TW201100954A - Photosensitive resin composition and liquid crystal panel - Google Patents

Abstract

The present invention provides a photosensitive resin composition with an appropriate developing time and capable of forming a spacer which is good in shape or has good adhesion to substrates; and a liquid crystal panel having the spacer formed from the photosensitive resin composition. The photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a photopolymerization monomer (B) and a photopolymerization initiator (C). The alkali-soluble resin (A) comprises, for example, a constituent unit (a1) derived from unsaturated carboxylic acids, a constituent unit (a2) derived from an unsaturated compound of an epoxy group without an alicyclic group, and a constituent unit (a3) derived from an unsaturated compound of an alicyclic epoxy group, wherein the summation of the proportion of the constituent unit (a2) and the proportion of the constituent unit (a3) is more than 71 mass percent.

Description

201100954 VI. Description of the Invention: [Technical Field] The present invention relates to a photosensitive resin composition and a liquid crystal panel. More specifically, it relates to an interval suitable for forming between two substrates formed on a liquid crystal panel. A photosensitive resin composition in the case of a material, and a liquid crystal panel having a spacer formed of the photosensitive resin composition. [Prior Art] In the liquid crystal panel of a liquid crystal display device, since a sandwich structure in which a liquid crystal material is sandwiched by a transparent substrate such as two glass substrates is used, it is necessary to form a liquid crystal material between two substrates. Spacer. Conventionally, in order to form a spacer, a method of dispersing beads forming a spacer over the entire substrate is used, but only on the pixel display portion; beads are also attached, and the contrast of the image or the display image quality is lowered. . Therefore, various methods for forming the spacer by the photosensitive resin composition have been proposed in recent years (see Patent Documents 1, 2, etc.). In this method, a photosensitive resin composition is applied onto a substrate, exposed to light through a predetermined mask, and developed to form spacers such as dots, and spacers can be formed only in a predetermined portion other than the pixel display portion. . [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2006-108841 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei No. 2006-308961 No. 201100954 When the excess load causes plastic deformation or damage of the spacer, the spacer formed must have sufficient breaking strength. Therefore, an alkali-soluble resin having a constituent unit derived from an epoxy group-containing unsaturated compound such as glycidyl methacrylate is usually used as the resin contained in the photosensitive resin composition. However, as a result of intensive review, the inventors of the present invention found that the ratio of the constituent units derived from glycidyl methacrylate or the like to the breaking strength is, for example, 71% by mass or more, which is broken during development. The point (BP; the time when the unexposed portion is completely dissolved) becomes extremely short, and development is not easily performed properly. Further, it is understood that the shape of the spacer is deteriorated at the same time, and the adhesion to the substrate is lowered. The present invention is directed to a photosensitive resin composition having a suitable developability and capable of forming a spacer having a good shape or adhesion to a substrate, and having a photosensitive resin composition. The liquid crystal panel of the spacer formed by the object is for the purpose. In order to solve the above problems, the inventors of the present invention have conducted in-depth review. As a result, it was found that by using a constituent unit derived from an unsaturated carboxylic acid and a constituent unit derived from an epoxy group-containing unsaturated compound having no alicyclic group, and an unsaturated group containing an alicyclic epoxy group The above-mentioned problem can be solved by the constituent unit derived from the compound or the alkali-soluble resin derived from the constituent unit derived from the unsaturated compound containing an alicyclic group, and the present invention has been completed. Specifically, the present invention provides the following. -6 - 201100954 The first aspect of the present invention relates to a photosensitive resin composition comprising a photosensitive resin comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C). And the alkali-soluble resin (A) is a constituent unit derived from a constituent unit (al) derived from an unsaturated carboxylic acid and derived from an unsaturated compound having an epoxy group having no alicyclic group (a2) And a constituent unit (a3) derived from an unsaturated compound containing an alicyclic epoxy group, and the total ratio of the ratio of the q of the constituent unit (a2) to the ratio of the constituent unit (a3) is 7 1 by mass. % the above. The second aspect of the present invention relates to a photosensitive resin composition containing a photosensitive resin composition of an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), which are characterized by The alkali-soluble resin (A) is a constituent unit (a2) having a constituent unit derived from an unsaturated carboxylic acid (al), an unsaturated compound having an epoxy group having no alicyclic group, and The constituent unit (a4) derived from the alicyclic group-containing unsaturated compound Q, and the ratio of the above-mentioned constituent unit (a2) is 71% by mass or more. A third aspect of the present invention relates to a liquid crystal panel characterized by comprising a spacer formed of the photosensitive resin composition of the present invention. [Effect of the Invention] According to the present invention, it is possible to provide a photosensitive resin composition which has a suitable developability and can form a spacer having a good shape or adhesion to a substrate, and a composition formed of the photosensitive resin composition. Spacer 201100954 panel for spacers. [In order to carry out the invention] <<Photosensitive resin composition>> The photosensitive resin composition of the present invention contains at least an alkali-soluble resin (A), a photopolymerizable monomer (B), and photopolymerization. Initiator (C). Each component contained in the photosensitive resin composition of the present invention will be described below. <Alkali-soluble resin (A) > The alkali-soluble resin refers to a resin film having a film thickness i formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, at 2.38 When the mass% of tetramethylammonium hydroxide (TMAH) is immersed in an aqueous solution for 1 minute, the film thickness is O.Olym or more. The alkali-soluble resin (A) (hereinafter also referred to as "(A) component)) contained in the photosensitive resin composition of the present invention has a constituent unit (al) derived from an unsaturated carboxylic acid, and contains no a constituent unit (a 2 ) derived from an alicyclic group-containing epoxy group-containing unsaturated compound, and a constituent unit (a3) derived from an alicyclic epoxy group-containing unsaturated compound (hereinafter, the resin is also referred to as "(A1) resin")" and a constituent unit (a4) derived from the above-mentioned constituent unit (al), the above-mentioned constituent unit (a2), and an unsaturated compound containing an alicyclic group (hereinafter, the resin is also referred to as " (A2) Resin"). In the following, the sequence describes various situations related to these. -8- 201100954 ((A1) resin) The resin (A1) has at least the above-mentioned structural unit (a1), the above-mentioned structural unit (a2), and the above-mentioned constituent unit (a3). An unsaturated carboxylic acid such as (meth)acrylic acid or crotonic acid; or a monocarboxylic acid such as (meth)acrylic acid or crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid, which are derived from the constituent unit (a 1 ). Dicarboxylic acid such as acid; acid anhydride of such dicarboxylic acid, and the like. Among these, (meth)acrylic acid and maleic anhydride are preferred in terms of copolymerization reactivity, alkali solubility of the obtained resin, ease of availability, and the like. These unsaturated carboxylic acids may be used singly or in combination of two or more kinds. In order to obtain the epoxy group-unsaturated compound having no alicyclic group when the constituent unit (a2) is derived, for example, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, Methyl)acrylic acid 3,4-epoxybutyl acrylate, (meth)acrylic acid 6,7-epoxyheptyl ester, etc. (meth)acrylic acid epoxy phthalic acid '-ethyl propylene storage acid Epoxy propylene vinegar, Q; - n-propyl propyl enoyl methacrylate, n-butyl acrylate butyl acrylate, α-ethyl acrylate 6,7-epoxy heptyl ester, etc.: -alkyl Cycloalkyl acrylates and the like. Among these, 'in terms of copolymerization reactivity, resin strength after curing, etc., 'glycidyl methacrylate, 2-methylglycidyl (meth)acrylate, and (methyl) The 6,7-epoxyheptyl acrylate is preferred. These epoxy group-containing unsaturated compounds having no alicyclic group may be used singly or in combination of two or more kinds. In order to make the alicyclic epoxy group-unsaturated compound when the constituent unit (a3) is derivatized, only the unsaturated compound having an alicyclic epoxy group can be used without any particular limitation. The alicyclic group constituting the alicyclic epoxy group may be a single ring or a polycyclic ring. The monocyclic alicyclic group is, for example, a cyclopentyl group, a cyclohexyl group or the like. Further, the polycyclic alicyclic group is, for example, a norbornyl group, an isobornyl group, a tricyclodecyl group, a tricyclodecyl group or a tetracyclododecyl group. Specifically, the alicyclic epoxy group-containing unsaturated compound is, for example, a compound represented by the following formula (a3-1) to (a3-15). In the above, in order to make the developability suitable, the compounds represented by the following formulas (a3_1) to (a3·5) are preferably represented by the following formulas (a3-1) to (a3-3). The compound is better. 【化1】 R11

(a3-1) (a3-2)

(a3-3)

(a3-4)

-10- 201100954

(a3-7)

(a3-10) -11 - 201100954 [Chemical 3]

In the above formula, R11 represents a hydrogen atom or a methyl group, R12 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R 13 represents a divalent hydrocarbon group having 1 to 1 carbon number, and η represents 0 to 0. An integer of 10. R12 is a linear or branched alkyl group such as methylene, ethyl, propyl, tetramethylene, ethylethyl, pentamethylene or hexamethylene. R13 is, for example, methylene, ethyl, propyl, tetramethylene, ethylethyl, pentamethylene, hexamethylene, phenylene, cyclohexyl, -CH2-Ph-CH2- ( Ph is a phenylene group. In addition, the total amount of the ratio of the ratio of the constituent unit (a2) to the constituent unit (a3) of the (A1) resin may be 71% by mass or more and 12 to 201100954, and may have the following constituent units (a4). ). The effect of the present invention can be improved by combining the constituent units (a4). Further, the (A1) resin may have other constituent units other than the above-described constituent units (al), (a2), (a3), and (a4). The compound in the case where the other constituent unit is derived is, for example, a (meth) acrylate, a (meth) acrylamide, an allyl compound, a vinyl ether, a vinyl ester, a styrene or the like. These compounds may be used alone or in combination of two or more. (Meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, 3-octyl (meth) acrylate Linear or branched alkyl (meth)acrylate; ethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-(meth)acrylate Hydroxyethyl ester, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, decyl (meth)acrylate, and the like. Ruthenium (meth) acrylamides such as (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, n, N-dialkyl ( Methyl) acrylamide, N,N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl _N-methyl (A Base) acrylamide and the like. Dilute propyl compounds such as allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, benzoic acid, acetonitrile, acetaminoacetic acid Allyl esters such as allyl ester and allyl lactate; allyloxyethanol and the like. -13- 201100954 Vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl vinyl ether, ethyl vinyl chloride , 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, An alkyl vinyl ether such as diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether or tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl toluene ether, vinyl A vinyl aryl ether such as phenyl chloride, vinyl-2,4-diphenyl ether, vinyl naphthyl ether or vinyl anthracene. Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl acetate, vinyl acetate Ester, methoxyvinyl acetate, butoxy vinyl acetate, phenyl vinyl acetate, ethylene glycol acetate, vinyl laurate, vinyl 3-phenylbutyrate, vinyl benzoate, water Vinyl salicylate, vinyl benzoate, vinyl benzoate, vinyl naphthate, and the like. Styrenes such as styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, An alkane such as cyclohexylstyrene, mercaptostyrene, benzyl styrene, methyl styrene chloride, methyl styrene trifluoride, ethoxymethyl styrene, ethoxymethyl methene styrene Styrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene; styrene chloride, styrene dichloride, trichloro Styrene, styrene tetrachloride, styrene pentachloride, phenylethyl bromide-14- 201100954 olefin, styrene dibromide, styrene iodide, fluorinated styrene, styrene trifluoride, 2- Halogenated styrene such as bromo-4-trifluoromethylstyrene or 4-fluoro-3-trifluoromethylstyrene. The ratio of the above-mentioned constituent unit (a 1 ) in the resin (A 1 ) is preferably 5 to 29% by mass, more preferably 1 to 25% by mass. Further, the total ratio of the ratio of the constituent unit (a2) in the (A1) resin to the constituent unit (a3) is 71% by mass or more, and 0 is preferably 71 to 95% by mass, more preferably It is 75 to 90% by mass. The ratio of the constituent unit (a2) is preferably from 10 to 70% by mass, more preferably from 20 to 45% by mass. Further, the ratio of the above-mentioned constituent unit (a3) is preferably 20 to 65 mass%, more preferably 30 to 50 mass%. By setting the ratio of the constituent unit (a3) within the above range, the developability can be made appropriate, and the specific dielectric constant of the cured product can be lowered. Further, the ratio of the above-mentioned constituent unit (a4) in the (A 1 ) resin is preferably from 1 to 15% by mass, more preferably from 3 to 10% by mass. Further, the ratio of the other constituent units in the (A1) resin is preferably 0 to 10% by mass, more preferably 0 to 5% by mass. By setting the ratio of each constituent unit within the above range, the developability of the photosensitive resin composition can be made appropriate, and the shape or the breaking strength of the cured product and the adhesion to the substrate can be improved. (A1) Mass average molecular weight of the resin (Mw: gel permeation chromatography (GPC)), measured by styrene. The same in this specification), preferably from 2000 to 50000, more preferably from 5000 to 30,000. By the above range, the film forming performance of the photosensitive resin composition -15-201100954 tends to be balanced with the development property after exposure. (A1) When the resin has a constituent unit other than the above constituent units (al), (a2), and (a3), the (A 1 ) resin can be produced by a conventional radical polymerization method. In other words, it can be produced by heating and stirring the respective compounds derived from the respective constituent units and a conventional radical polymerization initiator dissolved in a polymerization solvent. Further, when the (A1) resin does not have a constituent unit other than the above constituent units (al), (a2), and (), the general radical polymerization method is such that the carboxyl group of the constituent unit (al) and the constituent unit (a2), The epoxy group of a3) is reacted and gelled. Therefore, in the above case, 'the reaction mixture is prepared by first reacting an unsaturated carboxylic acid with a specific reactive compound (reaction step)', and then the reaction mixture and the epoxy group having no alicyclic group are not The saturated compound and the unsaturated compound containing an alicyclic epoxy group are subjected to copolymerization (polymerization step) to produce a (A1) resin. The refining and washing treatment (refining step) can also be carried out at the end depending on the needs. First, the reaction step is carried out by adding an unsaturated carboxylic acid and at least one compound selected from the group consisting of the compounds represented by the following formulas (1) to (3) (reactive compounds) to a suitable reaction vessel such as a flask. The mixture was heated and stirred to prepare a reaction mixture. R1—〇—R3-0—R2 (1) (wherein R1 and R2 each represent an independent alkyl group having 1 to 4 carbon atoms, and R3 represents a carbon number 1 which may also contain an oxygen atom. 4 linear or branched hydrocarbons-16- 201100954 base)

[Chemical 5 I r\/X/r5 (2) (wherein R4 and R5 each represent an independent alkyl group having 1 to 4 carbon atoms) [Chemical 6]

R6—Ο o r7-° (wherein R6 and R7 each represent an independent alkyl group having 1 to 4 carbon atoms, and R8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) by the above formula (1) a compound such as 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dipropoxyethane, 1,2-dibutoxyethane, two Ethoxymethane, dipropoxymethane, dibutoxymethane, 1,1-dimethoxypropane ' 1,1-diethoxypropane, 1,1-dipropoxypropane, 1,1 -dibutoxypropane, 2,2-dimethoxypropane, 2,2-diethoxypropane, 2,2-dipropoxypropane, 2,2-dibutoxypropane, diethyl Diol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and the like. a compound represented by the above formula (2), for example, 2,5-dimethoxytetrahydrofuran, 2,5-diethoxytetrahydrofuran, 2,5-dipropoxytetrahydrofuran, 2,5-dibutoxy Tetrahydrofuran and the like. a compound represented by the above formula (3), for example, 3,4-dimethoxytoluene, 3,4-diethoxytoluene, 3,4-dipropoxytoluene, 3,4-dibutoxy Toluene, 1,2-dimethoxybenzene, 1,2-diethoxybenzene, 1,2-dipropoxy-17-201100954 benzene, 1,2-dibutoxybenzene, and the like. In such reactive compounds, 'in terms of reactivity with unsaturated decanoic acid, diethoxymethane, 1,2-dimethoxyethane, hydrazine, 2-diethoxy ethoxylate, Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, 2,5-dimethoxytetrahydrofuran, 1,1-diethoxypropane, and 2,2-diethoxypropene are preferred. . These reactive compounds may be used singly or in combination of two or more kinds. The molar ratio of the unsaturated carboxylic acid to the reactive compound is not particularly limited, and is preferably from 1:0.5 to 1:3, more preferably from 1:8 to 1:2. Further, the reaction temperature is preferably 60 to 150 ° C and 80 to 120. (: More preferably. The reaction time is preferably from 10 minutes to 10 hours, preferably from 30 minutes to 5 hours, and the polymerization step is carried out by reacting the reaction mixture obtained in the reaction step with a non-alicyclic ring. The epoxy group-containing unsaturated compound and the alicyclic epoxy group-containing unsaturated compound are dissolved in a conventional radical polymerization initiator and a polymerization solvent, and then heated and stirred to obtain a copolymer. Finally, the purification step is, for example, borrowed. The content of the resin (A 1 ) is preferably 40 to 230% by mass based on the content of the photopolymerizable monomer (B). 'It is more preferably 60 to 22% by mass, and most preferably 70 to 215% by mass. ((A2) Resin) (A2) Resin has at least the above-mentioned constituent unit (a 1 ), the above-mentioned constituent unit (a2), and the aforementioned constitution (a4). The compound in the case of deriving the constituent unit -18-201100954 (a 1 ) and (a2) is a tree of (A 1 ), and therefore the description is omitted. (A2) The resin may have a constituent unit ( Other components other than a2) and (s). For example, the same configuration as the other constituent unit of the (A1) resin is an alicyclic group-containing compound in the case where the constituent unit (a4) is derivatized, and is particularly limited as long as it is an unsaturated compound having an alicyclic epoxy group. An alicyclic group which may be a monocyclic ring or an alicyclic group having more than 0, such as a cyclopentyl group, a cyclohexyl group, etc. In addition, a polycyclic group such as an adamantyl group, a norbornyl group, an isobornyl group, a tricyclic ring. The sulfhydryl group-containing epoxy group-containing unsaturated compound is a compound represented by the following formula (a4_1) to (a4-7). When it is appropriate, it is preferable to use the following formula (a4-3) to (the compound shown is preferably the following formula (a4-3) or (a4-4). The same as the resin (al), the constituent unit Unit. Saturated compound, no ring. Monocyclic alicyclic group, tricyclic ring, for example, etc., a 4 - 8) shown in -19-201100954 [Chem. 7]

(a4-1) (a4-2) (a4-3)

R21

(a4-4) (a4-5)

(a4-6) t

(a4-7)

(a4-8) -20- 201100954 In the above formula, R21 represents a hydrogen atom or a methyl group, a R single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R23 scorpion or a carbon number of 1 to 5 alkyl. R22 is a single bond, a linear chain or a branched group, for example, a methylene group, an ethyl group, a propyl group, a tetramethylene group, a benzyl group, a pentamethylene group or a hexamethylene group. The ratio of the above-mentioned constituent unit (al) in R23 such as a methyl group or an anthracene (A2) resin is preferably 255% by mass, more preferably 5 to 25% by mass. Further, the above-mentioned constituent unit (a2) in the (A2) resin is 71% by mass or more, preferably 71 to 95% by mass, more preferably 90% by mass. Further, the above-mentioned constituent unit (a4) in the (A2) resin is preferably from 1 to 25% by mass, more preferably from 3 to 20% by mass, most preferably from 5% by mass. By making the ratio of the constituent unit (a4) to the above-mentioned range, the developability is appropriate, and the ratio of the cured product can be lowered to the dielectric constant Q. Further, the other constituent sheets in the (A2) resin are 0 to 10 by mass. % is more preferably 0 to 5% by mass. When the ratio of each constituent unit is within the above range, the developability of the resin composition is appropriate, and the strength of the cured product and the adhesion to the substrate can be improved. (A2) The average molecular weight of the resin, preferably 2 00 00 to 00 00, more preferably 5,000 to 30,000 00. By the above range, the film forming ability of the photosensitive resin composition and the tendency to balance after exposure are obtained. 22 series means (representing hydrogenogen: chain-like alkylene ethyl ethyl ketone is preferably used in a ratio of 3 to 75 to a ratio of ~15 by mass, countable. The ratio of the position makes the photosensitive shape or Breaking 50000 is easier to develop - 21 - 201100954 (A2) Resin can be produced by a conventional free radical polymerization method, and each compound derived from each constituent unit, and a conventional polymerization initiator can be used. After being dissolved in a polymerization solvent, the mixture is heated and stirred. The content of the resin (A2) is preferably 40 to 230% by mass, more preferably 60 to 5% by mass based on the content of the photopolymerizable single). , with 70 to 215 mass% best. Further, the component (A) may contain other conventional alkali-soluble resins in addition to the (A1) resin or the (Α2) tree. In this case, it is preferable that the ratio of the specific mass of the constituent unit having an epoxy group is equal to or higher than the constituent unit of the epoxy group. Further, the content of the component (A) is 40% with respect to the solid content of the photosensitive resin. ～85 mass% is more preferably 45 to 75. Further, in the above range, developability can be easily obtained. <Photopolymerizable monomer (B) &gt; Photosensitive resin composition of the present invention The photopolymerization oxime contained in the substance (hereinafter also referred to as "(B) component") is preferably a monomer having an ethyl group. The monomeric functional monomer having a ethylenically unsaturated group and a polyfunctional monomer. Monofunctional monomers such as (meth) acrylamide, hydroxymethyl (acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl) acrylamide 'propoxymethyl ( Methyl) acrylamide, . In other words, the self-made system: the body (B 220 lipid, outside), the composition [J to 5 0 composition of the mass% of the balance: body (B ene is not, is monomethyl) methyl (butoxy-22- 201100954 methoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylate, fumaric acid, Maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-propenylamine-2-methylpropanesulfonic acid, 3-butylacrylamide Sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (A) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2 -(Methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethyl (meth)acrylate Ester, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, phthalic acid The semi-functional (meth) acrylate, etc. These monofunctional monomers may be used alone or in combination of two or more. Q Further, a polyfunctional monomer such as ethylene glycol di(meth)acrylate 'di(methyl) Diethylene glycol acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, Pentaerythritol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropionate tris(methyl)propanoate, di(methyl)propyl citrate Glycerol vinegar, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, tetra(methyl) -23- 201100954 Pentaerythritol Acrylate, Penta(meth)acrylate II Pentaerythritol ester, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl) Propylene decyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloxypropyl (meth) acrylate, ethylene glycol diglycidyl di(meth) acrylate Ester, diethylene glycol diglycidyl ether di(meth) acrylate, diglycidyl phthalate di(meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether Poly(meth)acrylate, urethane (meth) acrylate (ie, methyl phenyl diisocyanate), trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate, etc. _Hydroxyethyl (meth) acrylate reactant, methylene bis(meth) acrylamide, (meth) acrylamide methyl ether, polyol and N-methylol (meth) propylene A polyfunctional monomer such as a condensate of guanamine or a tripropylene acetal or the like. These polyfunctional monomers can be used singly or in combination of two or more kinds. In the monomer having an ethylenically unsaturated group, the "adhesiveness of the photosensitive resin composition to the substrate is improved." The trifunctional or higher polyfunctional monomer is used for the breaking strength of the photosensitive resin composition after curing. More preferably, a polyfunctional monomer having 6 or more functions is more preferable. The content of the component (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, based on the solid content of the photosensitive resin composition. By being within the above range, sensitivity can be easily obtained. The tendency to balance the developability and resolution. &lt;Photopolymerization Initiator (C) &gt; -24- 201100954 The photopolymerization initiator (c) (hereinafter also referred to as "(c) component)) contained in the photosensitive resin composition of the present invention is not particularly As a limitation, a conventional photopolymerization initiator can be used. Specifically, a photopolymerization initiator such as 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4_(2-propenylethoxy) Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-( 4-dodecylphenyl)-2-hydroxy- 2-0 methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-i-ketone, double 4-Dimethylaminophenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2 -Dimethylamino-indole-(4.morpholinylphenyl)-butan-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)- 9H-carbazol-3-yl], 1-(anthracene-ethenyl), 2,4,6-trimethylbenzimidyldiphenyl oxide scale, 4-benzylidene- 4'- Methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzene Butyl formate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-/3-methoxyethylethyl Awakening, benzyldimethyl Fermentation: I-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) hydrazine, methyl benzoyl benzoate, 2,4-diethyl thioxanthone, 2 _Chloroxynone, 2,4-dimethylhydrazine, 1-chloro-4-propoxysalazine, hydrazine, 2-cyanopyrene, 2,4-diethyl thioxanthene , 2-methylthioxanthene, 2_isopropylthioxanthene, 2-ethyloxime' octamethylguanidine, 1,2-benzopyrene, 2,3-diphenylanthracene, occasional Biisobutyronitrile, benzammonium peroxide, cumene peroxide '2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(anthracene-chlorobenzene) 25- 201100954 base)-4,5-bis(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-benzoic benzophenone, p,p'-bisdimethyl Aminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-diphenyl ketone, 3,3-dimethyl-4-methoxy Benzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, phenyl b Ketone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, P -dimethylaminopropiophenone, acetophenone dichloride, acetophenone trichloride, P-tert-butylacetophenone, p-dimethylaminoacetophenone, p-third Butyl trimethyl acetophenone, p-tert 3-butyl acetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone , 2-isopropylthioxanthone, dibenzocycloheptanone, pentyl-4-dimethylaminobenzoate, 9-phenyl acridine, 1, 7-bis-(9-acridine Heptane, 1,5-bis(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, ρ-methoxytriazine, 2,4,6-para (methyl chloride)-s-triazine, 2-methyl-4,6-bis(methyl chloride)-s-triazine, 2-[2-(5-methylfuran-2- Benzene]ethylidene]-4,6-bis(methyl chloride)-s-triazine, 2-[2-(furan-2-yl)ethylidene]-4,6-bis(trichloro) Methyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethylidene]-4,6-bis(methyl chloride)-3 -triazine, 2-(3,4-dimethoxyphenyl)ethylidene]-4,6-bis(methyl chloride)-s-triazine, 2-(4-methoxybenzene Base)-4,6-bis(methyl chloride)-s-triazine, 2-(4-ethoxyphene) Alkenyl)-4,6-bis(methyl chloride)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(methyl chloride)-s- Triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-tri-26-201100954 Chloromethyl-6-(3-bromo-4-methoxy)benzene Dilyl phenyl-s_trisyl, 2,4-bis-trichloromethyl-6-(2-bromo-4(methoxy)styrylphenyl-s-triazine, and the like. Among them, the use of a photopolymerization initiator is preferable in terms of sensitivity. The photopolymerization initiator may be used singly or in combination of two or more kinds, and the content of the cerium (C) component is preferably from 0.5 to 30% by mass, preferably from 1 to 20% by mass based on the solid content of the photosensitive resin composition. % is better. In the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved to suppress the curing failure. Further, in the component (C), a photoinitiator may be combined. Photoinitiating aids such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylamino Isoamyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate 'N,N-dimethyl-p-toluidine, 4,4'-double ( Dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethyloxy oxime, 9,10-diethoxy onion, 2-B Base-9,10-diethoxyanthracene, and the like. These photoinitiating aids may be used singly or in combination of two or more kinds. &lt;Organic solvent (S) &gt; The photosensitive resin composition of the present invention preferably contains an organic solvent (S) (hereinafter also referred to as "(S) component") in order to improve coatability and adjust viscosity. Specifically, an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether-27-201100954, two Glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol single positive (poly)alkane such as propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl (poly)alkylene glycol monoalkyl ether acetates such as ether acetate (PGMEA), propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol Other ethers such as diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; 2-hydroxypropyl Ethyl lactate such as methyl ester or ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxy Butyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate Ester, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoxyacetate, ethyl acetoacetate, ethyl 2-carbonylbutyrate; toluene, xylene, etc. Aromatic hydrocarbons; amides such as N-methylpyrrolidone, hydrazine, hydrazine-dimethylformamide, N,N-dimethylacetamide, and the like. Among these, alkanediol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, -28-201100954, other ethers, alkyl lactates, and the other esters described above are preferably used. The diol monoalkyl ether acetates, the other ethers described above, and the other esters described above are more preferred. These solvents may be used singly or in combination of two or more kinds. The content of the component (S) is not particularly limited, and the concentration which can be applied to the substrate or the like is appropriately set depending on the thickness of the coating. The viscosity of the photosensitive resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and most preferably 20 to 30 cp. Further, the solid content concentration is preferably 5 to 100% by mass 0, more preferably 20 to 50% by mass. &lt;Other components&gt; The photosensitive resin composition of the present invention may contain an additive such as an surfactant, an adhesion improver, a thermal polymerization inhibitor, or an antifoaming agent as needed. Any one of the additives can be used by a person skilled in the art. The surfactant is a compound such as an anion, a cation or a nonionic system, and an adhesion improving agent such as a conventional decane coupling agent, a thermal polymerization inhibitor such as hydroquinone or hydroquinone monoethyl ether, and an antifoaming agent such as a hydrazine. Fluorine compounds and the like. &lt;Preparation method of photosensitive resin composition&gt; The photosensitive resin composition of the present invention can be mixed (dispersed and kneaded) by a mixer such as three roll milling, ball milling, sanding, etc., depending on the It is prepared by filtering with a filter such as a membrane filter of 5 μm. &lt;&lt;Liquid Crystal Panel&gt;&gt; -29-201100954 The liquid crystal panel of the present invention has a spacer formed of a photosensitive resin composition. The point other than the spacer is the same as that of the general liquid crystal panel, and only the method of forming the spacer will be described below. First, on a substrate on which a spacer is formed, a contact copy type coating device or a rotator (rotary coating device) using a roll coater, a reversible coater, a bar coater, or the like, a curtain flow coating In the non-contact type coating apparatus such as a cloth, the photosensitive resin composition of the present invention is applied and dried, and a solvent is removed to form a photosensitive resin layer. Next, the photosensitive resin layer is irradiated with an active energy ray such as ultraviolet ray or excimer laser light through a negative mask to perform partial exposure processing. When exposed, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like can be used to emit ultraviolet light. The amount of exposure may also differ depending on the composition of the photosensitive resin composition, and is preferably, for example, about 50 to 600 mJ/cm2. Then, the photosensitive resin layer after the exposure is developed as a developing solution to form a spacer. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developing solution include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, aqueous ammonia, and a quaternary ammonium salt. Since the photosensitive resin composition of the present invention has moderate developability, development can be appropriately performed. Next, a post-baking treatment is performed on the spacer after development to be heat-hardened. The temperature of the post-baking treatment is preferably 150 to 250 °C. The spacer formed by using the photosensitive resin composition of the present invention has high breaking strength and good shape or adhesion to a substrate. Further, since the specific dielectric constant is low, it is effective when a spacer is formed on the array substrate. -30- 201100954 [Embodiment] The present invention will be described in more detail by way of examples, but the invention is not limited by the embodiments. [Examples] &lt;Examples 1 to 5, Comparative Examples 1 to 3 &gt; Each component shown in the following Table 1 was mixed and dissolved in a solvent to prepare a photosensitive resin composition. [Table 1] (A) (B) (C) (5) Example 1 (A)-l (B)-l (C)-l (C)-2 (S)-1 Γ1001 Γ1001 Γ2.71 n〇i Example 2 (A)-2 (B)-l (C)-l (C)-2 (S)-l Γ1001 _ P.71 『101 [2301 Example 3 (A)-3 (B) )-l (C)-l (C)-2 (S)-l _ "1001 "2.71 "101 『2301 Comparative Example 1 (A)-4 (B)-l (C)-l (C)-2 (S)-l _ _ [2.71 [101 [2301 Comparative Example 2 (8)-5 (B)-l (C)-l (C)-2 (S)-l [1001 Γ2-71 [101 『2301 Example 4 (A)-6 (B)-l (C)-3 (S)-2 riooi "521 Γ4.61 Γ3071 Example 5 (A)-7 (B)-l (C)-3 (S)- 2 [1001 [521 『4.61 Γ3071 Comparative Example 3 (A)-4 (B)-l (C)-3 (S)-2 [1001 [521 F4.61 [3071 -31 - 201100954 in Table 1, each The abbreviations are as follows, and the number in the scratch is the compounding amount (parts by mass). (A) -1: Glycidyl methacrylate: methacrylic acid: 3,4-epoxycyclohexyl methacrylate Methyl ester = 60 : 20 : 20 (mass ratio) resin (mass average molecular weight 1 3 000 ) (A) _2 · · Glycidyl methacrylate: methacrylic acid: 2,3-epoxy methacrylate Cyclopentyl methyl ester = 60 · · 20 : 20 (mass ratio) of resin Amount average molecular weight 1 5000 ) (A) -3: Glycidyl methacrylate: methacrylic acid: tricyclodecyl methacrylate = 72: 18: 1 〇 (mass ratio) of resin (mass average molecular weight 1 4000 (A) -4: Glycidyl methacrylate: 40: 20 (mass ratio) of methacrylic resin (mass average molecular weight 1 5000) (A) -5: Glycidyl methacrylate: methyl Acrylic acid: isobutyl methacrylate = 72: 181 1 〇 (mass ratio) resin (mass average molecular weight 15000) (A) -6: methyl propylene succinic acid propyl acrylate: methacrylic acid: methacrylic acid Cyclodecyl ester = 71: 20: 9 (mass ratio) resin (mass average molecular weight 1 2800 ) (A) -7: methyl propylene succinic acid propyl acrylate · methacrylic acid: methacrylic acid 3,4- Epoxycyclohexylmethyl ester: tricyclodecyl methacrylate = 3 5.5 : 20 : 3 5_5 : 9 (mass ratio) resin (mass average molecular weight 11000) (B) -1: dipentaerythritol hexaacrylate (DPHA) -32- 201100954 (C ) -1 ·· 2-Methyl-1-(4-methylthiophenyl)_2_morpholinylpropan-1-one (IRGACURE, Chiba Special Chemical Co., Ltd. 907") (C) _2: 2 - Methyl-2-dimethylaminomorpholinophenyl)-butanone-1 ("IRGACURE 369" manufactured by Chiba Specialty Chemical Co., Ltd.) (〇)-3: Ethyl ketone, 1-[9-ethyl-6 -(2-Methylbenzylidene)-9H-carbazol-3-yl], 1-(anthracene-ethenyl) (IRGACURE OXE02, manufactured by Chiba Specialty Chemicals Co., Ltd.) 0 (S)-1: PGMEA/diethylene glycol methyl ether/3_methoxypropionic acid methyl ester 42/22/56 (mass ratio) mixed solvent (S) -2: PGMEA/diethylene glycol methyl ether = 50/50 (mass ratio) of the mixed solvent &lt;Evaluation&gt; [Development evaluation] On a 6-inch glass substrate (manufactured by Dow Corning Co., Ltd., 173 7 glass crucible), the coating was prepared by the above respective examples and comparative examples. After the photosensitive resin composition was dried at 100 ° C for 2 minutes, a photosensitive resin layer having a film thickness of 3 -8 &quot; m was obtained. Next, ultraviolet light was selectively irradiated onto the photosensitive resin layer by a negative mask, and a 0.5% aqueous solution of tetramethylammonium hydroxide was used as a developing solution, at 2321. (: Agitated and developed to form a dot pattern. Next, the developability was evaluated by measuring the time until the unexposed portion was completely dissolved (BP: break point). The results are shown in Table 2. [Adhesion evaluation] - 33-201100954 A dot pattern is formed in the same manner as the "developability evaluation" described above. The development time is bPx1 5 based on the above-described breakpoint (BP). Then, it is washed with pure water and the formed pattern is formed. For example, the post-baking treatment was carried out for 1 minute at 1 〇 (rc for 10 minutes, and then post-baking treatment was carried out at 220 ° C for 4 minutes to form a dot pattern. Then, the optimum exposure necessary for the size reproduction of the mask was formed. The amount (EOP) and the exposure amount were 50 m J/cm 2 , and the dot pattern size which can be developed was examined, and the adhesion was evaluated. The results are shown in Table 2. Moreover, "None" in Table 2 means that even after development, even It is a case where the pattern size of 20 μm is still not adhered and the pattern is peeled off. [Shape evaluation] The exposure amount is the aforementioned Ε Ο Ρ 'The dot pattern of the diameter of 1 5 &quot; m is formed in the same manner as the above-mentioned "adhesion evaluation" Then, observe the shape of the pattern with s Ε Μ The results are shown in Table 2. The results are shown in Table 2. 〇: The surface has no rough and good shape. △: The surface has a rough condition. χ: The surface and the side surface have large irregularities. The dissolution residue can be seen. [Specific dielectric constant evaluation] Exposure amount In the same manner as the above-mentioned "adhesive evaluation", a dot pattern having a diameter of 15/m was formed. Then, a dielectric constant measuring device SSM495 (manufactured by SSM Co., Ltd., Japan) was used to measure the film thickness direction of the dot pattern. The specific dielectric constant for vacuum. The results are shown in Table 2. -34- 201100954 [Table 2]

BP adhesion (50 mJ/cm2) Adhesion (EOP) Shape specific dielectric constant Example 1 20-3Osec 9μηη 6 μιη 〇3.9 Example 2 15-25sec 1 1 μπι 7 μηι 〇 4.0 Example 3 15sec 1 5 μηι 7 Μπι Δ 4.1 Comparative Example 1 &lt;10 sec m 8 μηη X 4.2 Comparative Example 2 &lt;10 sec irrr 8 μπι X 4.2 Example 4 15-20 sec 1 5 μηα 7 μηη Δ 7 Example 5 24 sec 9 μηη 6 μηι 〇 Comparative Example 3 &lt;10sec Arrr. None 1 0 μιη X

As is clear from Table 2, a constituent unit derived from an unsaturated compound containing an epoxy group having no alicyclic group, and an unsaturated compound containing an alicyclic epoxy group or an unsaturated compound containing an alicyclic group are used. Each of the examples of the resin of the constituent unit derived has a moderate developability with a breakpoint of 15 to 30 seconds. Further, the dot pattern of 9 to 15 μm can be developed by an exposure amount of 5 〇 mJ/cm 2 , and the adhesion is excellent, and the pattern shape is also good. Further, with respect to Examples 1 to 3, the specific dielectric constant was lower than Comparative Examples 1 and 2. Further, the specific dielectric constants of Examples 4 and 5 were less than or equal to those of Comparative Example 3. On the other hand, in the comparative examples using the resin having no alicyclic group, the breakage point was less than 10 seconds, and the development resistance was deteriorated. Further, the pattern cannot be formed with an exposure amount of 50 mJ/cm 2 and the adhesion is low. Further, when exposed by EOP, the pattern shape was not good, and the case where the shape was poor due to the elution residue in Comparative Example 3 was confirmed. -35-

Claims (1)

201100954 VII. Patent application scope: 1 . A photosensitive resin composition containing a photosensitive resin composition of an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), The alkali-soluble resin (A) is characterized by having a constituent unit (al) derived from an unsaturated carboxylic acid, a constituent unit (a2) derived from an unsaturated compound having an epoxy group having no alicyclic group, and The constituent unit (a3) derived from the unsaturated compound containing an alicyclic epoxy group, and the total ratio of the ratio of the constituent unit (a2) to the constituent unit (a3) is 71% by mass or more. 2. A photosensitive resin composition comprising a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), which is characterized by the alkali-soluble resin (A) is a structural unit (al) derived from an unsaturated carboxylic acid, a constituent unit (a2) derived from an unsaturated compound containing an epoxy group having no alicyclic group, and an alicyclic group The constituent unit (a4)' derived from the unsaturated compound and the ratio of the above-mentioned constituent unit (a2) are 71% by mass or more. 3. The photosensitive resin composition of claim 1, wherein the ratio of the constituent unit (a3) is ～6% by mass. 4. The photosensitive resin composition of claim 2, wherein the ratio of the constituent unit (a4) is 1 to 25% by mass. The photosensitive resin composition according to any one of claims 1 to 4, which is used for forming a spacer for a liquid crystal panel. A liquid crystal panel characterized by having a spacer formed of the photosensitive resin composition according to any one of claims 1 to 5. -37- 201100954 IV. Designated representative map: (1) The designated representative figure of this case is: None (2), the symbol of the representative figure is simple: no 〇 201100954 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none