TW200811599A - Curable composition, cured object, color filter, and liquid-crystal display - Google Patents

Abstract

A curable composition which, when applied by die coating, gives a cured object having excellent evenness in height. The curable composition comprises an ethylenic compound (ingredient A), a photopolymerization initiator (ingredient B), a polymerizable monomer having a high viscosity (ingredient C), and a solvent (ingredient D). The curable composition as a coating fluid has a leveling resistance RL expressed with the viscosity μ of the coating fluid and the solid concentration C thereof (RL=μxC3) of 0.01-0.05 and a sagging resistance (RS=μxC2) of 0.1 or more.

Description

In the present invention, the present invention relates to a curable composition and the like, and more particularly to a color composition suitable for forming a liquid crystal display device or the like.旺 [Prior Art] In recent years, a color ray-receiving sheet for liquid crystal display devices and the like has been developed to develop a high-density color grading sheet for achieving the required performance. The main step of the coating step of the composition (photoresist) is to drop the photoresist in the central portion of the substrate and to coat it by spin coating. However, the size of the substrate used in the manufacture of the liquid crystal panel of the TV center is large, and the use of the photoresist is in the shape of a large pong, and further, there is a limitation on the coating of the spin coater (the ability of the motor) In the meantime, a coating technique using a die coating method has recently been developed, and some of them have been put into practical use (refer to the patent document [Patent Document 1], Japanese Patent Laid-Open Publication No. 2005-266783 (Invention). The problem is that the photosensitive spacer (phot〇 spacer) is used to keep the two substrates at a constant interval in the liquid crystal panel, and if the substrate spacing is not uniform, the display is defective, and the like. The color calender sheet requires a high degree of high uniformity compared with the hardenable composition. However, in the case of coating by the die coating method, the shape of the front end of the die is uneven, or the die is mounted, Uneven flow rate of discharge, 3 (supplement) /96_Q9/96l25G23 200811599

And there is a coated gland: P

The tendency to distribute in the direction of motion? In the width direction of the die and the movement of the die, in the 'die coating method, g A is applied by the influence of gravity; the problem is that the thickness distribution tends to become large. And U, the result 'film of coating film H our research' knows: the film thickness distribution of the coating film, the more beautiful the board, the more significant 'because of the coating on the crucible; damage, for example, as a spacer The present invention has been made to solve the above problems. The purpose of the present invention is to provide a hard (four) composition of a cured product which is excellent in highly uniformity in the coating of the mold coating method. The purpose of the invention is to provide a color filter having such a high degree of uniformity. The other object of the present invention is to provide a color filter excellent in high uniformity. Liquid crystal display device. (Means for Solving the Problem) As a result of intensive studies on the above-mentioned problems, the present inventors have found that the problem can be solved by adjusting the coating liquid of the curable composition according to the following points. That is, according to the present invention, there is provided a curable composition which satisfies the following (a) and (b). (a) using the viscosity (#) of the coating liquid and the solid concentration (c) to indicate that the 312XP/invention specification (supplement)/96-09/96125023 7 200811599 is the RTL:=) leveling resistance value 0.01~. · The scope of 05. (Formula: 1) ' RL is the leveling resistance value, " viscosity of the coating liquid (single mPa.s), C system solid concentration (unit: kg / kg). (b) The lower flow resistance value (RS) is represented by the following formula (2): 0.1 or more. RS=^xC2 (2) (In the formula (2), the RS resistance value of the flow resistance, "the viscosity of the coating liquid (single H) 'c solid concentration (unit: kg/kg).), I is used for The curable composition of the present invention is preferably a coating for coating: a color filter for forming a liquid crystal display device or the like, and a cured product, characterized in that: The hardenable composition is hardened. Further, according to the present invention, there is provided a color filter characterized by comprising the cured product. Further, according to the present invention, there is provided a liquid crystal display device comprising the color filter. VIII. (Effect of the Invention) According to the curable composition of the invention, it is possible to form a cured product excellent in uniformity of twist by coating by a die coating method. [Embodiment] Hereinafter, the best mode for carrying out the invention (hereinafter, the apricot form of the invention) will be described in detail. Further, the present invention is not limited to the following two modifications, and various modifications can be made without departing from the spirit and scope of the invention. 312XP/Invention Manual (Supplement)/96-09/96125023 8 200811599 [1] Leveling resistance value (RL), downflow resistance value (RS) Applicable to the curable composition of the present embodiment, depending on the viscosity of the coating liquid [# (mPa, s)] and the solid concentration [C (kg / kg)], and the value of the leveling resistance value (RL) expressed by the following formula (1) is preferably 0.01 to 〇〇 5 | Dad | Wai, better for the range of 01~0· 045, especially for 〇·〇1~〇·〇4. Scope. RL = μ x C1 (1 ) , and when the coating liquid is a Newtonian fluid, the resistance when the unevenness after coating is leveled is expressed by the following formula (3). Leveling resistance 〇c(3/z)/(167r h1)〇c(3;r /16)x/z xC1 (3) Here, in the above formula, /z : viscosity of the coating liquid, h: wet Coating film thickness, c ·· The solid content concentration of the coating liquid. In the present embodiment, #xC1 is defined as a leveling resistance value (RL) (formula (1)). According to the formula (1), the lower the viscosity (#), the thicker the wet coating film thickness. In other words, the lower the solid content concentration (C), the flattening (smoothing) of the unevenness generated during the die coating application. The smaller the resistance, the better the leveling. Further, the curable composition of the present embodiment is expressed by the following formula (2) according to the viscosity [//(mPa.s)] of the coating liquid and the solid content concentration [c (kg/kg)]. The value of the flow resistance value (RS) is preferably 〇1 or more, more preferably 0.13 or more, and particularly preferably 〇15 or more.

Rs= // xC2 (2) The coating liquid applied to the inclined surface flows, causing uneven streaks or accumulation, and the coating film is partially thickened. This condition is called downflow, and the reason is gravity. . In the case where the coating liquid is a Newtonian fluid, due to gravity 1

Disclosure of the Invention (Repair)/96-09/96125023 Q 200811599 The surface velocity at which the flow is generated is expressed by the following formula (4). Surface speed = (l/2)x(pg/#)xh2 (4) Here, in the above formula (4), //: viscosity of the coating liquid, h··wet coating film thickness, g is gravity Number, p is the density. Therefore, the resistance to the downflow is expressed by the following formula (5). Downstream resistance 〇c2///(pgh2)〇c//Xc2 (5) In the present embodiment, //xC2 is defined as a downflow resistance value (RS) (formula (2)). According to the formula (2), the higher the viscosity, the thinner the wet coating film thickness, in other words, the higher the solid content concentration, the higher the flow force due to the action of gravity, and the more difficult the unevenness of the coating film is. . For the above reasons, the improvement of the leveling property is the opposite of the method of suppressing the downflow, but the viscosity of the coating liquid is adjusted by focusing on the difference between the index values of the respective resistance values and the solid concentration [c(kg/kg)] [ # (mPa.s)] and the solid concentration [C (kg / kg)], both the improvement of the leveling and the suppression of the downflow. 1_2" Below the viscosity (//) _ 丨 々 々 又 又 又 ί ί ί 于 于 于 于 适用 适用 适用 适用 适用 适用 适用 适用 适用 适用 适用 适用 适用 适用 适用 适用 适用 。 。 。 。 。 。 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布In particular, in the die coating method, after the drying (that is, after the final step), the coating film having a thickness of the film is a color filter of the film: in the case where the viscosity of the coating liquid is preferably h5 mPa.s or more, More preferably 2 mPa.s or more 'more preferably 2.5 mPa.s or more. However, the viscosity of the coating liquid is usually 10 mPa^s or less. & usually refers to the coating film "film". Here, the coating film thickness after drying is a film, and the thickness of the film is less than 1.5 //m (hereinafter, it is noted that 312XP/invention specification (supplement)/96-09/96125023 10 200811599 In addition, the thickness of the coating film after drying is a thick film of the thickness of the film. For example, in the case of photosensitive interval~Badyou film, coating mPa · s or more, better Λ q 9 ^ degree' Preferably, the thickness of 3 is more than 3. 2 mpa.s. The thickness of the coating film is thick film, usually here, after the film is thicker, the thickness of the film is 15 lbs. (The following may be referred to as "thick film".) " By setting the viscosity of the coating liquid to the above range from the viscosity, the following advantages are obtained in the die coating method, that is, In the case of the earthenware color filter in the earthworm, even if it is a sputum, it is a guanamine: even if the coating speed is not the same as the coating liquid, it can be lowered (4) because the front end of the lip is not coated. The color filter of the stripe stripe. The so-called coating limit speed means that a stripe-like coating film due to deliquoring is not formed on the fixed coating portion. The upper limit coating speed of uniform coating can be performed. The coating speed is usually 01 m/sec, preferably 0·2 m/sec, more preferably 〇·3 jn/sec. The solid content concentration (C)' of the coating liquid applied to the curable composition of the present embodiment is preferably 2% by weight to 5% by weight, more preferably 10% by weight to 30% by weight, particularly preferably In the range of 15% by weight to 25% by weight, if the solid content concentration (C) of the curable composition is too high, there is a tendency that coating streaks are liable to occur. Further, if the solid content concentration (c) is too low, it exists. The tendency of the viscosity (#) to be lowered is applied to the curable composition of the present embodiment in the range of the viscosity (//) and the solid content concentration (C) of the coating liquid resulting from the die coating method. The leveling resistance value (RL) is in the range of 0·01 to 0.05, and the downflow resistance 312ΧΡ/invention specification (supplement)/96-09/96125023 11 200811599 value (RS) is 〇·1 or more, preferably minus Small solids concentration ((:) to lower the leveling resistance value (RL), on the other hand, increase the viscosity (//) to increase the downstream resistance value (RS). That is, the leveling resistance value (RL) is proportional to the solid concentration ((:) to the third power, so the leveling resistance value (RL) can be greatly reduced by reducing the solid concentration (c). On the other hand, the downstream resistance value (RS) is proportional to the solid concentration ((:) to the second power, so even if the solid concentration (c) becomes smaller, it will not decrease as the leveling resistance value (RL). The decrease in the resistance value (RS) is suppressed by increasing the viscosity (#). Specific examples are shown in Table 1 below. [Table 1] Solid concentration (C) _ (kg/kg) Viscosity (#) -- -»(jnPa · s) 0. 25 -Ll~ 3. 2 0.2 2. h ~ ft 9C; 0. 15 -1ιΛ1^14. 81 Method, for example, the following methods (a) to (〇) can be cited. (a) Use a binder resin of south viscosity. Here, as a high-viscosity binder resin, a weight average molecule can be cited.

The amount (Mw) is preferably 5,000 or more, and the refractory helmet is nnnn, and the L L is more than 1,000,000, and more preferably ι5 〇〇〇 or more. In this case, the acid value is preferably 20 or more, and more preferably 4 or more and 60 or more. As the high-viscosity binder resin, it can be described as (4) ethylene non-312XP/invention specification (supplement)/96-09/96125023 12 200811599 saturated compound, or (8) resin having no ethylenic unsaturated group. More preferably, it is selected from the group consisting of [A-1] a vinyl group-containing resin having an ethylenically unsaturated group in the side chain and (8) a resin having no ethyl group and a group. (b) Using a highly viscous polymerizable monomer. Here, the high-viscosity polymerizable monomer may, for example, be a monomer having a viscosity of preferably 10 mPa·s or more, more preferably 100 mPa·s or more, and still more preferably i mp a s or more. As the polymerizable monomer having a high viscosity, it is preferable that the polymerizable monomer (c) described later has two or more ethylenically unsaturated groups from the viewpoint of polymerizability and crosslinkability. The compound, more preferably a compound having three or more ethylenically unsaturated groups, is selected. Further, by adding a small amount of a polymerizable monomer having a viscosity of more than 1,000,000 mpa.s, the various properties of the curable composition are not changed, and only the method of controlling the viscosity is preferable. (C) Use a solvent with a high viscosity. Here, the solvent having a high viscosity is preferably a solvent having a viscosity of preferably 1 mPa·s or more, more preferably 1 · 2 mPa · S or more, and still more preferably 1 · 5 fflPa · s or more. However, the solvent is not selected only in terms of viscosity, but also in accordance with the balance of various materials such as materials used, solubility, vapor pressure, drying speed, and odor. [3] The constituents and compositions of the curable composition are not particularly limited as long as they are applied to the curable composition of the present embodiment, and the components of the following components (A) to (D) and, if necessary, may be blended as needed. 312XP/Invention Manual (Supplement)/96-09/96125023 13 200811599 Other components ((E) component to (η) component) are obtained. Hereinafter, each component will be described. Knife edge (A) ethylenically unsaturated compound (B) photopolymerization initiator and / or thermal polymerization initiator · (C) polymerizable monomer, (D) solvent other components (E) epoxy compound (F) The amine-based compound (G) surfactant (Η) is a resin which does not have an ethylenically unsaturated group. In the present embodiment, the term "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid". Further, the term "total solid content" means the total amount of components of the curable composition from which the solvent is removed. (A) Ethylene unsaturated compound (Ethylene used in the curable composition of the present embodiment: an unsaturated compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule, The radically polymerizable ethylenically unsaturated bond may be a polymerization initiating system containing a photopolymerization initiator and/or a thermal polymerization initiator described later when the curable composition is irradiated with active light or when heated. The effect is additive polymerization, and cross-linking and hardening occur depending on the situation. In the ethylenically unsaturated compound, the leveling resistance value (RL) or the downflow resistance value (Rs) of the curable composition of the present embodiment satisfies the requirements of the present invention, and the hardening obtained from the curable composition is hardened. The product has the characteristics of 312XP / invention manual (supplement) / 96-09/96125023 14 200811599, which can be appropriately selected from the following. Further, in the case where the cured product obtained from the stone-reforming composition of the present embodiment is used as the photosensitive spacer, the ethylenically unsaturated compound preferably has a double bond equivalent of 4 in order to achieve mechanical properties. 〇〇 The following: an ethylenically unsaturated compound which is preferably 350 or less, more preferably 300 or less. The smaller the double bond equivalent, that is, the more double bonds per unit weight, the greater the elastic recovery rate and recovery rate of the hardened material obtained. The lower limit of the double bond equivalent of the ethylenically unsaturated compound is usually 1 Å or more. Here, the term "double bond equivalent" means that the weight i' of every 1 mole of the double bond of the compound is calculated by the following formula (6), and the more the double bond per unit weight, the smaller the value of the double bond equivalent. Double bond equivalent = weight of compound (g) / mole number of double bond containing compound (6 / Further, in the present embodiment, the smaller the double bond equivalent of the entire curable composition is 'according to the above-mentioned ethylenic unsaturated The reason why the double bond equivalent of the compound is the same is preferable because the elastic recovery rate and the recovery rate of the obtained cured product are larger. Specifically, the curable composition is dissolved or dispersed in a solvent (hereinafter, sometimes The double bond equivalent of the solid portion under the so-called "hardened composition solution" is preferably 300 or less, more preferably 250 or less. However, as a solid bond of the hardenable composition solution, the double bond equivalent is The lower limit is usually 10 or more. Here, the double bond equivalent of the solid content in the hardening composition solution may be an ethylenic double bond according to the above formula (6) according to the formula (6). The amount of the compound is calculated and calculated. 312ΧΡ/Invention Manual (Supplement)/96-09/96125023 15 200811599 The amount of the solid component of the hardenable composition is determined by the method of the method. The hunting is calculated by the following formula (7): double bond equivalent = double bond equivalent of the hardening composition solution X solid concentration 3, ,,, (7), 'described ethylenically unsaturated compound, using the hardening of the present invention Where the substance is an alkali-developing type, it is particularly preferable to have an acid group. Here, //, a fluorenyl group means that the enthalpy determined by giving a drop of Κ0Η (potassium hydroxide) is larger than The term "specifically" means a carboxylate, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, etc., and particularly preferably a carboxyl group. It is suitable for use in the curable composition of the present embodiment (A) The content of the compound of the feminine compound is '25% by weight or more, preferably 3% by weight or more, more preferably 4% by weight or more, based on the total solid content in the curable composition. A) When the content of the ethylenically unsaturated compound is too large, the viscosity of the curable composition solution is too high or the curability is deteriorated, which is not preferable. On the other hand, if the content is too small, the cured product may not be obtained. Sufficient mechanical properties. As the ethylenically unsaturated compound, hydrazine can be used. And a resin having at least one ethylenically unsaturated group in the resin used in the resin composition for a known color filter. Examples of such a resin include (meth)acrylic acid. Copolymer of saturated carboxylic acid and ethylene compound, acid-modified epoxy (mercapto) acrylate, polyamine, polyester, polyether, polyamino phthalate, polyvinyl butyral, polyvinyl alcohol, poly Ethylene hydrogen ratio _, cellulose acetate, etc. 312XP / invention manual (supplement) / 96-09/96125023 16 200811599 In the above, in terms of alkali developability, etc., it is preferably [4_1; A wire-containing vinyl resin having an ethylenically unsaturated group and a [a_2] acid-modified epoxy (meth) acrylate. [A1] A vinyl group-containing resin having a carboxyl group having an ethylenically unsaturated group in the side chain is used as an ethylene group in the present embodiment as used in the present embodiment [A_n has a vinyl group in the side chain The resin may, for example, be a reaction product of an ethyl hydrazine resin having a carboxyl group and an unsaturated compound containing an oxy group, [A-Bu 2] a compound having two or more kinds of unsaturated groups and an unsaturated group. Copolymer or resin of carboxylic acid or unsaturated carboxylic acid ester. [A-:l-1] The reaction product of the carboxyl group-containing vinyl resin and the epoxy group-containing unsaturated compound is the silk-containing vinyl resin used in the present embodiment, and specific examples thereof include an unsaturated carboxylic acid and a copolymer of a vinyl compound. Here, examples of the unsaturated carboxylic acid include (meth)acrylic acid, barley acid, isocrotonic acid, maleic acid, cis-butanoic acid liver, itaconic acid, and citraconic acid. Further, examples of the vinyl compound include styrene, α-methylstyrene, styrene styrene, methyl methacrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , (butyl) (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (methyl Dicyclopentyl acrylate, adamantyl (meth) acrylate, isodecyl (meth) acrylate, hydroxymethyl (meth) acrylate, (meth) acrylate, ethyl acetate, (methyl) propyl Dilute acid propylene 312 ΧΡ / invention specification (supplement) / 96-09/96125023 200811599 ester, (f-) benzyl acrylate, (meth) acrylate N, N dimethyl acetamide, n- (a Base) propylene oxime, (meth) acrylonitrile, (meth) propylamine, hydrazine-f-based (meth) acrylamide, hydrazine, hydrazine monomethyl (meth) propyl Emulsion amine, Ν'Ν-dimethylaminoethyl (meth) acrylamide, vinyl acetate, and the like. Among the ethylenic resins containing a carboxyl group, a (meth)acrylic acid-(meth)acrylic acid copolymer and a styrene-(mercapto)acrylic acid (meth)acrylic acid copolymer are preferred. More preferably, in the (meth) acrylate-(meth)acrylic acid copolymer, a copolymer containing 5 to 80 mol% of (meth) acrylate and 2 〇 to 95 mol% of (meth)acrylic acid. More preferably, it is a copolymer containing 10 to 90 mol% of (meth) acrylate and 10 to 90 mol% of (meth)acrylic acid. Further, in the styrene-(meth)acrylate-(meth)acrylic acid copolymer, it is more preferable to contain 3 to 60 mol% of styrene, 1 〇 to mol% (meth) acrylate, and 10 to 10 A copolymer of 60 mole % (meth)acrylic acid, particularly preferably containing 5 to 50 moles. / styrene, 20 to 60 mole % (meth) acrylate and 15 to 55 mole % (meth) acrylic acid copolymer. Further, the acid value of such a vinyl group-containing resin is adjusted according to the amount of the phosphotium-containing unsaturated compound reacted with the reaction and the acid value necessary for the obtained reaction product. It is usually 5 〇 mg - KOH / g ~ 500 mg - KOH / g. The standard polystyrene-equivalent weight average molecular weight (Mw) of the carboxyl group-containing vinyl resin is preferably 1, 〇〇〇~300, 000 0 and the 'weight average molecular weight (Mw) system, by gel permeation layer Gel Permeation Chromatography (GPC) was measured as the molecular weight of the standard 312XP/invention specification (supplement)/96-09/96125023 18 200811599 quasi-polystyrene baking. Further, as the epoxy group-containing unsaturated compound, τ includes an aliphatic epoxy group-containing unsaturated compound and an alicyclic epoxy group-containing unsaturated compound as the aliphatic epoxy group-containing unsaturated compound. For example, propylene propyl epoxy propyl, (meth)acrylic acid propylene vinegar, (meth)acrylic acid α-ethyl epoxypropyl acrylate, crotonyl butyl acrylate, isocrotonate oxime Ester, barium decyl epoxy propyl ether, itaconic acid monoalkyl ester monoglycidyl ester, fumaric acid monoalkyl ester monoglycidyl ester, maleic acid monoalkyl ester monoepoxypropyl Ester and the like. Further, examples of the unsaturated compound containing an alicyclic epoxy group include 3,4-epoxycyclohexylmethyl (meth)acrylate and 2,3-epoxycyclopentyl (meth)acrylate. Ester, (meth)acrylic acid 7 [5.2.L0] indol-2-yl] oxymethyl vinegar and the like. " The carboxyl group-containing vinyl resin and the epoxy group-containing unsaturated compound are reacted in the following ratio, and a carboxyl group of a carboxyl group-containing vinyl resin of 5 mol% to 9 mol% is preferably used. It is an epoxy group-containing unsaturated compound of about 3 〇 to 7 〇 mol%. Further, the reaction can be carried out by a known method. [A-1 -1 ] The acid value of the reaction product of the ethylenic resin containing a carboxyl group and the unsaturated compound containing an epoxy group is preferably 3 〇 mg-K 〇 H / g 〜 25 〇 mg-KOH / g . Further, the weight average molecular weight (Mw) in terms of standard polystyrene is preferably 1,000 to 300, 〇〇〇. [A-1 -2] Copolymer of a compound having two or more kinds of unsaturated groups and an unsaturated carboxylic acid or an unsaturated carboxylic acid ester 312XP / Invention specification (supplement) / 96-09/96125023 19 200811599 As [Al] The carboxyl group-containing vinyl resin having an ethylenically unsaturated group in the side chain may be a compound having two or more kinds of unsaturated groups and a copolymer with an unsaturated carboxylic acid or an unsaturated carboxylic acid ester. Examples of the compound having two or more kinds of unsaturated groups include: ·(mercapto)acrylic acid allyl ester, (mercapto)acrylic acid 3-allyloxy-2-hydroxypropionate; ester, (meth) Cinnamyl acrylate, crotonyl (meth)acrylate, methylallyl (meth) acrylate, N,N-diallyl (mercapto) acrylamide, vinyl (mercapto) acrylate,丨 chlorovinyl acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, ethyl crotonate, ethenyl (decyl) acrylamide. Examples of the unsaturated ortho-acidic or unsaturated carboxylic acid vinegar include (mercapto)acrylic acid or (fluorenyl)acrylate. The ratio of the compound having two or more kinds of unsaturated groups to the total amount of the copolymer is from 10 mol% to 90 mol%, preferably from about 30 mol% to about 80 mol%. [A-1-2] The acid value of the copolymer of the compound having two or more kinds of unsaturated groups and the unsaturated carboxylic acid or unsaturated carboxylic acid ester is preferably 3 〇 mg - K 〇 H / g 〜 250 mg - KOH / g. Further, the weight average molecular weight (Mw) in terms of standard polystyrene is preferably 1, 〇〇〇 〜 3 〇〇, 〇〇〇. [A-1-3] "E-R-N-T resin" The so-called E-R-N-T resin is 5 mol% to 90 mol. /Q "(E) component: an epoxy group-containing (mercapto) acrylate", and 1 mol% % to 95 mol % "(R) component · other radicals copolymerizable with (E) component The polymerizable compound is copolymerized and added to the epoxy group of 312 ΧΡ/invention specification (supplement)/96-09/96125023 20 200811599 m obtained at 10 mol% to 1 mol%. "(n) component: unsaturated-acidic acid", A upper Λ, "%~1 〇 °% molar addition of the above-mentioned (N) component produced by the addition of (7) component · polybasic anhydride The resin that comes with it. :: The component (8): an epoxy group-containing (meth)acrylic acid vinegar, for example, a cow, a (meth)acrylic acid acrylonitrile, a (meth)acrylic acid 3,4 ringworm η, ( Methyl) propyl benzoic acid (3, 4-epoxycyclohexyl) methyl hydrazine, (M-Ming 酉夂 酉夂 4 red butyl gB & oxypropyl ether, etc. Among them, preferably (meth) propylene, Epoxy _. The #(8) component can be used singly or in combination of two or more kinds in any combination and ratio. The copolymerization ratio of the component (E) of the copolymer (E) and the component (R) is, for example, The above is usually 5 mol% or more, preferably 2 mol% or more, more preferably 30 mol% or more. Further, it is usually 9 mol% or less, preferably 80 mol% or less, and more preferably It is preferably 7 〇 mol% or less. Here, ("component system, other radical polymerizable compound copolymerizable with (E) component. If the right (E) component has too much copolymerization ratio, there is ({^ component Reduce, resist

The tendency to reduce heat or strength. When the copolymerization ratio of the component (E) is too small, the amount of addition of the polymerizable component and the alkali-soluble component tends to be insufficient. On the other hand, the copolymerization ratio of the (R) component in the copolymer of the component (E) and the component (R) is, as described above, 10 mol% or more, preferably 2 mol% or more, more preferably 30% or more. Further, it is usually g5 mol%, preferably 80 mol% or less, more preferably 70 mol% or less. When the copolymerization ratio of the (R) component is too large, the component (E) is decreased, and the amount of addition of the polymerizable component and the insoluble component tends to be insufficient. Further, if the copolymerization ratio of the component 312XP/invention specification (supplement)/96-09/96125023 21 200811599 is too small, there is a tendency that the component (8) is, for example, = two low. ester. a single (meth)acrylic acid of a part of the formula ()

(In the formula (13), ' Rid~R6d ' independently represent a gas atom or a methyl group, an ethyl group: a propyl group such as a propyl group, and R7d and R8d are independently independent. An alkyl group having a carbon number of 1 to 3 such as an ethyl group or a propyl group, and "R" may be bonded to form a ring. The ring formed by the connection with R8d is more than: % is saturated or unsaturated, or saturated or unsaturated. Preferably, the carbon number is 5 to 6. In the above formula (13), a mono(indenyl) acrylate having a structure represented by the following formula (14), formula (15), or formula (16) is preferred. The heat resistance or strength of the mono(indenyl) acrylate can be increased by introducing the partial structures. Further, the mono(indenyl) acrylate can be used alone or in combination. Two or more ratios are used in combination. [Chem. 2] 312XP/Invention Manual (supplement)/96-09/96125023 22 (14) 200811599

(15) (16) As the mono(indenyl) acrylate having a partial structure represented by the above formula (13), various known ones can be used, and those represented by the following formula (17) are particularly preferable. R (17) H2C = Lro - RlOd Ο (In the formula (R), R9d represents a hydrogen atom or a methyl group, and R1Dd represents an upper (13) 〇) In the eighth embodiment, the '(E) component and The content of the mono(meth)acrylate having a partial structure represented by the formula U3) in the copolymer of the component R) is usually 5 mol% or more, preferably 1 mol% or more, more preferably The best is 15% or more. Further, it is usually 9 〇 mol% or less, preferably 莫 312XP/invention specification (supplement)/96-09/96125023 〇3 200811599 ear% or less, more preferably 50% by mole or less. (The content of the mono-xanthene represented by the formula (13) in the copolymer of the two E! bis and (8) components tends to be insufficient, and the heat resistance is insufficient. The right (13) is represented by the single (meth)acrylic acid. When the content of the ester is too large, the compatibility of the components of the composition of the composition of the composition is deteriorated, and whitening or the like at the time of film formation may occur. In the present embodiment, a radical polymerizable compound other than mono(indenyl)glycolate having a partial structure represented by the above formula (13) is exemplified as the oxime component. Specific examples include, for example, styrene, α, o-, m-, p-alkyl, nitro, cyano, decyl, ester derivatives; butadiene, 2, 3, 2 Diene such as methylbutadiene, isoprene, chloroprene; decyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylate Propyl ester, n-butyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, Isoamyl methacrylate, hexyl (methyl) propyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (mercapto) acrylate, (曱Cyclopentyl acrylate, cyclohexyl (decyl) acrylate, 2-mercaptocyclohexyl (decyl) acrylate, dicyclohexyl (decyl) acrylate, isodecyl (decyl) acrylate, (曱Adamantyl acrylate, allyl (mercapto) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, ) naphthyl acrylate, decyl (meth) acrylate, decyl acrylate, decyl acrylate to eugenol, decyl acrylate, furyl acrylate, (a) 312ΧΡ/Invention Manual (supplement)/96-09/96125023 24 200811599 base) decyl acrylate, tetrahydrofurfuryl (meth) acrylate, methyl methacrylate, benzyl (meth) acrylate, Benzyl acrylate, toluene (meth)acrylate, (meth)acrylic acid-1,1,;[-trifluoroethyl ester, (methyl)propionic acid perfluoroacetic acid, (decyl)acrylic acid Fluorinated vinegar, (fluorenyl): perfluoroisopropyl isopropyl acrylate, triphenyl sulfonate (mercapto) acrylate, (fluorenyl); cumene acrylate, 3-(N) , N-dimethylamino) propyl vinegar, 2-ethylidene ethyl (meth) acrylate, (mercapto) acrylic acid - 2-(propyl) acrylate, etc.; (mercapto) acrylamide , (mercapto) propylene N,N-didecyl decylamine, (fluorenyl) propylene N,N-diethyl decylamine, (mercapto) propylene N,N-dipropyl hydrazine , (meth) propylene N,N-isopropyl isopropyl amide, (fluorenyl) propylene decyl amide or the like (mercapto) acrylamide; (meth) acryl anilide, (mercapto) acrylonitrile , acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl hydropyrrolidone, vinyl pyridine, vinyl acetate and other vinyl compounds; #康酸 diethyl, maleic acid II Ethyl ester, diethyl fumarate, itaconic acid monoethyl acrylate monounsaturated dicarboxylic acid diester; N-phenyl cis-butyl diamide: quinone imine, N-cyclohexyl-n-butylene A mono-n-butenylene imine such as an amine, N-lauryl maleimide, N-(4-hydroxyphenyl) maleimide or the like; N-(methyl) acrylonitrile Benzodiazepine and the like. In order to impart more excellent heat resistance and strength, it is effective to use at least one selected from the group consisting of styrene, benzyl (meth) acrylate, and mono-n-butylene diimide as the (R) component. . In this case, the copolymerization ratio of at least one selected from the group consisting of styrene, benzyl (meth) acrylate, and mono-n-butylene diimide is usually 丨 Moer 312XP / invention specification (supplement) / 96 -09/96125023 25 200811599% or more, preferably 3 mol% or more, preferably 50 mol% or less. Further, it is usually 70 mol% or less, and then the component (8) (unsaturated-carboxylic acid) which is added to the copolymer of the component (8) and the component (8) can be known. \乍; Such an unsaturated-acid acid, for example, (meth)acrylic acid, crotonic acid, iso-baric acid, maleic acid, cis-butan 2 ^ ^ 耵衣康齩, 柃An anhydrous carboxylic acid having an ethylenically unsaturated double bond. The 荨(N) component can be used alone. __ t... Tian 9 can be used alone or in combination of two or more types. Further, the component (N) is added to the epoxy group contained in the copolymer obtained by the copolymerization reaction of the component (8) and the component (R). In the copolymer, the amount of the (N) component is added to the ear % of the epoxy group contained in the copolymer, preferably 30 mol% or more, more preferably 50 mol% or more. When the addition ratio of (8) is too small, there is a tendency that the stability is deteriorated with time and the like, and the adverse effect is caused by the residual % oxygen. Further, as a method of adding (8) a copolymer to the copolymer of the component (8) and the component (8), a known method can be employed. Further, the (τ) component (polybasic acid anhydride) is added to the base formed by adding the (N) component to the (E) component and the (R) forming U-material. The polyanhydride is not particularly limited, and a known one can be used. As specific examples thereof, there are listed: succinic anhydride, maleic anhydride, itaconic acid, tetrahydrophthalic acid: fluorenyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and Base:: phthalic anhydride, decyl endomethylene tetrahydrophthalic acid liver 'o-benzene, gas bridge saturated or unsaturated di(tetra) acid 312XP / invention manual (supplement) / 96-09 /96125023 26 200811599 Anhydride; trimellitic anhydride; pyromellitic anhydride, diphenyl ketone tetracarboxylic anhydride, biphenyl tetracarboxylic anhydride, diphenyl ether tetracarboxylic anhydride, hydrazine, 2, 3, 4-butane tetracarboxylate An acid anhydride such as an acid anhydride or the like. These (T) components may be used singly or in combination of two or more kinds in any combination and ratio. The amount of the (T) component to be added is usually 1 〇 mol% of the hydroxyl group formed when the (N) component is added to the copolymer of the component (E) and the component (R), preferably 20 mol% or more, more preferably 30 mol% or more. Further, it is usually 100 mol% or less, preferably 90 mol% or less, more preferably 8 mol% or less. When the amount of addition of the component (T) is too large, the residual film ratio at the time of development tends to decrease. When the amount of addition of the component (T) is too small, the solubility tends to be insufficient. Further, as a method of adding (N) a hydroxyl group addition (T) component formed by the formation of the (E) component and the (R) component to the copolymer of the component (R), a known method can be arbitrarily employed. The EHT resin can be further added to a part of a group formed by the addition of the component (7), and further added with a glycidyl (meth)acrylate or a compound having a condensed unsaturated group, and further . In addition, as the above-mentioned E-R-N-T resin, for example, the resin disclosed in Japanese Laid-Open Patent Publication No. Hei. Further, the average molecular weight of the above ERNT resin is not particularly limited, and is a weight average of 312 XP/invention specification (supplement)/96-09/96125023 0Ί 200811599 by the GPC. Mw), usually 3, 〇〇〇 or more, preferably 5, 〇〇〇 or more, again,

Usually it is 100,000 or less, preferably 50 or less. When the weight average molecular weight (Mw) of the E-R-N-T resin is too small, heat resistance and film strength tend to be inferior. When the weight average molecular weight qjw) of the E-R-N-T resin is too large, the solubility in the developer tends to decrease. Further, the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2·〇~5·0. [A - 2 ] Acid-modified epoxy (fluorenyl) acrylate The acid-modified epoxy (meth) acrylate in the present embodiment may be a compound represented by the following formula (A-I). The method for producing the same may, for example, be a method in which a compound containing an epoxy group is reacted with a carboxylic acid having an ethylenically unsaturated group, and further with a group of a free polycarboxylic acid, an acid anhydride thereof, and a compound having an isocyanate group. The compound selected from the above species is reacted, but is not limited thereto. [Chemical 4]

R 12 CH2-j; FhCH2TM (〇i V〇 (A- I) 13

[In the formula (Ad), a stretching group which may have a substituent or an exoaryl group which may be derived from a group. : represents an ethylidene-rich 1 Rl4 which may have a substituent, and each independently represents an arbitrary substituent. n is an integer of 〇~10. ...the above integer. Any organic group of thiol. ] Eight substituted 312Χρ/Invention manual (supplement)/96-09/96125023 200811599 ~ 通式 General formula =:: is the stretching base of RI1, preferably the carbon number is 1 and more is methylene, stretching Base, propyl, and butyl. Further, the stretching is preferably a carbon number of 6 to 10, and more preferably a stretching base. In the present embodiment, the alkyl group is preferably an alkyl group. a substituent which may have a stretching group or an aryl group, for example, an atom which can be listed, a carbon number of 1 to 15, preferably a carbon number of 10: 2: an alkenyl group having an inverse of 2 to 10' Phenyl, carboxyl, thiolsulfanyl, phosphino, amine, nitro, and the like. Further, η is an integer of 〇~1〇, preferably 〇~5, and more preferably η exceeds the above range, and there is a tendency that when the obtained hardenability or the like is formed: = when the cured product is formed, The image portion is caused to have a film depletion or the like, or the heat resistance is lowered. The carbon number of the (tetra) group containing the ethylenic unsaturated soil of R1 in the formula „), the lower limit is usually 3, preferably 5, more preferably 1 〇. The upper limit is not particularly limited. Preferably, it is 50, more preferably 4, and particularly preferably 35. In the case where the carbon number is too large or the carbon number is too small, the mechanical properties of the cured product formed of the curable composition of the present embodiment are obtained. The carbonoxy group having an ethylenically unsaturated group which may have a substituent represented by R12 is more preferably a group represented by the following formula (Α-Π). 312ΧΡ/Invention Manual (supplement)/96-09/96125023 200811599

[In the formula (Α- Π ), R15, R16, and R17 are combined to think n^^ . ^ ^ The knife is J independently of a gas atom or a methyl group, and Q may not exist or represent an arbitrary two-valent group. Further, in the formula α-π), Q is preferably absent or represents a stretching group having a substituent and/or a aryl group having an substituent and an oxy group. More preferably, Q is absent or represents a stretching group having a number of 1 to 1 Å or a substituent having a substituent of 1 to 10 and a carbonyloxy group. The 2 price base. In the formula (A-I), F is preferably a hydrogen atom, a substituent represented by the formula a), or a substituent represented by the following formula (A_mb). 0 n) 0 (A-DIb) II Η _ q _ each net and 22 [in the formula (eight-111 &), (eight-11113), 1?21, ruler 22 indicates that it may have a substituent 312XP/Inventive Specification (Supplement)/96-09/96125023 30 200811599 An alkyl group, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, a cycloalkenyl group which may have a substituent or may have a substituent Aryl. Here, the alkyl group is preferably a carbon number. Further, as the alkenyl group, a carbon number of 2 to 2 is preferred. Further, as the cycloalkane, it is preferred that the carbon number is from 3 to 20. Further, the cycloalkenyl group is preferably 3 to 20 members. Further, as the aryl group, those having a carbon number of 6 to 2 are preferred. And the substituents which R21 and β may have, and examples thereof include a subgroup, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a carbon number of 2 to 1 phenyl group, a hydroxyl group, a group, and sulfur. The group, the phosphino group, the amine group, the exact group, etc., have a hydroxyl group as a substituent in the group. The compound which is one of the compounds represented by the above formula (Α-Ϊ) is not particularly limited, and examples thereof include the substituents shown below.武(A~IV) [化7] (A-iv) R -gh2-ch-ch2- (orIi) a- ! a ο

I R13 [In the formula (A-IV), R11 and R12 are defined. And n in the above formula (A to ) are the same as those in the compound represented by the above formula (A-I), any of the organic groups of the watch factory and the substituent. , Hai X, has the effect of taking the double 鐽:::: to take the role, in order not to make the double bond of the compound as a whole, the base of your, Q, Q is increased, and has 312XP / invention manual (supplement )/96-09/96125023 200811599 provides a function as a functional group that bonds a moderate molecular weight and a moderate number of substituents. The molecular weight of ruthenium in the compound represented by the formula (A-I) is usually 14 or more, preferably 28 or more, and usually 3,000 or less, preferably 2, 000 or less. In the present embodiment, as the organic group which can be used as the organic group of fluorene, the organic group having a chain or a cyclic organic group = a linear chain, for example, may be exemplified by a hydrocarbon-based or a dilute smoke-based group. Acrylic acid, (fluorenyl) acrylate, (fluorenyl) 1 eye (methyl) acesulfame amide, cis-butane dicarboxylic acid, styrene, acetic acid, ethyl, right, pot, vinylidene chloride, butadiene Separate or copolymer base of di-iminoimide; from acid-modified propylene glycol vinegar, polyolefin, polyamine, ether, polyurethane, polyvinyl butyric acid, polyethylene glycol An organic group such as polyvinylpyrrolidone or cellulose acetate. Lipid 2: is a ring-ring 2: an organic group derived from an alicyclic ring, an aromatic ring, and an organic group derived from the condensed ring, and a person who is bonded by a linking group. The ring w is produced as an alicyclic ring, and examples thereof include a ring (tetra) ring, a cyclohexyl ring, a hexene, and a tricyclodecane ring.环作=香: It can be as follows: benzene ring, biphenyl ring, Caihuan's onion ring, Philippine clothing, Erhe nuclear, extended benzene ring, anthraquinone ring and so on. As an alicyclic heterocyclic or heterocyclic ring, f w wah ring, 1 (four). Fu 0 south nucleus, phenocyclic ring, pyridinium, than saliva ring, ~ ring, heart ring, hetero-ring, taste ring,衣二0坐比环环,口比0定环,塔耕环,素素312ΧΡ/invention specification (supplement)/96 side 612 Jane 32 200811599 pyridine ring, pyridin ring, etc. as a bond of the % organic group The #结结, or a linking group of two or more valences. As a = base group: a direct bond is known, for example, a stretching atom / a linking group, and an S atom, (4) / / an oxygen (tetra) group can be used. Amine, hydrogen atom, sulfhydryl group, thioketo group, 〇, guanamine,

As Sb Bi, Si, B and other metals, any combination of these, etc. The square 裱, the heteroaromatic ring and the organic group represented by X, for example, may preferably be an alkylene group having a carbon number of 2 to 10; a carbon number of 6 2 4 1 to 20, and a carbon number of 2 to 50; Preferably, the carbon number is 2 to 3 Å, and the more the aryl group; the ::A, the double F# double hope; the third; the removal of the acid varnish, etc., the residue of the base of the substance, etc. Alcoholization [Chemical 8] ° 312xw Invention Manual (supplement) /96-〇9/96125〇23 33 200811599

312XP/Invention Manual (supplement)/96-09/96125023 34 200811599 [Chemistry 9]

Further, in the above formula of the organic group represented by X, z represents 0 to 312XP/invention specification (supplement)/96-09/96125023 35 200811599 key. In the above-mentioned exemplary structures, the 'key* is three or more. / the lower one' is the number of the keys of the joint X. At least two of the keys & In this case, examples of the substituent which is bonded to one or more bonds of the remaining and the sigma side may be any substituents, and the ringer is "", and the ring is limited to, and preferably, the above formula ( A-IV). Further, the compound represented by the above formula (Η) has a benzene ring, and the benzene ring may have a (iv) substituent, and for example, an alkyl group having a carbon number of , the carbon number is a 15 alkoxy group, the carbon number is 2 to 'the base: the carbon number is 6 to 14 aryl group, fluorenyl group, the base group, the carbon number is the "burning carbon group, carboxyl group, halogen" Atoms, etc. Among these, a pyridyl group having a carbon number of i to 5, a phenyl group or a halogen atom is more preferred. The method for producing the compound represented by the above formula (U)) is not particularly limited as long as it can obtain a compound having a structure represented by the formula (H), and the following formula (A_v) can be used. The method for producing the epoxy group-containing compound is described as an example. In other words, a compound represented by the following formula (AV) is used as a raw material, and a carbonyloxy group having an ethylenically unsaturated group is formed thereon, and then a compound having an m-oxy group having an ethylenically unsaturated group is formed. The compound represented by the formula (AI) can be produced by reacting one or more compounds selected from the group consisting of a free polycarboxylic acid and a compound thereof and a compound having an isocyanate group. 312XP/Invention Manual (supplement)/96-09/96125023 36 200811599 [化 ίο] q^CH-CHriOiThrO,

(A-V) [In the formula (A-V), R11, X and n are synonymous with the formula (A-J), respectively. R18 is synonymous with R" of the general formula (A-I). Examples of the epoxy group-containing compound represented by the above formula (Av) include (poly)ethylene glycol polyepoxypropyl ether, (poly)propylene glycol polyepoxyether, and (poly)1. , 4-butanediol polyepoxypropyl ether, (poly) fluorene, 5-pentanediol polyepoxypropyl ether, (poly) neopentyl glycol polyepoxypropyl ether, (poly) fluorene, 6 Monohexylene glycol polyepoxypropyl scale, (poly) trimethyl methacrylate polyepoxypropyl bond, ^ oil polyepoxypropyl ether, (poly) sorbitol polyepoxypropyl light, etc. Oxide compound; 2 secret varnish polyepoxide 1 "secret varnish polyepoxidized a, (o, m, p) cresol

¥ ^ ^ ^ , Xiao lacquer poly% milk compound, bisphenol A to the latex compound, double F polyepoxy poly epoxy compound and other aromatic poly dream u character & (匕 basic base) type base shout, different Cyanuric acid triglycol propylene, mountain: private anhydride, propyl isocyanuric acid vinegar, etc. Heterocyclic polyepoxy = earthy (2_monoethyl) The polyepoxide-containing compound represented by the formula U-ν). One type can also be used in combination of two or more types. The compound of the bentonite may be used alone or in the form of ethylene containing the epoxy group-containing compound 312XP/invention specification (supplement)/96-09/96125023 37 200811599 which is represented by the above formula (A~). The lower limit of the number of carbon atoms of the oxy group of the unsaturated group is usually 3, preferably 5, more preferably 1 Å. The upper limit is not particularly limited, and is preferably 5 Å, more preferably 40, and particularly preferably 35. When the carbon number is less than the above range, when the curable composition is made into a cured product, the flexibility is insufficient and the adhesion to the substrate tends to be poor. On the other hand, if the carbon number is too large, the heat resistance tends to decrease. The (tetra) group having an ethylenic acid group is preferably a group represented by the above formula (A- Π ). Here, the carbonyl group having an ethylenically unsaturated group represented by the above formula (A-n) The method for forming the oxy group is not particularly limited as long as it can form a carbonyloxy group containing an ethylenically unsaturated group as a result of the reaction of the compound represented by the above formula (A-v) as a raw material, and examples thereof include, for example, : a compound represented by the above formula (AV), and a vinyl group A method of reacting an unsaturated acid (A-2-a) with an unsaturated group, etc. As the carboxylic acid u_2_a) containing an ethylenically unsaturated group, for example, (meth)acrylic acid, (meth)propyl a reaction product of a dilute acid with an internal vinegar or a polyacetic acid; a saturated or unsaturated dicarboxylic anhydride, a half ester obtained by reacting a (meth) acrylate derivative having more than one hydroxy group in the oxime molecule; An unsaturated dicarboxylic anhydride, a half ester obtained by reacting with an epoxy group-containing compound having an unsaturated group, and the like. As a saturated or unsaturated two, for example, succinic acid liver, adipic acid needle, cis-butadiene bis, itaconic acid liver, tetrahydrophthalic acid field,: tetrahydrophthalic acid Anhydride, hexahydrophthalic acid, methyl hexahydro- ortho-? Anhydride, methyl endomethylenetetrahydrophthalic anhydride, o-phthalene 312XP/invention specification (supplement)/96-09/96125023 38 200811599 Anhydride or the like.乍 is 1 knife tj? has more than one (A, it, for example, 歹im.mi, (methyl) propyl acrylate-derived J + · (meth) hydroxyethyl acrylate, ( Methyl) hydroxy hydroxy hydrazide - 曰 ^ )) butyl acrylate, polyethylene glycol mono (meth) acrylate in 曰 匕 ^ (meth) acrylate, tri-methyl propylene bis (methyl Acrylic, pentaerythritol di(meth)acrylate, pentaerythritol tris(fluorenyl) propylene S-ester, dipentaerythritol penta (meth) acrylate, and the like. Examples of the epoxy group-containing epoxy group-containing compound include (meth)acrylic acid epoxide, (meth)acryl oxime 3,4-epoxycyclohexylmethyl hydrazine, and one ring. W bicyclo[4.3.0]壬_3_yl](meth)acrylic acid 酉 甲 甲 虱 裱 [裱 裱 [4. 3. 0] 壬-3-yl] oxymethyl (meth) acrylate, etc. . In the present embodiment, it is preferably "mercapto)acrylic acid or saturated or unsaturated dicarboxylic anhydride and hydrazine as "the ethyl ketone U-2-a containing an ethylenically unsaturated group". A half ester obtained by reacting a (mercapto) acrylate derivative having more than one hydroxyl group in the molecule. In the case of hydrazine, as the saturated or unsaturated dicarboxylic anhydride, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride or phthalic anhydride is preferred. Further, 'as a (meth)acrylic acid vinegar derivative having one or more warp groups in one molecule, preferably hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or hydroxybutyl (meth)acrylate Ester, pentaerythritol tri(meth) acrylate, pentaerythritol penta (meth) acrylate. These carboxylic acids (A-2a) having an ethylenically unsaturated group may be used alone or in combination of two or more. 312Χρ/发明发明(补件)/96-09/96125023 39 200811599 A carboxylic acid containing an ethylenically unsaturated group (A-2—a), which contains an epoxy group as a raw material with respect to 1 + equivalent The epoxy group of the compound is usually added in an amount of 0.8 chemical equivalents to hr 5 chemical equivalents, preferably 〇9 chemical equivalents to 1:1 chemical equivalents. 2 J乍 is a polycarboxylic acid which is subjected to a reaction in which an epoxy group is represented by the above formula (AV): a raw material is formed thereon to form a hydroxyl group containing an ethylenically unsaturated group. The acid Sf is exemplified by the following compounds. For example, it can be exemplified by: ruthenium, succinic acid, itaconic acid, tetrahydroortylene:: bis = tetrachlorophthalic acid, hexaphthalic phthalic acid, methyl hexa" A saturated or unsaturated dicarboxylic acid such as a methyltetrahydrophthalic acid, a phthalic acid or a chlorinated acid, and an anhydride thereof; a benzoic acid: an acid and an anhydride, a pyromellitic acid, Benzene, tetrakisole, biphenyl anhydride, etc. ', tetracycline, tetracycline, tetraterpenic acid, etc., and the like, as a curable composition, in view of the solubility removal of the test part In other words, it is preferably succinic acid, tetra--formic acid, phthalic acid and the like, and acid field, trimellitic anhydride, pyromellitic acid, biphenyltetracarboxylic acid, tetraacrylic acid and acid thereof. a dianhydride or the like. u'3'4-butadiene tetra(10), etc. Further, among these, an acid dissociation constant is preferred (an acid anhydride of a polydecanoic acid having a first dissociation of 3.5 or more. Acid dissociation... For example, the above-mentioned polyacid-reactive acid liver phthalic anhydride having a number of acid-dissociation numbers of 3.5 or more is exemplified by: succinic acid 312 ΧΡ / invention specification (supplement) / 96- 0 9/96125023 4〇200811599 Anhydride, an anhydride of tetrahydrophthalic acid, an acid anhydride of 1,2,3,4-butanetetracarboxylic acid, of which 'especially succinic acid anhydride, tetrahydroortylene benzene An acid anhydride of dicarboxylic acid. Here, the acid dissociation constant can be referred to the Determination of Organic: Structures by Physical Methods, Academic Press, New • Y〇rk, 1 955 (Brown, H. C., etc.) From the viewpoint of storage stability, it is preferred to use a dicarboxylic acid such as succinic acid, tetrahydrophthalic acid or phthalic acid and an acid anhydride thereof, trimellitic acid and an anhydride thereof. The selection can be appropriately adjusted according to the properties required for the curable composition. In the present embodiment, 'the above polycarboxylic acid and its anhydride may be used singly or in combination of two or more kinds. The acid anhydride is usually added with a chemical equivalent of 1 eq. to the hydroxyl group formed by the addition reaction of the epoxy group-containing compound and the carboxylic acid having an ethylenically unsaturated group. Preferably, it is an amount of ~〇·9 chemical equivalent. In addition, as the compound having an epoxy group-containing compound represented by the above formula (Α-ν), a compound having an isocyanate group which is further reacted after forming a carbonyloxy group having an ethylenically unsaturated group, and the following compounds For example, butyl isocyanate, 3-chlorobenzene isocyanate, % hexyl hexanoate, 3-isopropene indigo-α, α-dimethyl ketone vinegar Etc. organic monoisocyanate, p-phenylene dHS〇Cyanate, 2,4-toluene diisocyanate (2, 4 — t〇lyiene 312XP/invention manual (supplement) )/96-09/96125023 41 200811599 diiS〇^yanate), 2,6-toluene diisocyanate, 4, 4, _diphenylmethane-isocyanate, naphthalene-1,5-diisocyanate, An aromatic diisocyanate such as tolidine diisocyanate; a fat such as hexamethylene diisocyanate or 2,4,4-trimethylhexamethylene diisoxazone monohydrate or isocyanate Group of diisocyanates; isophorone diisocyanate, 4, 4,-methylene bis(cyclohexyl isocyanate), diisocyanate dimethylcyclohexane, etc. Cyanate ester; benzodiazepine acid ester, α,α,α',α,-tetramethylbenzenedimethyl diisocyanate and the like, an aliphatic diisocyanate having an aromatic oxime; an isocyanate triisocyanate, 1,6,1 undecane triisocyanate, hydrazine, 8-diisocyanate 4-isocyanate decyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, di(isocyanate benzene a triisocyanate such as a decane or a tris(isocyanate phenyl) phosphorothioate; a trimer of the above isocyanate compound, a water adduct, and a polyol adduct thereof. Among these, a dimer or a trimer of an organic diisocyanate is preferred, and a trimethylolpropane adduct of a diisocyanate, a dimer of toluene diisocyanate, and a trimer of isophorone diisocyanate are more preferred. Things. The above compounds may be used singly or in combination of two or more. Further, a compound having an isocyanate group is generally added with respect to a hydroxyl group formed in an addition reaction of a compound having an epoxy group and a carboxylic acid having an ethylenically unsaturated group. 〇5 chemical equivalent 〜1· 〇 chemical equivalent, preferably 〇·1 chemical equivalent 〇·5 chemical equivalent amount. Further, the acid value of the compound represented by the above formula (A-I) in the present embodiment is preferably 30 mg-KOH/g to 150 mg-KOH/g, more preferably 4〇312XP/inventive Instruction manual (supplement) / 9 dip 9/96125023 42 200811599 mg-K^H/g~l〇〇mg_K〇H/g. Further, the weight average molecular weight 〇^) in terms of standard polystyrene measured by GPC of the compound represented by the general formula (A-j) is preferably 1,000 to 1,000 00, more preferably 15 Å. 10,000, especially good for 2, 〇〇〇~1〇, 〇〇〇. An example of a specific synthesis method of the compound represented by the formula (H) used in the present embodiment is disclosed in, for example, JP-A-4-355450.

Further, in the present embodiment, the compound represented by the above formula (A-form) thus synthesized may be contained in addition to the influence of the mixture contained in the raw material or the thermal polymerization of the double bond in the reaction. A compound other than the compound represented by the formula (A-j). / N

[A-2] Acid-modified epoxy (fluorenyl) acrylate In the present embodiment, the [A-2] acid-modified epoxy (meth) acrylate is divided by the above formula (A-I). In addition to the compound represented by the formula, for example, a compound represented by the following formula (A-VI) can be added. [化11]

R1 R13 [wherein '^^^ is synonymous with '(6)' respectively. As a method for producing a compound represented by the general formula (A-VI), #, ] / , right is available for 312XP/invention specification ( Supplement) /96-09/96125023 43 200811599 In particular, there is no method for the compound of the structure of the A magical structure, and the method of the compound represented by the above formula (A-" In the same manner, the following production method can be exemplified: a raw material of a diepoxypropyl 2 material is formed thereon, and a carbonyloxy group having a ethylenically unsaturated group is formed thereon, and further, a self-poly-acid and an oleic acid vinegar are formed. The compound of the compound t or the compound of the above-mentioned compound is reacted. 2. In the curable composition of the present embodiment, (1) the woman's sexual remedy may be used alone or as a mixture of two or more. (Β) Photopolymerization initiator and/or thermal polymerization initiator. The photopolymerization initiator used in the form and/or thermal polymerization initiation =, right is the active light of the continent and / or The compound which is thermally unsaturated and is unsaturated is not particularly limited, and a known agent and/or a thermal polymerization initiator may be used. Specific examples of the photopolymerization initiator include 2-(phenyl)-u-bis(trichloromethyl)-trimethylmorphine and 2-p-methoxynaphthalene-mono-(trichloromethyl)- All three, 2-(4-ethoxymethylnaphthyl)_46_"monochloromethyl)-average three-till and other tooth methylated trimorphine derivatives; 2_three gas again = -5-(2'- Benzoindolyl h, 3, 4h, 2_trichloromethylenediamine oxadiazole derivatives; spears, benzoin, benzoin, benzoin, benzoin, and benzoin alkyl ether; - anthracene derivatives such as methyl hydrazine, 2-ethyl hydrazine, 2_third hydrazine, and chloropurine; diphenyl ketone, Michelin:, 312XP / invention specification (supplement) / 96-09/96125023 200811599 4,4-bis(diethylamino)diphenyl ketone, 2-methyldiphenyl ketone, decyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chloro Diphenyl s-iso-derivatives such as diphenyl = ketone and ketodiphenyl ketone; odor-based 2, 2-monodecyloxy-2-phenylacetophenone, 2,2-diethoxybenzene B, hydroxycyclohexyl phenyl ketone, hydroxy-2-methyl phenyl ketone, hydroxy-1-methylethyl - (p- cumene) Ketone, hydroxy-helium to dodecyl phenyl) ketone, 2-pyryl-2-dimethylamino-indole-(4-quinolinylphenyl)-butanone-methyl- Acetophenone derivatives such as [4-(methylthio)phenyl]-2- morpholinyl-bupropion, dichloromethyl-(p-butylphenyl) ketone; thioxanthone, 2-B Thiophenone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthene, 2,4-diiso Propyl thioxanthene, isothioxanthone derivative; phenyl phthalate derivative such as ethyl p-dimethylaminobenzoate or ethyl p-diethyl benzoate; 9-phenyl acridine, 9-(pair) Acridine derivatives such as methoxyphenyl)acridine; morphine derivatives such as 9,10-dimercaptobenzophenone; anthrone derivatives such as benzofluorenone; , dicyclopentadienyl bisphenyltitanium, dicyclopentamethylene bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, dicyclopentadiene meringue, 5, 6-tetrafluorobenzene+yl)titanium, dicyclopentadienyl (2di^-3-(pyrrole-1-yl)-benzene-;[_base) titanium and other titanocene derivatives; Japanese patent Bulletin 2000-80068, special Acetophenone oxime-o-acetate, 1,2-octanedione-1-[4-(phenyl sulphide) disclosed in the publication of Japanese Patent Publication No. 2004-183593 (Japanese Patent Application No. 2004-183593) Base 2 —(o-benzylidene fluorenyl)], 丨-[9-ethyl-6-(2-phenylhydrazinyl)-9-9-carbazole-3-yl] Ethyl ketone-1-(〇-B An oxime ester compound or the like. These may be used alone or in combination of two or more kinds in the 312 ΧΡ/invention specification (supplement)/96-09/96125023 45 200811599. In addition, for example, fine chemistry ((10) Chemicai), 1 gw year March 1 、, ν〇1· 2〇, Ν〇·4, ρ·16~ρ·26, or 曰本专利公开昭59 An initiator disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Further, in addition to the photopolymerization initiators, a hydrogen-donating compound as a polymerization accelerator may be used in combination. As the hydrogen-donating compound, for example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzazole, 3-indolyl 1,2,4-diazole, 2- Mercapto-4(3Η)-quinazoline, valinophthalene, ethylene glycol dithiopropionate, trimethylolpropane trithiopropionate, pentaerythritol tetrathiopropionate, etc. a compound; a polyfunctional thiol compound such as hexanedithiol, trimethylolpropane trithiogluconate or pentaerythritol tetrathiopropionate; hydrazine, hydrazine-dialkylamino benzoate, hydrazine-benzene a derivative such as a glycine acid, an ammonium salt or a sodium salt of stilbene phenylglycine; a derivative such as an ammonium salt or a sodium salt of phenylalanine or phenylalanine; a derivative such as an ester of phenylalanine or the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of the sensitivity of the curable composition, as the suggestive compound, a mercapto group such as 2-mercaptobenzothiazole or 2-mercaptobenzimidazolium 2-sulfenylbenzoxazole is preferred. Heterocyclic compound. Specific examples of the thermal polymerization initiator include azo compounds, organic peroxides, and hydrogen peroxide. These may be used alone or in combination of two or more. As the azo compound, 2, 2, - azobisisobutyl, 2 2, 312 ΧΡ / invention specification (supplement) / 96-09/96125023 46 200811599 azobis(2-mercaptobutyronitrile) ),[,i,-azobis(cyclohexene-ii-carbonitrile), 2,2'-azobis(2,4-didecyl valeronitrile), Bu [(1_cyano) I-mercaptoethyl) azo]carbamamine (2-(aminomethyl azo azo) isobutyronitrile), 2, 2-azobis[2-indolyl-N-[1,1-double (hydroxymethyl)-2-hydroxyethyl]propanamine], 2, 2,-azo: bis[N-(2-propenyl)-2-methylpropionamide], 2,2,- Azobis[N-(2-propenyl)-2-ethylpropanamide], 2, 2,-azobis[N-butyl-2-methylpropanamide], 2,2' - azobis <^-cyclohexyl-2-mercaptopropionamide, 2,2, azobis(dimethyl-2-methylpropionamide), 2, 2, monoazo (dimercapto-indenyl propionate), 2, 2,-azobis(2,4,4-tridecylpentene), and the like. Among them, preferred are 2,2'-azobisisobutyronitrile, 2,2, azobis(2,4-monomethylvaleronitrile) and the like. Examples of the organic peroxide include benzamidine peroxide, peroxymono(tert-butyl), and cumene hydroperoxide. Specifically, it can be as follows::: oxygen:: cumene butyl chlorate, vinegar, peroxynonanoic acid;; (di-U-tert-butylcyclohexyl) vinegar ^, peroxidation Dimethylethyl ester, carbon dioxide peroxide::: 1-cyclohexyldicarbonate di(2-ethylpyryl, decylethyl) ester, peroxynonyl U ethylhexyl), Peroxidation: dimethoxy butyl sulphate, peroxy neodecanoic acid 4 nd hexyl, peroxidized pivalic acid third brewed, peroxidized pivalic acid third; dibutyl vinegar, peroxygen Oxidized di(3,5,5-trimethylhexanide), trans-di-anthracene, dilaurin, peroxydisteal, rhodium: n-octyl, peroxytetramethylbutyrate, peroxidation Ethylhexanide 3ΐ2χΡ/Invention Manual (supplement)/96·09/96125023 nv _ 2,5~Dimethyl-2,5~ 47 200811599 One (over 2, 2-ethylhexyl) hexane, Ester, peroxide II (Buckle A & emulsified 2-ethylhexanoic acid third butyl vinegar, peroxidation - 2 - ethylhexanoic acid peroxide third), emulsification: Ben, bismuth, peroxidic isobutyric acid The third vinegar, (four) three-hearted /5 base) sentence base ring has ^ 卜 _ hexyl) ring appearance,;, Dihexidine, Buji (peroxidized third (4, 4-two (peroxidized second 'di-tributyl) cyclohexane, 2, 2-two-stone mountain Chu- soil) cyclohexyl) propyl, Bismuth peroxide, a "5 2, 5-dicentric, dibutyl, butyl laurate, isopropyl peroxydicarbonate, second π π butyl vinegar, peroxidation 2 monoethylhexyl monomethane - butyl hydrazine, benzoic acid benzoic acid second (benzophenone peroxide) hexane, peroxy; methyl = oxidized first butyl 9 cardinic benzoic acid third vinegar, 4 , 4-di(peryl)benzene, dicumyl peroxide, Xunqi 2 dibutyl isopropanyl 9R, produced by bismuth (third hexyl), 2,5-di 2,5 a (t-butylperoxy) hexane, an upper oxidation of a (second butyl), hydrogen peroxide to peppermint, 2,5-dimethyl dimethyl bis (peroxidized tert-butyl) hexa- 3. Dicumyl peroxide, ','" tetramethylbutyl hydroperoxide, cumene hydroperoxide, tributyl ruthenium peroxide, second butyl dimethyl sulphur Oxide, 2,3-dimethyl-3-diphenylbutane, bis(3_f-benzamide) and Peroxidation A mixture of methacrylate (3-methylbenzhydramidine) and benzoic acid peroxide. Further, it is suitable for use in the curable composition of the present embodiment, (8) Photopolymerization 312XP/Invention Manual (Supplement)/96-09/96125023 48 200811599 Oral initiator and/or thermal polymerization initiator (using 2 kinds) In the above case, the total solid content of the hardening composition is usually q qi weight% or more, preferably 0.1% by weight or more, in the case where it is used together with the polymerization accelerator. More preferably, it is 5% by weight or more. However, it is usually 30% by weight or less, preferably 2% by weight or less. When the content ratio of the photopolymerization initiator and/or the thermal polymerization initiator is too large, the adhesion to the substrate may be lowered. On the other hand, if it is too small, there is a case of hardenability. Further, as the (four) ratio of the (8) photopolymerization initiator and/or the thermal polymerization initiator to the ethylenically unsaturated compound, as (ethylenically unsaturated compound) / (photopolymerization initiator and/or thermal polymerization) The value of the starting agent) (weight ratio) is usually 〇/1)~(1〇〇/1), preferably (2/1)~(50/1). If the blending ratio is out of the above range, the adhesion or the curability may be lowered. (C) The polymerizable monomer mouth is suitable for the concept of the polymerizable early dindolic finger used in the curable composition of the present embodiment as opposed to a so-called high molecular substance, and means a term other than the narrowly defined "monomer". It also includes the "dimer", "trimer", and "oligomer" (hereinafter referred to as "women's monomers"). a sigma species having at least one ethylidene unsaturated group. Specific examples of the compound having an ethylenically unsaturated group in the molecule include, for example, (meth)acrylic acid, alkyl (meth)acrylic acid ester, (iv) nitrile, styrene, and i-ethylation. A monoester of a carboxylic acid and an unsaturated monohydric alcohol of an unsaturated bond. In the present embodiment, it is preferred to use a polyfunctional ethylenic monomer having two or more 312XP/inventive instructions (supplement)/96-09/96125023 49 200811599 olefinic unsaturated group in one molecule. Examples of the polyfunctional ethylenic steroid include, for example, an aliphatic poly-based compound and an unsaturated mono- oxime aromatic hydroxy compound and an unsaturated carboxylic acid ester; by an aliphatic poly-based compound, aromatic A vinegar obtained by a valence reaction of a polyvalent group-based compound such as a polybasic compound with an unsaturated acid and a polybasic acid. • Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include diol diol diacrylate, triethylene glycol diacrylate, trimethyl methacrylate, pentaerythritol triacrylate, and pentaerythritol tetrapropene. Acrylic acid of an aliphatic polyhydroxy compound such as pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, or the like, and the acrylate of the exemplified compounds is replaced by a methacrylic acid sulfonate group. Acrylate; likewise replaces the itaconate of the itaconate; replaces the crotonate of balsam vinegar; replaces the maleic acid succinate with maleic acid ester, and the like. As an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, for example, p-phenylene phenol diacrylate, hydroquinone dimercapto acrylate, benzoyl acrylate, resorcin Acrylates and methacrylates of aromatic polyhydroxy compounds such as dimercapto acrylate and pyrogallol triacrylate. The ester obtained by the esterification reaction of a polyvalent hydroxy compound with a polyvalent carboxylic acid and an unsaturated carboxylic acid is not necessarily a single substance, and examples of the representative specific examples include acrylic acid, o-p-dicarboxylic acid and ethylene. Alcohol condensate, condensate of C, acid, maleic acid and diethylene glycol, methacrylic acid, condensate of nitric acid and pentaerythritol, acrylic acid, adipic acid, dibutyl 312XP / invention Instruction manual (supplement)/96·09/96125023 50 200811599 A condensate of alcohol and glycerin, etc. Further, as an example of the polyfunctional ethylenic monomer, for example, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate or polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate are useful. (meth)acrylic acid amine-based f-ester; propylene phthalamide such as ethyl bis acrylamide; allyl ester such as diallyl phthalate; monoethyl phthalate A compound containing a vinyl group or the like. The content of the (c) polymerizable monomer to be used in the curable composition of the present embodiment is usually less than 8% by weight, preferably less than 70% by weight, based on the total solid content, preferably 1% by weight or more. When the content of the polymerizable monomer is out of the above range, it is difficult to obtain an image having a good pattern. Further, the ratio of (C) polymerizable monomer to (A) ethylenically unsaturated compound, (ethylenically unsaturated compound) / (polymerizable monomer) (weight ratio) is usually (10) ) (1/10), preferably (5/1) to (1/5). The polymerizable monomer to be used in the curable composition of the present embodiment will be described in further detail. Examples of the compound having one ethylenically unsaturated bond in the molecule include unsaturated carboxylic acids such as (meth)acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, and citraconic acid. Its alkyl ester, (mercapto) two women's moon month '(meth) acrylamide, styrene and the like. Further, as a compound having two or more ethylenically unsaturated bonds in the molecule, for example, (a) an ester of an unsaturated carboxylic acid and a polyhydroxy compound (hereinafter, sometimes referred to as "vinegar (meth) acrylate) ()) Phosphate containing (meth) propylene oxime, (c) hydroxy (meth) acrylate compound and polyisocyanate. 312XP/Invention Manual (Supplement)/96-09/96125023 51 200811599 (b) An epoxy (meth) acrylate of a compound (meth) acrylate, (d) a (meth)acrylic acid or a (f-) hydroxy acrylate compound, and a polyepoxy compound. These may be used alone or in combination of two or more. Among them, in terms of polymerizability, crosslinking, and expansion, it is preferable to have two or more ethylenically unsaturated bonds in the molecule in terms of the difference in solubility of the developing solution and the non-exposed portion. The compound, in addition, is preferably an acrylate compound derived from a (meth) propylene oxime group whose unsaturated bond is derived. Examples of the (a) ester (meth) acrylate include an unsaturated carboxylic acid, ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, and polypropylene glycol (addition number 2 to 14) ), 1,3-propanediol, iota, butanediol, 1,6-hexanediol, trihydrocarbylpropane, glycerin, pentaerythritol, dipentaerythritol, and their ethylene oxide adducts, epoxy A reactant of an aliphatic polyhydroxy compound such as a propane adduct, diethanolamine or diethanolamine. More specifically, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(decyl)acrylate, propylene glycol bis(indenyl)acrylate, dihydroxydecylpropane di(methyl) Acrylate, trihydroxymercaptopropane tris(decyl) acrylate, dimethylolpropane ethylene oxide addition tris(meth) acrylate, glycerol di(meth) acrylate, glycerol Acrylate, glycerol, oxypropylene, tris(decyl) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tris(decyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol曱 )) acrylate, dipentaquat 312XP / invention manual (supplement) / 96-09/96125023 52 200811599 Alcohol hexa(methyl) acrylate acid t rong Wen 曰 曰, and the same crotonate, different Crotonic acid s hydrazine, maleic acid ester, itaconate acid ester, citraconate, and the like. Examples of (4) & (meth) acrylates include unsaturated carboxylic acids, aromatic polyhydroxy compounds such as diphenol, m-diphenol, pyrogallol, bisphenol F, and bisphenol A, and hydrazine. The reaction product of the lactine ethane adduct of β 7 a A攸4. 雔,=言, for example, a: A: (meth)acrylic acid vinegar, double hope A double [oxyethylene (Methyl) propyl vinegar vinegar], double bismuth [epoxy propyl ether (methyl) acrylate], etc.; such as ruthy, such as isoindole uric acid tris (2-hydroxyethyl) ester a reaction product of a heterocyclic polycarbophilic compound such as di(meth)propene (tetra), tris(methyl)(tetra) acid, age (four), and diuritic acid di(2-Methyl); a condensate of acrylic acid with phthalic acid and ethylene glycol, a base of acrylic acid and maleic acid, and a bismuth-sodium sulphate, (mercapto) decanoic acid and terephthalic acid and The wall of pentaerythritol is I, the (meth)acrylic acid, the acid and the butyl, the δ?* and the glycerin are shortened. The sputum, the unsaturated carboxylic acid and the polyacid And a reactant of a polyhydroxy compound. The (b) is a phosphate ester containing a (meth) acryloxy group, and is not particularly limited as long as it contains a propyl acetoacetate compound, and is represented by the following formula (la) to ( Ic) Representation.乂 [Chem. 12] 312XP/Invention Manual (supplement)/96-09/96125023 53 200811599 H2C: ^10 〇

