TW200804976A - Thermosetting composition for protective film, hardened product and liquid crystal display device - Google Patents

Abstract

The present invention relates to a thermosetting composition for a protective film, which can be used to form a dried coating film (protective film) having a reduced adhesive property, will not be colored when subjected to baking, and has good transmittance in the visible region. The thermosetting composition of the present invention comprises (A) an alkali soluble resin, (B) a compound having ethylene unsaturated groups, and (C) a photopolymerization initiator. The component (A) has an acid value of 80 mg-KOH/g or above. The resin film formed of the component (A) to a film thickness of 1 μm has a break point of 10 seconds or above in a 0.4 wt.% of tetramethylammonium hydroxide solution (25 DEG C).

Description

200804976 IX. Description of the invention: [Technical field to which the invention pertains] # The present invention relates to a thermosetting composition for a protective film using light or heat. More specifically, for example, regarding a printed wiring board, a liquid crystal display, a plasma display, a large-scale integrated circuit, a thin transistor, a half =: a packaged roll color; a light-proof sheet, an organic electroluminescence, or the like A curable composition which is useful for forming a solder resist film or a cover film and an insulating coating layer of various electronic parts. Further, the present invention relates to a curable composition which is useful for a color filter, a black matrix, a protective layer, a rib portion, and a spacer used in a liquid crystal panel such as a liquid crystal display, and is formed using the same. A cured product, and a liquid crystal display device having the same. [Prior Art] Thin film transistor used in a liquid crystal display device (TFT, Thin)

On the active matrix substrate, an interlayer insulating film for protecting the tft array is formed between the TFT array element and the transparent conductive film which is formed as a pixel electrode. Here, a contact hole for connecting the tantalum electrode of the TFT array and the wiring formed of the transparent conductive film is usually formed on the interlayer insulating film. Therefore, the material of the interlayer insulating film generally uses a photosensitive thermosetting property. w Also, the thermosetting composition used in such a use, more specifically the mouth as a positive photosensitive composition, is known to contain a composition of a soluble resin and a 1 '2-azepine nitride (for example, Refer to Patent Document 1). Further, as a negative-type thermosetting composition, a photopolymerizable composition is known (Example 312XP/Invention Manual (Supplement)/96·09/96119465 6 200804976, for example, see Patent Document 2). In the conventional positive photosensitive composition v disclosed in Patent Document 1, for example, there is a patent document 2: Japanese Patent Laid-Open No. Hei. No. 2004-131899. In the case of hard baking after exposure and development, 1,2-quinonediazide is colored by thermal decomposition, and the light transmittance in the visible light region is lowered. On the other hand, in the photopolymerizable negative photosensitive composition disclosed in Patent Document 2, the coloring problem as described above does not occur, but the coating film is soft and adhesive (hereinafter referred to as tackiness) is high. In addition, there is still room for improvement, that is, a photopolymerizable negative photosensitive composition having a low molecular weight and a compound having an ethylenic unsaturated group in view of improvement in sensitivity and resolution, the viscosity is increased. High tendency. If the viscosity of the coating film is high, there is a case where the film is in contact with the reticle and adheres to the reticle during exposure, or contamination is caused on the reticle, or dust is adsorbed on the coating film to become φ image formation. The reason for the defect. Further, in the use of the TFT active matrix substrate as described above, it is necessary to form a cured film (a cured film having chemical resistance) which is resistant to the etching liquid when the upper transparent conductive film is formed after the formation of the contact hole. Conventionally, in order to improve the chemical resistance, a large amount of a compound having an ethylenically unsaturated group is added to increase the crosslinking density. That is, it is difficult to improve the chemical resistance and the viscosity reduction. SUMMARY OF THE INVENTION An object of the present invention is to provide a thermosetting composition for a protective film which can form a coating dry film 312XP/invention specification (supplement)/96-09/96119465 7 200804976 (edge film) which can reduce viscosity. . Further, another object of the present invention is to provide a thermosetting composition for a protective film which is free from coloring during hard baking and has a good light transmittance in a visible light region. Further, another object of the present invention is to provide a thermosetting composition for a protective film which can form a protective layer excellent in chemical resistance after thermosetting. Further, another object of the present invention is to provide a cured product formed of such a thermosetting composition for a protective film, and a liquid crystal display device having the cured product as a protective plate. A thermosetting composition for a protective film according to the invention of the present invention, which comprises (A) an alkali-soluble resin, (B) a compound having two or more ethylenically unsaturated groups, and (C) photopolymerization initiation The composition of the agent, the acid value of the component (A) is 80 mg-KOH/g or more, and the resin film of the component (A) is formed into a ruthenium 4% by weight aqueous solution of tetradecyl ammonium hydroxide ( 25. The break point in the crucible is 1 sec. or more. The cured product of the present invention is formed using the thermosetting composition of the protective film. The liquid crystal display device of the present invention includes the cured product as a protective film. According to the present invention, it is possible to provide a thermosetting composition for a protective film which can form a coating-dried film (protective film) which can reduce viscosity, and can provide light-transmissive, non-colored, visible light-transmitting regions. A thermosetting composition for a protective film having a good rate is provided. Further, a thermosetting composition for a protective film which can form a protective layer excellent in chemical resistance after thermosetting is provided. 312XP/Invention Manual (Supplement)/96- 09/96119465 200804976 Furthermore, with this protection The cured product formed of the thermosetting composition for a film is a protective film which has no coloration during hard baking and has a good light transmittance in a visible light region: 'Therefore, the quality is high. · The liquid crystal display device of the present invention uses such high quality In addition, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention. _ Π] for protective film Thermosetting composition The thermosetting composition for a protective film of the present embodiment (hereinafter sometimes referred to simply as "thermosetting composition") contains the following components (A) to (c). (A) an alkali-soluble resin, (B) a compound having two or more ethylenically unsaturated groups, (C) a photopolymerization initiator, and the acid value of the component (A) is 80 mg-KOH/g or more, and The resin film formed by filming the thickness of the component (A) at a film thickness of 1 /zm in a 4 wt% tetradecylphosphonium hydroxide aqueous solution (25 ° C) has a break point of 1 sec. or more. After the exposure is exposed, it is obtained at 22 (TC baking treatment i hours*) The hot-hardened film is preferably dissolved in 20 parts by weight / ◦ hydrochloric acid (4 ° C) (hereinafter, abbreviated as "hydrochloric acid dissolution rate") preferably 〇. 丨 min or less. "Acid Price", "Breakpoint", "Optimum Exposure", and "Dissolution Rate of Hydrochloric Acid" are explained. 312XP/Invention Manual (Repair)/96-09/96119465 9 200804976 [Acid Price] In this embodiment The "acid value" is a value measured in accordance with JIS-K0070 (standard oil test method). * In the present embodiment, the acid value of the component (A) is 80 mg-KOH/g or more, preferably 90 mg-K〇H/g or more, more preferably 100 mg-K〇H/g or more. Further, the upper limit is usually 3 〇〇 mg-K 〇H/g or less, preferably 2 (10) mg_K0H/g or less. When the value of the acid value is small, it is difficult to obtain a thermosetting composition for a protective film which lowers the viscosity. _ Furthermore, the acid value is closely related to the viscosity, and is newly discovered in this embodiment. D ^ [Breakpoint] The soluble resin is applied to the film thickness of the dry thickness. The diameter of 4 Yingnu ♦ on the substrate, baked on the heating plate for seconds. