosensitive composition was applied by a spin coating method to form a uniform thin film, and then a pre-bake process was performed at 100 ° C. for 200 seconds to dry the solvent. The thickness of the dried thin film was about 4 mm. Thereafter, exposure was performed with an energy of 100 mJ / cm ² under a high-pressure mercury lamp using a photomask. The exposed substrate was developed by spraying at a temperature of 25 ° C. and 0.04% KOH aqueous solution, washed with pure water, and dried by air blowing.

  At this stage, the acrylate conversion was measured to compare the photosensitivity of the thin film.

  Then, after carrying out post heat treatment (postbake) for 20 minutes in a convection oven at 220 ° C., the film strength of the manufactured thin film was measured using a barcovic tip equipped with nanoindentation.

  The results are shown in Table 1.

(Example 2)
Example 1 except that 4 parts by weight of the compound of general formula 1 and 4 parts by weight of pentaerythritol triacrylate were added as a crosslinkable compound in Example 1 instead of 8 parts by weight of the compound of general formula 1 It is the same.

Example 3
Example 1 is the same as Example 1 except that 8 parts by weight of the compound of the general formula 1 is added as a crosslinkable compound instead of 8 parts by weight of the compound of the general formula 1.

Example 4
Example 1 except that 4 parts by weight of the compound of the general formula 2 and 4 parts by weight of dipentaerythritol pentaacrylate were added as a crosslinkable compound in Example 1 instead of 8 parts by weight of the compound of the general formula 1. It is the same.

(Comparative Example 1)
Example 1 is the same as Example 1 except that 8 parts by weight of pentaerythritol triacrylate is added in place of 8 parts by weight of the compound of the general formula 1 as the crosslinkable compound.

(Comparative Example 2)
Example 1 is the same as Example 1 except that 8 parts by weight of dipentaerythritol pentaacrylate is added instead of 8 parts by weight of the compound of general formula 1 as the crosslinkable compound.

  Table 1 shows the experimental results obtained by the examples and comparative examples. In the case of Example 1 and Example 2 including the crosslinkable compound of the general formula 1, both the conversion rate and the film strength are higher than those of Comparative Example 1 using the acrylic crosslinkable compound conventionally used. Similarly, in the case of Example 3 and Example 4 including the crosslinkable compound of the general formula 2, both the conversion rate and the film strength are higher than those in Comparative Example 2, and therefore, a crosslinkable compound including a cinnamic acid group is used. It can be seen that both the photosensitivity and the film strength are improved.

Claims (15)

A crosslinkable compound represented by the following general formula 1.

[Where,
R is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a halogen element. ] A crosslinkable compound represented by the following general formula 2.

[Where,
R is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a halogen element. ] A method for producing a crosslinkable compound represented by the general formula 1 according to claim 1, wherein pentaerythritol triacrylate is reacted with an anhydrous chloride of a cinnamic acid derivative represented by the following general formula 3.

[Where,
R is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a halogen element. ] A method for producing a crosslinkable compound represented by the general formula 2 according to claim 2, wherein dipentaerythritol pentaacrylate is reacted with an anhydrous chloride of a cinnamic acid derivative represented by the following general formula 3.

[Where,
R is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a halogen element. ]   A photosensitive composition comprising a crosslinkable compound represented by the general formula 1 or the general formula 2, a binder resin, a photopolymerization initiator, and a solvent.   The crosslinkable compound is a compound obtained by esterifying a polyhydric alcohol with an α, β-unsaturated carboxylic acid to the compound represented by the general formula 1 or 2, and a compound containing a glycidyl group (meth) A compound obtained by adding acrylic acid, an ester compound of a compound having a hydroxyl group or ethylenically unsaturated bond and a polycarboxylic acid, an adduct of a compound having a hydroxyl group or ethylenically unsaturated bond and a polyisocyanate, 6) One or more kinds selected from alkyl ester of acrylic acid and 9,9′-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene are mixed. Photosensitive composition.   The photosensitive composition according to claim 5, wherein the crosslinkable compound is contained in an amount of 5 to 70% by weight based on the total solid content of the photosensitive composition.   The photosensitive composition according to claim 5, wherein the binder resin is an alkali-soluble acrylic binder resin containing a carboxyl group.   The photopolymerization initiator is one selected from triazine compounds, biimidazole compounds, acetophenone compounds, O-acyloxime compounds, benzophenone compounds, thioxanthone compounds, phosphine oxide compounds, and coumarin compounds. It is the above, The photosensitive composition of Claim 5 characterized by the above-mentioned.   The solvent is methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxy Propanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate And wherein the at least one selected from the group consisting of dipropylene glycol monomethyl ether, photosensitive composition according to claim 5.   The photosensitive composition comprises at least one additive selected from a colorant, a curing accelerator, a thermal polymerization inhibitor, a surfactant, a photosensitizer, a plasticizer, an adhesion promoter, and a filler. The photosensitive composition according to claim 5, further comprising:   The photosensitive composition according to claim 11, wherein the colorant is a pigment, a dye, or a mixture thereof.   The curing accelerator is 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, Pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2 -Mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), and trimethylolethane tris (3-mercaptopropionate) The photosensitive composition according to claim 11, wherein the photosensitive composition is one or more.   The thermal polymerization inhibitor is one or more selected from the group consisting of p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine aluminum salt, and phenothiazine. The photosensitive composition according to claim 11, wherein the composition is a photosensitive composition.   The photosensitive composition is 1 to 30 parts by weight of a crosslinkable compound represented by the general formula 1 or 2 with respect to 100 parts by weight of the photosensitive composition, 1 to 20 parts by weight of a binder resin, and 0. The photosensitive composition according to claim 5, comprising 1 to 5 parts by weight and 45 to 95 parts by weight of a solvent.