°^CH2^〇--S 十 OH 3-q (la) R10 C H2C—C—Ci 〇jcH2-CH2—--p-^-i-P 十 OH丨(4) (lb) >10 H2C=c —Ci 0^GH2^GH2-〇^〇C(«〇)CH2CH2CH2CH2CH2^—j 十 OH ) (Ic) (Formula (^, (...^(^^, “ represents a hydrogen atom or a sulfhydryl group, P, P' It is an integer of 1 to 25, and q is 2, or 3.) Here, p and p are M0, and particularly preferably 4. As a specific example of such a compound, for example, (meth)acrylic acid oxime Oxyethyl phosphate, bis[(indenyl) propylene Itoxyethyl] linoleic acid, (meth) propylene methoxy ethoxy sulphate S, etc., these can be used separately, It can be used as a mixture. (C) The (mercapto) acrylamide phthalate may, for example, be a reaction product of a (hydroxy) hydroxy acrylate compound and a polyisocyanate compound. Illustrative examples include: (comparable to propylene), acetonitrile, acetoacetate, acetoacetate, bis(indenyl) acrylate, etc. Further, as the polyisocyanate compound, for example, 1 6 — 六亚曱基Isocyanic acid vinegar, 1,8-diisocyanate-4-isocyanate thiol octyl sulphate and other moon-shaped fat poly-glycolic acid g, j Chen has burned ^ an isogas acid g, two 曱 base net two different Cool acid, 4,4-Azain bis(cyclohexyl isocyanate), Isophorone diiso 312xp/Invention Manual (supplement)/96-09/96125023 54 200811599 酉曰 环 环 烧 二 diisocyanate An alicyclic polyisocyanate; an aromatic polyisocyanate such as 4, 4-diphenyldecane diisocyanate or tris(isocyanate phenyl) phosphorothioate; or a polyisocyanate compound such as a heterocyclic polyisocyanate such as isocyanurate. (C) The (mercapto)acrylic acid urethane preferably has 4 or more (preferably 6 or more, more preferably 8 or more) amino citrate bonds in one molecule [-NH- C0-〇-], and 4 or more (preferably 6 or more, more preferably 8 or more) (mercapto) acryloxy compounds. The compound can be, for example, made by the following (I) The compound is obtained by reacting the compound of the following (1). (i) A compound having four or more isocyanate groups in one molecule, for example, pentaerythritol, polyglycol a compound having four or more mesogenic groups in an anthracene molecule such as oil, and anthracene, 6-hexamethylene diisocyanate, trimethyl 1,6 /, methylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, etc. A compound (丨-1) obtained by reacting a diisocyanate compound, a compound having two or more hydroxyl groups in one molecule such as ethylene glycol, and "Duranate 24A-丨〇〇" manufactured by Asahi Kasei Kogyo Co., Ltd., and Duranate 22A-75PX , "Duranate21s-75E", "DuranatelSH-70B" and other biuret type, "DuranateP-301-75E", "DuranateE-4〇2-9〇τ", "DuranateE-405-80Τ" and other adducts A compound (i-2) obtained by reacting a compound having three or more isocyanate groups in an isomer molecule, and a compound (i-3) obtained by polymerizing or copolymerizing ethyl isocyanate (meth)acrylate or the like. 312XP/Inventive Manual (Repair)/96-09/96125023 55 200811599 As such a compound, it can be used in the chemical industry manufactured by Shisei Co., Ltd.) = Sub-I has more than one base and 2 Examples of the above (?) propylene include pentaerythritol di(methyl) propylene vinegar, dipentaerythritol tris(meth) acrylate vinegar, dipentaerythritol tetrakis(methyl) propyl acetonate, dipentaerythritol pentoxide (methyl) A compound having one or more hydroxyl groups and two or more, preferably three or more (fluorenyl) acryloxy groups in one molecule such as an acrylate. Here, the molecular weight of the compound (i) is preferably 500 to 200,000, as a weight average molecular weight (Mw) in terms of standard polystyrene measured by gel chromatography (GPC method). Good for 〗, 〇〇〇 ~ 150,000. Further, as the standard polystyrene of (meth)acrylic acid urethane, the weight average molecular weight (Mw) is preferably 600 to 150, 〇〇〇. Further, such an amino acid methacrylate may be produced, for example, by subjecting the compound of the above (i) to the compound of the above (jj) in an organic solvent such as toluene or ethyl acetate. , react at l ° ° C ~ 150 ° C for 5 minutes ~ 3 hours or so. In this case, it is preferred to set the molar ratio of the former isocyanate group to the hydroxyl group of the latter to a ratio of (1/10) to (10/1), and a catalyst such as n-butyltin dilaurate is used as needed. In the present embodiment, the (mercapto)acrylic acid urethane is preferably used in the following formula (?). [Chem. 13]

(π) 312XP/Invention Manual (supplement)/96-09/96125023 56 200811599

Soil [In the formula (π), Ra represents a repeating structure having an extended alkoxy group or an extended aryloxy group, and has 4 to 20 groups which are bondable to Rb. The ribs and Rc, each independently represent an alkyl group having a carbon number, such as an organic residue having a (meth) propylene fluorenyloxy group. Ra, Rb, Rc & RdM have a substituent. X is an integer of 4 to 20, and 7 is an integer of 〇 15 to an integer of -15. Here, 'the repeating structure of the alkylene oxide in the formula (1) is exemplified by (iv) glycerin, glycerin, pentaerythritol, and the like. Further, examples of the repeating structure of the stretching group of 1 Ra include those derived from 1,3, 5-benzenetriol, etc. 1. The carbon number of the alkyl group of 'Rb and RC is preferably respectively The (meth) propylene oxime group in the independent Rd is preferably a ruthenium: 〜5. 〜15, y is 1 to 1 〇, 2 is 1 to 1 〇. The soil horse X is 4, and further, as Ra, It is preferably the following formula [again, an integer of 1 。.] Further, as such and preferably, it is preferably a methylene group, a monomethyldiindenylene group or a triadenylene group. The independent second is preferably the following formula. As Rd, [Chem. 14] 312XP / invention specification (supplement) / 96-09/96125023 57 200811599 fH2. GHf^GH^OQ 93⁄4

R<i r-ChCHa卞CHi_0-CH2—p-CHa_0-Q H 93⁄4 ? 9

Q o -O-CftrCH^CHjrCh^g (wherein Q is ϋΗ^%) As the above (d) epoxy (meth) acrylate, (meth) propionate or hydroxy (meth) acrylate may be mentioned. a compound, a reactant with a polyepoxide. Examples of the polyepoxy compound include (poly)ethylene glycol polyepoxypropyl ether, (poly)propylene glycol polyepoxypropyl ether, (poly)pyrene, and 4-butanediol. Poly", 5-pentanediol polyepoxypropyl (IV), (poly) neopentadiene I epoxypropyl _, (poly) 1,6-hexanediol polyepoxypropyl _, (poly: propyl propylene Polyepoxypropyl scale, (poly)glycerol polyepoxypropyl scale polyvinyl alcohol polyepoxypropyl ether and other aliphatic polyepoxidized human Α) Hawthorn benzoquinone (four) varnish polyepoxide, benzene (four) take 3 Two pairs of 'pairs' ga _ varnish polyepoxide bismuth α 4 oxygen compound, bispan F polyepoxy compound and other aromatic wide and private a; sorbitan polyepoxypropyl ether, Li, Λ 虱Combination of oxypropyl three (2-p-cyanide cyanide, rat dioxin, hexa-cyclohexane, etc.) quot; uric acid heterocyclic polyepoxide 312 ΧΡ / invention manual (supplement /9W)9/96125〇23 58 200811599 _ 2 is a (meth)acrylic acid or a (hydroxy) hydroxy acrylate compound, and an epoxy (fluorenyl) acrylate of a poly-oxygen compound, such as these Gather An epoxidized a substance, a reaction product with the above (meth)acrylic acid or the above-mentioned (meth)acrylic acid hydroxyester compound, etc. As another ethylenically unsaturated compound, for example, ethyl bis-indenyl acrylonitrile is exemplified. a compound containing a vinyl group such as a (meth) acrylamide such as an amine, a diallyl phthalate, an allyl ester or a divinyl phthalate; and a phosphorus-containing compound such as phosphorus a compound containing a thioether bond which is sulfided by an ether bond of a scaly ethylenically unsaturated compound to form a thioether bond, and which has a crosslinking rate, and a decane coupling agent containing an isocyanate group or a fluorenyl group, for example, A polyfunctional (fluorenyl) acrylate compound disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 9-100111, and a bismuth sol having a particle diameter of 5 to 30 nm [for example, an isopropanol-dispersed organic cerium sol. ("IPA-ST" manufactured by Seiko Chemical Co., Ltd.), methyl ethyl ketone dispersed organic sol ("MEK-ST" manufactured by Seiko Chemical Co., Ltd.), and methyl isobutyl ketone dispersed organic oxime Sol (day a compound ("MIBK-ST") manufactured by Chemicals Co., Ltd.) (the ethylenically unsaturated compound is reacted with a ruthenium sol by a decane coupling agent to bond" to enhance the strength or heat resistance of the cured product. Sex compound). In the present embodiment, from the viewpoint of the mechanical strength of the cured product, (a) vinegar (meth) acrylate, (b) phosphate containing (meth) propylene decyloxy group, or ( c) (meth)acrylic acid urethane, more preferably (a) ester (meth) acrylate. 312XP/Invention Manual (Supplement)/96-09/96125023 59 200811599 Also, among (a) ester (meth) acrylate, polyethylene oxide, polypropylene glycol, bisphenol A polyepoxy is particularly preferred. A polyoxyalkylene group such as an ethane adduct or an ester (mercapto) acrylate containing two or more (meth) acryloxy groups. (D) Solvent The solvent used in the curable composition of the present embodiment is not particularly limited. Specific examples thereof include water, diisopropyl ether, mineral oil, n-pentyl alcohol, pentyl ketone, octoate vinegar, n-hexyl alcohol, diethyl ether, isoprene, ethyl isobutyl ether, and butyl stearate. N-octane, Vars〇1 # 2, Apco# 18 Solvent, diisobutylene, amyl acetate, butyl butyrate, Apc 〇 thinner (Apco thinner), dibutyl ether, diisobutyl ketone, decyl cyclohexene , mercapto ketone, propionic acid, twelve burning,

Socal solvent No. 1 and No. 2, amyl citrate, dihexyl ether, diisopropyl ketone, Sol vesso # 150, acetic acid (positive, second, third) butyl ester, hexene, She 11 TS28 Solvent , chlorobutane, ethyl amyl ketone, ethyl benzoate, chloropentane, ethylene glycol diethyl ether, ethyl orthophthalate, decyl decyl ketone, decyl butyl ketone, methyl hexyl Ketone, methyl isobutyrate, benzoquinone, ethyl propionate, mercapto cellosolve acetate, mercaptoisoamyl ketone, methyl isobutyl ketone, acetonitrile acetate, acetic acid Amyl decanoate, cyclohexyl acetate, bicyclohexane, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether acetate (viscosity 3 · 1 mPa · sec, 25 ° C), diethylene glycol monobutyl ether (viscosity 4 · 9 mPa-sec, 25 ° C), dipentene, decyloxymethylpentanol, decyl amyl ketone, mercapto isopropyl ketone , propyl propionate, propylene glycol tert-butyl, methyl ethyl ketone, thiol cellosolve, ethyl cellosolve, ethyl cellosolve acetate 60 312XP / invention manual (supplement) / 96-09 / 96125023 200811599 Ester, carbitol, cyclohexanone, acetic acid , propylene glycol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether (viscosity 1. 7 mPa. sec, 25 ° C), propylene glycol monomethyl ether acetate vinegar (viscosity 1 · 1 mPa · sec, 25 ° C), propylene glycol monolithic, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate g, dipropylene glycol monomethyl ether acetate vinegar, 3-methoxypropionic acid, 3 - ethoxypropionic acid, ethyl 3-ethoxypropionate (viscosity 1 · 2 mPa. sec, 25 ° C), methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethyl ether dimethyl ether (viscosity 0.98 mPa · sec, 25 ° C), diethyl carbitol (viscosity 1. 4 mPa) .sec, 25 ° C), diethylene glycol methyl ether (viscosity 1 · 2 mPa-sec, 20 ° C), dipropylene glycol monoterpene ether, ethylene glycol acetate, methyl carbitol (viscosity 3 · 5 mPa.sec, 25 ° C), ethyl carbitol (viscosity 3 · 9 mPa · sec, 25 C), butyl carbitol (viscosity 4.9 mPa · sec, 25 ° C), ethylene glycol monobutyl Ether, propylene glycol tert-butyl ether, 3-decyloxybutanol (viscosity 2.9 mP a · sec, 25 ° C), 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-mercapto-3-methoxybutyl acetate, 3-methoxybutyl acetate ( A solvent such as a viscosity of 1·2 mPa.sec or 25° C.). The solvent is not particularly limited as long as it can dissolve or disperse the respective components, and is appropriately selected depending on the method of using the curable composition. Among them, a solvent having a boiling point in the range of 60 ° C to 280 ° C is preferably selected. More preferably, it has a boiling point of 7 〇 ° c to 260 ° C. These solvents may be used singly or in combination. The solvent is usually used in an amount of 2% by weight or more and 5% by weight or less based on the ratio of the total solid content in the curable composition of the present embodiment. 31ZXP/Invention Manual (Supplement)/96-09/96125023 61 200811599 In the curable composition applicable to the present embodiment, an eight-component ((E) epoxy compound, (F) amine compound, (G) Interface activity Μ) The following 'describes other components. (Ε) Epoxy compound As the oxime compound, a repeating unit constituting an epoxy resin = a polyepoxypropyl etherified product obtained by reacting a hydroxy group compound with epichlorohydrin; a polycarboxylic acid compound A polyglycidyl ester compound obtained by reacting with epichlorohydrin, a polyepoxypropylamine compound obtained by reacting a polyamine compound with epichlorohydrin, or a compound derived from a low molecular weight substance to a high molecular weight substance. Examples of the polyepoxypropyl ether compound include a diepoxypropyl ether type epoxy resin of polyethylene glycol; a diepoxypropyl type test of bis(4-phenylphenyl) = , · ' Di-glycidyl propyl ether of bis(3,5-dimethylhydroxyphenyl) bis-epoxypropyl ether type ring; di-epoxypropyl group, ox oxygen, four Di-epoxypropyl ether type epoxy of bisphenolphthalein; cycloglycol addition and double-anti-epoxypropyl_epoxy; (4) double-disc 2' shouting epoxy; benzene (tetra) acid varnish Epoxy; a smear-type varnish-type cyclic polyepoxypropyl compound, which can be introduced into a carboxyl group by reacting a residual radical with an acid anhydride or a few hydrazine compounds. A: The 3 epoxypropyl ester compound, for example, may be exemplified by: a oxime propyl epoxide type hexahydro phthalate; the phthalic acid bis is a polyepoxypropylamine compound For example, it may be a di-epoxypropylamine type epoxy of pentylene or decane; an iso-tri-epoxypropylamine type epoxy or the like. Λ * The content of the second compound as the epoxy compound is usually 4〇312ΧΡ/inventive^ relative to the total solid content; the book (supplement)/96-09/96125023 62 200811599 wt% or less, preferably 30 In the case where the material has a stability t of the hardenable composition, (7) the amine compound is "successful", and is applied to the viewpoint of heat shrinkage in the hard process of the present embodiment. Inhibition of thermal hardening by adding an amine-based compound, and it is preferable to contain an amine-based compound. The degree of change is high. The thermal hardening is promoted, and the higher the temperature of the thermosetting is the content of the amine-based compound, preferably 30% by weight. In addition, it is usually: ί以上以上,车家佳为一重哥% ·Room%% The right content is too large, the storage stability of the hardenable composition is bad & = Recording = the heat in the heat hardening The anti-shrinkage-inhibiting effect is low. Examples of the amino-based compound include a hydroxymethyl group having at least two dichroyl groups, a ruthenium glycoside, and a ruthenium as an alcohol-reducing group having a carbon number of 1 to 8.汝βΜ Alkyl compound of alkoxymethyl group. & The eight-body and D' can be exemplified by: melamine-polyamine resin, condensing benzotrimerol with a plate; condensing (10)w "a 5" with a glycoluril resin; Formaldehyde polyurea resin; make melamine, benzene melamine, glycoluril, gourd count? A resin which is subjected to a copolymerization condensation of an alcohol, or a modified resin obtained by changing the hydroxyl group of the resin, or the like. 1 kind, or. f J used alone for the second time, preferably melamine resin and its modified resin, more preferably the modified resin with a ratio of 7 (10) or more, especially the 312XIV rewrite specification (supplement) / 96 Jue 9612 Lake 63 200811599 Modified resin. "1" is a specific example of an amine-based compound, and the melamine resin and its modification are, for example, "Cymel" (registered trademark) manufactured by Mitsui Cytec Co., Ltd. 3, 3, Π, 3, 3, 35〇, 736, (10), 37〇, 771, 325, 327, 703, 701, 266, 267, 285, 232, 238, 1141, 2?2, 254, 202, 1156, 1158; Sanwa-Chemical Co., Ltd. rNIKALAC" (Registry #) MW-390 ^ MW-100LM > MX-750LM ^ MW-30M > MX-45 > MX-302 and this generation of melamine resin And the modified resin, for example, can be listed as "Cymel" (registered trademark) 1123, 1125, 1128, etc. Examples of the glycoluril resin and its modified resin include "q: trademark" 1170, 1171, 1174. , 1172, and "registered trademark" MX-270, etc. "V» 王册 as a urea resin and its modified resin, for example, price 2 = "_" (registered trademark) 65, _, and "_

Trademark) MX-290 and so on. W 'In terms of reducing the heat shrinkage rate and increasing the heat hardening rate, "Kui is using the second chemical company;:;r9〇'Mff-i〇〇LM'Mx'75〇LM'--- --x-3:" (G) Surfactant as a surfactant, for example, can be listed with · ^ ^ ^ · Polyoxyethylene alkyl ether, polyethyl epoxide aryl ether, polyoxyethylene俨 虱 虱 虱 ( 四 四 四 四 四 四 四 四 四 四 四 针 针 针 针 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 Anionic surfactants such as naphthoate, (4) salt L (tetra) salt, contiguous (tetra) acid vinegar, etc., an amphoteric surfactant such as a beet test, an amino acid, etc. (Η) does not have an ethylenically unsaturated group In the curable composition suitable for the present embodiment, in order to adjust the viscosity of the curable composition material, the viscosity of the material is good (4), and it is possible to adjust (8) a resin having no ethylenic unsaturated group. The resin having an ethylenically unsaturated group, for example, can be listed as the above-mentioned [A+U-containing ethylene-based resin disclosed in the above. A copolymer containing a carboxyl group and an epoxy group, which is disclosed in the Japanese Patent No. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ A development improving agent, an ultraviolet absorbing agent, an inhibitor, an antioxidant, a decane coupling agent, etc. As the coloring agent, a known coloring agent such as a pigment or a dye can be used. Further, for example, when a pigment is used, the pigment can be used. Non-aggregating and stable in the hardening composition,

As a coating material or development, it is known that it is an ionic, anionic, nonionic, known, astringent, ruthenium, or osmium surfactant. Further, an organic carboxylic acid or an acid thereof can also be used. Further, the content thereof is preferably Π) by weight or less with respect to (four) solid/n. ...the hanging weight is 20% by weight or less, and examples of the polymerization inhibitor include a benzoic acid test and a methoxy group as an antioxidant, and examples thereof include 2 6 — — ( mmj *, b a (second butyl)-4-cresol. (βητ), etc. 312ΧΡ/Invention specification (supplement)/96-〇9/96125〇23 still 200811599 As such content, it is usually 5 ppm or more and 1000 ppm or less, preferably 1 〇ppm, based on the total solid content. When the content is too small, the stability tends to be deteriorated. On the other hand, if it is too large, for example, when it is cured by heat and/or light, it may have insufficient hardening. In the case of the photolithography method for the pass-f, it is necessary to set the optimum amount of the storage stability and the sensitivity of the sclerosing composition. / As the type of the decane coupling agent, epoxy can be used. Any of various types, such as a thiol acrylate = an amine group, is preferably an epoxy decane coupling agent, and the content thereof is usually 2% by weight or less, preferably 15% by weight or less based on the total solid content. [4] The method of using the curable composition, and the hardening applicable to the embodiment The composition is used in the same manner as the known color filter for the curable composition. Hereinafter, the case of use as a spacer will be described. Usually, on the substrate on which the spacer is to be provided, by coating In a method such as cloth, a curable composition dissolved or dispersed in a solvent is supplied into a film or a pattern to dry the bath, and after being supplied into a film form, a photolithography such as development by exposure 7 may be performed as needed. Then, pattern formation is performed. Thereafter, an additional exposure or a heat hardening treatment is performed as needed to form a spacer on the substrate. [4-1] The method of supplying to the substrate is applied to the curable composition of the present embodiment, and is usually It is supplied to the substrate in a state of being dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as spin coating, wire bar method, flow coating method, die coating 312XP/invention specification (supplement) can be used. /96-09/96125023 66 200811599 The method, the coating method, the spraying method, etc., wherein the use of the die coating method can greatly reduce the amount of the coating liquid used, and it does not exist at all: Fog, etc. The influence can suppress the occurrence of foreign matter, etc. (4), the hardening group of the appropriate poetry, especially the composition of the coating method by the die coating method. Different, for example in the case of spacers

The thickness of the dry film is usually 〇. 5 # m~1 〇# 较与一; A 仏 仏 is 1 #m~g, 士仏 is 1 P~7 "The range... It is important to dry the film thickness or eventually form The height of the spacer is uniform on the entire substrate. When the unevenness is large, unevenness is generated on the liquid crystal panel. Further, it can be supplied into a pattern by a method such as a helium method or a printing method. A known substrate such as a glass substrate can be used as the substrate. Further, it is preferable that the surface of the substrate is a flat surface. [4-2] Drying method After the curable composition is supplied onto the substrate and dried, it is preferably used: : Drying method of hot plate, IR oven, and convection oven. Further, it can be combined with a vacuum drying method which does not raise the temperature and is dried in a vacuum chamber. The drying conditions can be based on the type of solvent component and the dryer used. The performance is appropriately selected, etc. Between the dry materials, depending on the type of the solvent component and the performance of the dryer to be used, it is usually selected in the range of 4 seconds from rc to 13 (rc temperature = sec to 5 minutes). Preferably, it is 5 (rc~11〇/ it is in the range of 30 seconds to 3 minutes) F4 - 3] Exposure method is exposed on the coating film of the hardening composition, overlapping the negative mask 312XP / invention manual (supplement) / 96-09/96125023 67 200811599 case, through The reticle pattern 'illuminates the light source of the ultraviolet ray or the visible ray. Alternatively, the scanning exposure by the laser light without using the reticle pattern may be employed. In this case, the sensitivity of the photopolymerizable layer may be prevented from being lowered due to oxygen as needed. In the deoxidation environment, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerization layer and then exposed. The light source used for the above exposure is not particularly limited. Examples of the light source include a light source. :a lamp, _su lamp, xenon lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, camping lamp, lamp source, or argon ion laser, laser strike, laser Laser light sources such as green lasers, milk lasers, 氦-pot lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. Optical filters can also be used when irradiating light of a specific wavelength. . For the optical filter, for example, a type in which the light transmittance of the exposure wavelength can be controlled by the film can be used. In this case, as a material for the optical filter, for example, a Cr compound (oxide of Cr, nitrogen) can be cited. a compound, an oxynitride, a vapor, etc., 趟, ^1, 八1, etc., if a reticle that arbitrarily arranges such an optical glazing sheet in an opening portion (light transmitting portion) of a reticle pattern is used (ie, The field is provided with a photomask having an opening σ portion of the optical light sheet and an opening 未 without an optical filter. The photopolymerization rate of the light transmittance of the opening portion of the phase f can be formed by one exposure step. Different patterns. Again, for example, one exposure step can be used to simultaneously form a pattern of different heights. As an exposure, 'usually! mJ/cm2 or more, preferably 5 mJ/cm2 or more, more preferably 10 mJ/cm2 or more, and usually 1 〇〇〇mj/cm2 or less, preferably 80 G nJ/cm2 or less, more preferably _mJ/cm2 or less. . 312XP/Invention Manual (Supplement)/96-09/96125023 200811599 Further, the distance between the exposure target and the mask pattern is usually more than 50 z/m, more preferably 75 // m or more, usually It is 500 // m or less, preferably 400 // m or less, and more preferably 3 or less. [4 - 4] Development method After the above exposure, an image pattern can be formed on the substrate by using an aqueous solution of an alkaline compound or an organic solvent. Further, the aqueous solution may contain a surfactant, an organic solvent, a buffer, a binder, a dye or a pigment. Examples of the test compound include sodium hydroxide, potassium hydroxide, lithium gas oxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium aspartate, sodium metasilicate, and phosphoric acid. Nano, potassium phosphate, sodium hydrogen phosphate, hydrogen phosphate dehydrogenate, dihydrogen sodium dihydrogen phosphate, potassium dihydrogen phosphate, inorganic hydroxide, inorganic compound, mono- or triethanolamine, mono- or di-methylamine, single. Triethylamine, early or diisopropylamine, n-butylamine, mono- or di-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (deletion), specific test compound . These test compounds may be a mixture of two or more kinds. The same as the above may be mentioned as a surfactant. Examples of the solvent include, for example, isopropyl alcohol, (iv), ethyl cellulose, phenyl cellosolve, internal glycol, and dipropanol. Yes, Ling (4) can be used alone or in combination with an aqueous solution. 4 5 ] Additional exposure and thermal hardening treatment For the developed substrate, additional exposure may be performed by the same method as the loading method 312XP/invention manual (supplement)/96-09/96125023 69 200811599, and , Hardening treatment (4) a can also be thermally hardened. At this time; ;=. For 'temperature at iGG °c ~ ·. The range of c is preferably 15 〇C 〜25 〇C ^ 々々円 々々円 ^ 之 干 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择 选择[4-6] The total amount of deformation, the elastic recovery rate, and the rate of recovery of the sclerosing group are characterized by the use of a microhardness tester (mi(10) such as coffee = 9 load). In the charge-removal test, a cured product satisfying the following (1) and satisfying (2) and/or (3) can be formed. (1) The total deformation amount is 1·35 /ζιη or more (2) The elastic recovery rate is 50% or more. (3) The recovery rate is 8% or more. = For example, the spacers for liquid crystal display devices (hereinafter sometimes referred to as "panels") for large-size liquid crystal screen TVs have the following tendency: In the manufacturing step of the board, the load is liable to be generated, so that the total deformation amount of the spacer is large. Moreover, especially in the case of the panel of the large surface, the load is unevenly caused in each part. The curable composition of the present invention is It is meaningful in the following cases. Even in this case, the elastic recovery rate and/or the recovery rate of the cured product (spacer) are also high. Here, the load-de-loading test using the microhardness tester is carried out as follows. In the spacer pattern formed by the method of the above [4], the height is 4 /zm A pattern with an upper cross-sectional area of 8〇±1〇# m2 is measured using a microhardness tester. 312XP/Invention Manual (Supplement)/96-09/96125023 70 200811599 The upper part of the spacer pattern is cut off jL· The area below the guaranteed date. First::- a spacer pattern 'Using the ultra-deep color, == longitudinal section. The position of the longitudinal section is shown in Figure 2. The position Li: the longitudinal section of the figure (Figure 3 The length of the hopper, line AA parallel to the height of the spacer pattern is the height of the substrate surface of the schematic diagram to the height of the second=two=degree Γ(10). The line AA is used as the spacer pattern. The upper cross-sectional area. Medium: 13:: Medium '11 is the spacer pattern, 12 is the longitudinal section position of the spacer pattern. Also in 'Fig. 3, 'is the spacer pattern from A柘' and Guo 15 is the self-substrate. The height from the face to the highest position, 16 is

St? is the height of 9最高% of the height of the highest position, and 17 is the diameter AA' of the circle of the upper section. It was carried out using a Dynamic Ultra Micro Hardness Tester (Shimadzu Corporation's 刀 knife a 3 manufactured by Shimadzu Dynamic Ultra Micro Hardness Tester duh-W2〇1. y Test conditions: the measured temperature was 23t: 'Applicable diameter is 5〇^ "face", applying a load to the spacer at a fixed speed (0.22 gf/sec) for 5 seconds when the predetermined maximum load is 5 gf, and then de-loading at the same speed. The load obtained by using the test A displacement curve (Fig. / is a schematic diagram), and the maximum displacement H is determined [maximum displacement final Η [final]. The above maximum displacement H [maximum] is taken as the total deformation amount. Furthermore, Fig. 4 shows Load of the spacer __ Load in the load-removal test - a schematic diagram of the displacement curve. In Figure 4, the horizontal axis is the displacement H (unit: #瓜), 312ΧΡ/invention specification (supplement)/96_〇9/ 96125023 71 200811599 The vertical axis is the load L (unit··gf). The total deformation amount is preferably 1·4 or more, more preferably 15 or more, preferably 5 or less, more preferably 3 or less. If the total deformation is too large , the elastic recovery rate and/or the recovery rate deteriorate. On the other hand, if the total deformation is too small, the cured product The method corresponds to the unevenness of the load at the time of manufacture of the panel. ^, the elastic recovery rate and the recovery rate are calculated based on the values measured by the load-de-loading test using the above-described microhardness tester, respectively. Recovery rate (%) = 丨 (pattern height before test) Η [final]} / (pattern height before test) xl 〇〇 elastic recovery rate = (Η [maximum] - Η [final]) / Η [maximum The χΐ〇〇f ignition rate is preferably 85% or more, more preferably 9% or more. The elastic recovery rate is preferably 60% or more, more preferably 80% or more. If the recovery rate and/or elasticity When the recovery rate is too small, the cured product cannot correspond to the load unevenness at the time of manufacture of the panel. t The curable composition for the application of the mold is capable of supplying a high degree of uniformity in the application of the die coating method. Further, according to the present embodiment, it is possible to achieve such a high degree of uniformity in balance and to perform various hardening properties required for a curable composition such as a color filter. Sex composition. Applicable to the curable composition of the present embodiment, in liquid In a color filter such as a display, a curable resin composition which can be preferably used in forming a black matrix, a protective layer, a rib, a spacer, etc., can provide high quality according to the present invention. Color filter or liquid crystal display device, etc. 312XP/Invention manual (supplement)_/96125023 72 200811599 [5] Color filter, then, color filter is explained. Fig. 5 shows color filter As shown in FIG. 5, the color filter 20 has a black matrix 22, a pixel colored layer 23, and a protective layer 24 laminated on a glass substrate 21 as a transparent substrate. The black matrix 22 blocks external light and enhances the quality and contrast of the black display. The pixel colored layer 23 is formed by coating a pigment or a dye for displaying colors of three colors of RGB (red, green, and blue). The protective layer 24 fills in the difference in height between the portions of the pixel colored layer 23 and planarizes it. Examples of the material having properties equivalent to those of the glass substrate 21 as a transparent substrate include polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; and polycarbonate. A sheet made of a thermoplastic resin such as methyl acrylate or polysulfone; a thermosetting resin sheet such as an epoxy resin, an unsaturated polyester resin or a poly(meth)acrylic resin. On the glass substrate 21 as a transparent substrate, if necessary, can it be subjected to corona discharge treatment, ozone treatment, or a coupling agent or an amine group? The acid § is intended to form a film forming treatment of various resins such as a resin, and the surface properties such as adhesion can be improved. The thickness of the glass substrate 21 is usually in the range of 0 05 to 1 Å, preferably 0 to 1 mm to 7 mm. The black matrix 22 is formed on the glass substrate 21 using a light-shielding metal film or a black matrix dispersion. In the case of using a light-shielding metal film of the black matrix (4), the light metal film material may be a poor compound such as metal chromium or chromium oxide, a (four) alloy or the like, or a laminate layer of a plurality of layers. 312XP/Invention Manual (Supplement)/96-09/96125023 73 200811599 Generally, the light-shielding metal thin film material is formed on the glass substrate 21 by vapor deposition or sputtering, and then by positive light In the resist, after the desired pattern is formed into a film shape, an etching solution of ammonium cerium nitrate and perchloric acid is used for the chromium, and an etching solution suitable for the material is used for the etching of the other material, and finally the special etching is performed. The agent strips the positive photoresist, thereby forming a black matrix 22. In the case of using the pigment dispersion liquid for the black matrix 22, a black matrix 22 is formed using a curable composition containing a black color material. For example, a black color material containing carbon black, graphite, iron ink, nigrosine, cyanine black, titanium black, or the like may be used alone or in plural, or red or green, which is appropriately selected from inorganic or organic pigments and dyes. The curable composition of the black color material obtained by mixing blue or the like is formed in the same manner as the method of forming the red, green, and blue pixel colored layer 23, and a black matrix μ is formed. Then, on the glass substrate 21 provided with the black matrix 22, the pixel colored layer 23 of three colors of RGB (red, green, and blue) is formed by the cured product of the curable composition of the present embodiment, and further formed. The protective layer 24 fills in the difference in height of the portion of the pixel colored layer 23, and planarizes it to produce the color filter 20. The curable composition for forming the pixel colored layer 23 can be used as at least one coating liquid for forming a resist of red, green or blue. For red, green, and blue, a photoresist black forming surface is formed on a resin black matrix forming surface formed on the glass substrate 21, or a metal black matrix forming surface formed using a chromium compound and other light shielding metal materials, and a photoresist forming coating is applied. After the cloth is dried, the mask is superposed on the coating film by passing through the mask 312XP/invention manual (supplement)/96-09/96125023 74 200811599

The image is exposed, developed, and visualized by cloud I η , ..., or by photohardening to form a pixel coloring containing a hard :: group = hardened material, 23 . By performing the operation on the red color, the image, and the like, respectively, the color filter is formed, and the coating liquid for forming a photoresist is supplied to the glass substrate 2, the dry exposure method, the development method, The exposure and the heat hardening are the same as the operations and conditions described in the method of forming the spacer described above. In the case where the curable composition in the present embodiment of the present invention is excellent in the coating property by the smear coating method, the color filter 20 of the present embodiment is preferably produced. In terms of rate and product quality, the rutting is "made by using the above-mentioned curable composition by a coating step by a die coating method. [6] The liquid crystal display device will then be described with respect to the liquid crystal display device. Fig. 6 shows A schematic diagram of an example of a layer configuration of a liquid crystal display device (panel) LCD. As shown in FIG. 6, the liquid crystal display device (panel) LCD has a configuration in which a color filter 2 and a film are provided by a transparent electrode 25. The liquid crystal element 4 is formed between the array substrate 3 of the transistor (TFT) and the spacer 28 is filled with the liquid crystal 29. The color filter 20 is laminated on the glass substrate 21 with a black matrix. 22. A pixel colored layer 23 and a protective layer 24. A transparent electrode 25 containing IT0 (indium tin oxide) is disposed on the protective layer 24. On the transparent electrode 25, a liquid crystal alignment control protrusion (bump) 27 and a spacer are disposed. 28, into An alignment film 26 is laminated on the 312Xp/invention specification (supplement)/96-09/96125023 75 200811599, etc. The transparent electrode 25 controls the direction of the liquid crystal molecules by applying electricity to the liquid crystal 29. The alignment film 26 is In order to twist the molecules of the liquid crystal 29 into a special form, the thin film transistor array substrate 30 is provided with a thin film transistor 32 for controlling the display of the liquid crystal display device (panel) LCD on the glass substrate 31, The insulating film 33, the transparent electrode 34 containing no, the liquid crystal alignment control protrusion (projecting wall) 37, and the alignment film 35. Further, a polarizing plate (not shown) is attached to each of the glass substrates 21 and 31. Illumination I (BL) is provided on the outer side of the thin film transistor array substrate 3. As shown above, the color filter 2 of the liquid crystal display device (panel) LCD, in which the pixel colored layer 23 is used The curable composition of the present embodiment forms a pixel image as a color showing RGB (red, green, and blue). Further, the liquid crystal alignment control protrusions (bumps) 27, 37 and the spacer of the liquid crystal display (panel) LCD Item 28, both use this Further, the alignment films 26 and 35 are preferably resin films such as polyimine. For the formation of the alignment films 26 and 35, a gravure printing method or a flexographic printing method is usually used. The curing process is performed by thermal baking. The thickness of the alignment films 26 and 35 is usually 10 nm. The liquid crystal display device (panel) LCD is subjected to color filter 20, for example, by the following operation, on a glass substrate. A black matrix 22 and a pixel colored layer 23 are formed on 21. Then, the pixel colored layer 23 is covered with a protective layer 24 as needed, and the transparent electrode 25 is applied. Then, a liquid crystal alignment control 312XP/invention specification (supplement)/96-09/96125023 76 200811599 can be formed (dog wall) 27 and a spacer 28. Further, the alignment film 2 β is applied to the liquid crystal alignment control protrusion (dog wall) 27 and the spacer 28. The enamel film array substrate 3 is formed on the glass substrate 31, and a thin film transistor 32, an insulating film 33, a transparent electrode 34, a liquid crystal alignment control protrusion (dog wall) 37, and an alignment film 35 are formed. Then, the color filter 2 is bonded to the alignment film 26 of the thin film transistor array substrate 30 and the color light-receiving sheet 2, and the alignment film 35 of the thin film transistor array substrate 30 to form a liquid crystal element 40. Further, a liquid crystal 29 is injected into the formed liquid crystal element 4, and is connected to a counter electrode (not shown) to manufacture a liquid crystal display device (panel) LCD. (Embodiment) Hereinafter, the present invention will be described more specifically based on examples. Further, the present invention is not limited to the following embodiments as long as the gist of the invention is not exceeded. (1) Synthesis Example of Compound (Synthesis Example 1 · Ethylene-Unsaturated Compound (A1)) 180 parts of propylene glycol monomethyl ether (viscosity of 7 mPa.sec, 25 it), 7.3 injured azo polymerization The starting agent ("V-59" manufactured by Wako Pure Chemical Co., Ltd.) was put into a reaction vessel, and the temperature was raised to 8 (rc, 4 parts of methacrylate methacrylate, 7 parts of methacrylic acid, and 31 parts) under nitrogen atmosphere. The isodecyl methacrylate was further stirred for 4 hours. Then, the inside of the reaction vessel was replaced with air, and 1 part of p-methoxybenzene, 103.8 parts of glycidyl methacrylate and 4. 2 were placed. The tetraethylammonium chloride was continuously reacted at 85 ° C for 1 hour. A propylene glycol monomethyl group was added to the obtained reaction solution to prepare a solution having a solid concentration of 50% by weight. 312XP/Invention Manual (Repair) /96-09/96125023 ηη 200811599 The ethylenically unsaturated compound (A1) obtained has a solid content acid value of 22 mgKOH/g and a weight average molecular weight (.) of 16, 〇〇〇. 286) (Synthesis Example 2: ethylenically unsaturated compound (A2)): 90 parts of propylene glycol monomethyl ether acetate, 6 1 part of azo-based polymerization start-up, ("V-59" manufactured by Wako Pure Chemical Co., Ltd.) was put into a reaction vessel, and the temperature was raised to 8 (rc, dropping 15 parts of styrene, 42 曱 曱Glycidyl acrylate and a monodecyl acrylate having a tricyclic terrible skeleton ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.), and further stirred for 4 hours. 矣k and 'air in the reaction vessel Displacement, input 〇· 〇$ parts of p-methoxyphenol, 21.3 parts of acrylic acid, and 2. 丨 parts of tetraethylammonium chloride, and continuously reacted at 80 ° C for 8 hours. Thereafter, 12.5 parts of tetrahydroortylene was added. The phthalic anhydride was reacted in the milk for 4 hours. propylene glycol monoterpene ether acetate was added to the obtained reaction solution to prepare a solution having a solid concentration of 50% by weight. The obtained ethylenically unsaturated compound (A2) The solid content acid value is 38 • m § K 〇 H / g, and the weight average molecular weight (Mw) is 1 〇 000. (double bond equivalent is 409) (Compound (H) · · obtained by the following manufacturing examples Compound (Japanese Patent Laid-Open No. Hei 1-133600, Synthesis Example 3 (Section) 〇〇 43)) The acrylic resin disclosed)) In a flask equipped with a cooling tube and a stirrer, put 7 parts by weight 2, 2, a 312XP / invention manual (supplement) / 96-09/96125023 78 200811599 Nitrogen = (2, 4-dimethylvaleronitrile), 2 parts by weight of diethylene glycol dioxime. Continue to input ί parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of methacrylic acid Glycidyl ester, 25 parts by weight of dicyclopentanyl methacrylate, after aeration, began to slowly mix. The temperature of the solution was raised to 7 (TC, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (H). The obtained polymer solution had a solid content concentration of 33% and a solid acid value of 11 〇 mgK. 〇H / g, weight average molecular weight (Mw) is 18, 〇〇〇. (Synthesis Example 3: ethylenically unsaturated compound (A4)) in γ. 5 parts by weight of triethylamine, and 〇.25 parts by weight of benzene In the presence of diphenol, 118 parts by weight of succinic anhydride was reacted with 596 parts by weight of commercially available pentaerythritol triacrylate for 5 hours at 85 ° C. After the reaction, a molecule containing: % of one molecule had one carboxyl group and two or more were obtained. a polyfunctional acrylate of propylene fluorenyl, and a polyfunctional acrylate mixture of 34% pentaerythritol tetraacrylate (a carboxylic acid mixture AA oxime containing an ethylenically unsaturated group. The acid value of the multifunctional acrylate mixture is 9 2. 7. Then, in a 1000 ml four-necked flask, 231 g of 9 9_bis(4'-hydroxyphenyl)di-epoxypropyl etherate 231), 605 g of the above contains B. Private $Gan 4 3 hundred ethylenically unsaturated decanoic acid mixture (AA1) 6. 06 g diethyl Ammonium chloride, ruthenium 15 g p-methoxybenzene, no g propylene glycol monomethyl ether acetate. Then, make this equal to 7 〇. ~ 8 〇◦ ° C heated to dissolve, and then, the solution is white turbid Slowly warm up to π °C and completely dissolve. Then, it will become a transparent and viscous solution and continue to stir for 8 hours until the acid price reaches 3』_rog/g, and obtain the colorless transparent anti-312XP/invention manual (supplement) )/96-09/96125023 79 200811599 The product should be prepared. Further, propylene glycol monoterpene ether acetate was added to the obtained reaction product to prepare a solid fraction of 50%. Then, the solid fraction obtained at 100 g was classified. In a 50% solution, 8·7 g of 1,2,3,6-tetrahydrophthalic anhydride was added, and the temperature was slowly raised and reacted at 8〇85 C for 3 hours, thereby obtaining a compound (A4). The solution (the solid content concentration of the solution was 54%) obtained the compound (A4) having a solid acid value of 55 KOHmg/g and a weight average molecular weight (Mw) of 2,5 Å. (2) Sturability Evaluation of composition (i) Viscosity The above-mentioned ethylenically unsaturated compound U1)~U4 was stirred at room temperature in the proportion shown in Table 2. ((A) component), photopolymerization initiator (〇) component, polymerizable monomer (component (c)), solvent (component (D)), surfactant (component (G)), and The ethylenically unsaturated group-containing resin ((H) component) was prepared and the coating liquid was prepared at a temperature of < 23 t, and measured using a viscometer (E-type viscometer manufactured by Tokyo Keiki Co., Ltd.).

(Η) The leveling resistance value and the downflow resistance value are calculated based on the solid content concentration and the viscosity value of the curable composition prepared in the mixing ratio shown in Table 2, and the leveling resistance value (10) expressed by the above formula (1), and The lower flow resistance value (rs) is expressed by the formula (2). (iii) The leveling property and the downflow characteristic are evaluated for the hardening composition (color resist 4) prepared by the proportion of the ratio, which is filled with the dog's starting part la from the figure i(a) The slit 1 is spouted out at the discharge port 2a of the slot die 2 of the ^ 550 mm twist which is not in the manner shown in Fig. 1(b), and is coated at a speed of 100 mm/s. The gap was applied to the glass substrate 3 under the conditions of [〇〇312XP/invention specification (supplement)/96-09/96125023 80 200811599 and a dry film thickness of 4.5/zm. Furthermore, the unit of dimension in Fig. 1(a) is mm, the thickness of the shims 1 is • 05 mm, and the point line I - I in Fig. 1 (a) indicates the edge of the manifold, the dotted line Π - Π 'Represents the position of the front end of the slit die. In Fig. 1(b), 2 denotes a slit die, 3 denotes a glass substrate, 4 denotes a color photoresist, and 5 denotes unevenness of stripes. j "Height uniformity" of the leveling property, after coating, it was treated by decompression dry-coating for 20·5 Torrx for 20 seconds, and then treated in a convection oven at 23 〇 = 30 minutes, and the obtained was measured. The film thickness distribution in the width direction of the coating fixing portion of the coated substrate was evaluated, and the height distribution (standard deviation) was evaluated. Further, the occurrence of streak unevenness 5 of the coated substrate was macroscopically observed by a Na lamp, and evaluation was performed by the following two criteria. 〇··Without the range of i cm~2 cm from the coated end, there is no interference fringe on the entire surface. X: Strong interference fringes are visible on the entire surface of the substrate. For the "downflow" of the downflow characteristics, the coated substrate after coating was tilted at 30 degrees for 1 〇 second, and then treated by a vacuum drying apparatus for 5 seconds, and then treated in a convection oven at 23 {rc In 3 minutes, the film thickness distribution in the oblique direction of the obtained coated substrate was measured, and the film thickness variation due to the downstream flow was evaluated by the following criteria. 〇: The film thickness difference from the point of the both end portions 2 (10) in the oblique direction of the coated substrate is 0·4 mm or less. △: film 312XP/invention manual (supplement)/96-09/96125023 〇, 200811599 The thickness difference exceeds 0.4 mm from the edge of the coated substrate. (iv) Evaluation of total deformation amount, recovery rate, and elastic recovery rate (iv-Ι) The spacer pattern was formed on the IT tantalum film on which the glass substrate on which the ΙΤ0 film was formed, and coated with a spin coater. After the curable composition prepared by mixing the ratio shown in 2, it was heat-dried at 80 c on a hot plate for 3 minutes to form a coating film. A predetermined pattern mask was used on the obtained coating film, and ultraviolet rays having a intensity of 32 mW/cm2 were used for exposure, and exposure was performed at an exposure amount of i 〇〇 mj/cm 2 . The ultraviolet ray at this time is irradiated under the air. Then, it was spray-developed with a G.1% by weight aqueous potassium hydroxide solution of 23 C at a minimum development time of 2 碌, and then washed with pure water for 1 minute. Here, the minimum development time f refers to the time during which the unexposed portion is completely dissolved under the same development conditions. By the operation, the excess portion was removed, and the glass substrate ' having the pattern of the pattern formed was heat-hardened in the pass box in the 23rd generation to obtain a cylindrical spacer pattern having a height of 4. (iv - 2) The shape of the spacer pattern is measured by using the ultra-deep color 3D shape measuring microscope «manufactured by eyence Co., Ltd. · νκ_95〇〇), as shown in 2, ^ The upper cross-sectional area and height are measured by cutting through the longitudinal section of the shaft in the spacer pattern. The height from the substrate surface of the longitudinal section (the schematic view of FIG. 3) to the point (4) of the highest point (4) is taken as the height of the spacer, and the substrate in the pattern parallel to the spacer pattern is measured. The length of the line is ΑΑ, and the length of the circle is ΑΑ, and the area of the circle of the diameter is taken as the cross-sectional area of the upper part of the spacer pattern. 312ΧΡ/Invention Manual (supplement)/96-09/96125023 82 200811599 (iv-3) Evaluation of mechanical properties of spacers For the above Πν-. The obtained interval #m, the upper cross-sectional area is the training η 2 Τ the same degree is 4 丨 war (four) is 80 soil 1 〇 ^ "solid pattern filial Dynamic ultra-micro hardness tester (,, Yuan Yu " ^. ΠίίΗ W9nic, and the load of the company (DUH-W201S) - In addition to the 舛 舛 ^ ^ ^, 目 丨Λ 仃 仃 仃 4 4 4 4 4 4 仃 仃 仃 231 测定 231 231 231 231 231 231 231 The plane indenter of diameter π " . rm ^ ^ .Λ οο 仏 von 5〇# m applies a load to the spacer pattern by u (0.22 gf/sec) [to reach the established maximum load of 5. ^ — Gf% is held for 5 seconds, and then the load is released at the same speed. The load-displacement curve (Fig. 4 is a schematic diagram) obtained by the test is used to determine the maximum displacement (total deformation) H [maximum] And the final displacement Η [final], recovery rate 弹性, elastic recovery rate (%), based on the above measured values, calculated in the following manner, the results are shown in Table 2. - Recovery rate (%) = { (before the test Pattern height) _ H [final (pattern height before test) χ 1 〇〇 elastic recovery rate (%) = (Η [maximum] _H [final]) / H [maximum] χ 1 〇 () (Examples 1 to 6 and Comparative Examples 1 to 3) The use of an ethylenically unsaturated compound (Ai) to (Α4) ((Α) component), a photopolymerization initiator ((Β a component), a polymerizable monomer ((C) component), a solvent ((D) component), a surfactant ((G) component), and a resin ((Η) component) having no ethylenically unsaturated group, The curable composition prepared by the blending ratio shown in Table 2 was evaluated for viscosity (μ), leveling resistance value (RL), and downflow resistance value (RS). Further, the height uniformity and the downflow characteristics were evaluated. Table 2 〇 312XP / Invention Manual (Supplement) / 96-09/96125023 83 200811599 [Table 2] Example Comparative Example Curable Composition 1 2 3 4 5 6 1 2 3 (A) Acetate Unsaturated Compound A1 100 - a 100 100 - a - - A2 - 100 a - - 70 - - an A4 - - 92.6 one - one 92.6 92.6 (B) photopolymerization initiator B 3 3 3 3 3 3 3 3 3 (C ) Polymeric monomer C1 40 40 40 30 40 40 40 40 40 C2 - - - 10 - One-one (D) Solvent D1 374 415 330 322 334 389 228 241 485 D2 - - - One 40 - - _ - ( G) surfactant G 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (H) Resin without ethylenic unsaturated group 一 - One-to-45 152 - One solid concentration C kg/kg 0.18 0.17 0.20 0. 20 0.18 0.17 0.22 0.25 0.15 Intrinsic viscosity of the hardenable composition # mPa-s 4.7 3.3 3.2 5.4 5.3 3.7 5.0 4.0 2.5 Leveling resistance RL 0. 027 0.016 0. 026 0.043 0.031 0.018 0.053 0.060 0. 008 Downflow resistance value RS 0.15 0.10 0.13 0. 22 0.17 0.11 0. 24 0.24 0. 06 Evaluation results Highly uniformity Height distribution (1〇2) 0. 76 0. 60 0.81 0. 77 0.76 0. 63 1.50 1.60 1.65 Evaluation 〇〇〇〇〇〇XXX Lower flow 〇 Δ △ 〇〇Δ 〇〇Δ Total deformation Η[maximum](/zm) 1.50 1.45 1.45 1.62 1.51 1.60 1.50 1.45 1.44 Final displacement ΗΪ final ί (// m) 0.65 0. 65 0. 60 0. 75 0. 65 0.80 0. 85 0.59 0. 58 Recovery rate (8) 84 84 85 81 84 80 79 85 86 Elastic recovery rate (%) 57 55 59 53 57 50 43 59 60 Here, in Table 2, component (B) Starting agent), (C) component (polymerizable monomer), (D) component (solvent), and (G) component (surfactant) are as follows . (B) Photopolymerization initiator: "Irgacure 907" (C) Dipentaerythritol hexaacrylate manufactured by Ciba Specialty Chemicals Co., Ltd.: "KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd. (viscosity 5500 to 8000 mPa) .sec, 25°C) (C2) pentaerythritol triacrylate 1,6-hexamethylene diisocyanate urethane prepolymer: manufactured by Kyoeisha Chemical Co., Ltd. 312XP / invention manual (supplement) / 96-09/96125023 84 200811599 "1^-30611" (viscosity 10000~40000 11^&.36., 25°(:) (D1) propylene glycol monoterpene ether acetate (viscosity 1 · 1 mPa· sec, 25°C) (D2) 3-methoxybutanol (viscosity 2·9 mPa-sec, 25°C) (G) Surfactant: MEGAFACE F475 manufactured by Dainippon Ink Chemical Industry Co., Ltd. According to the results of Table 2, It is understood that an ethylenically unsaturated compound (A1) to (A4) (component (A)), a photopolymerization initiator (component (B)), a polymerizable monomer (component (C)), and a solvent ((D) are used. In the curable composition prepared by the component) and the surfactant (component (g)), the leveling resistance value (RL) is at 〇·〇1~〇.〇 In the range of 5' and the downflow resistance value (RS) is 〇·1 or more (Examples 1 to 6), the uniformity of the southness of the die coating is good, the leveling property is excellent, and the downflow characteristics are good. When the leveling resistance value (RL) exceeds 〇·〇5 (Comparative Examples 1, 2) or the case where 〇·01 is not satisfied (Comparative Example 3), the height uniformity of the mold coating is poor, and the leveling property is impaired. BRIEF DESCRIPTION OF THE DRAWINGS ^ Figure uw shows a plan view of a shim for evaluation test, and Fig. = a perspective view of a coated state of a slit die to which the shim is attached. FIG. 3 is a view showing the position of the longitudinal section when the spacer case is viewed from above, and FIG. 3 is a schematic view showing the rim of the spacer. The schematic diagram of the line. Negative t de-loading test Fig. 6 is a schematic view showing a layered structure of a liquid crystal display device (panel). Fig. 6 is a schematic view showing a layered structure of a liquid crystal display device (panel). A schematic diagram of an example. [Description of main component symbols] 1 la 2 2a Shrug protrusions Slit die spit π 31 glass substrate 21 4 color photoresist 5 stripe unevenness 11 spacer pattern 12 spacer pattern middle axis 13 longitudinal section position 14 profile of longitudinal section of spacer pattern 15 height from substrate surface to highest position 16 self-substrate Height to face to the highest position 17 Diameter of the circle of the upper profile AA' 20 Color filter 22 Black matrix 23 Pixel colored layer 24 Protective layer 25, 34 Transparent electrode 26, 35 Alignment film 27, 37 Liquid crystal alignment control protrusion 312XP/Invention Manual (Supplement)/96-09/96125023 86 200811599 28 Spacer 29 Liquid Crystal 30 Thin Film Transistor Substrate 32 Thin Film Transistor 33 Insulation Film 40 Liquid Crystal Element 312XP/Invention Manual (Supplement)/96-09 /96125023 87

Claims (1)

200811599 X. Patent application Fan Park·· 1· A curable composition characterized in that it satisfies the following (a) and (b), (a) the viscosity (#) of the coating liquid and the solid concentration ( c) The leveling resistance value (RL) expressed by the following formula (1) is in the range of 〇· 〇1 to 〇· 05; RL = // xC3 (1) • (in the formula (1), the RL system is adjusted The flat resistance value, the viscosity of the coating liquid (unit: mPa.s), the solid concentration of the C system (unit: kg/kg), and r (b) the lower flow resistance value (RS) expressed by the following formula (2) ) is 〇·丨 or more, β xc2 (2) (in equation (2), RS system downflow resistance value, #system coating liquid viscosity (unit··mPa.s), C system solid concentration (unit·· Kg/kg)). 2. A sclerosing composition according to claim 1 of the patent scope, which can be used for coating in a molding manner. 3. A sclerosing composition as claimed in claim 2 or 2, which can be used to form a color filter. 〃 4· A cured product characterized in that the curable composition of the first application of the patent scope is cured. The fifth color filter is characterized in that it contains a cured product of the patent application. The first set is characterized by: the patent application scope 312XP / invention manual (supplement) / 96-〇 9/96125023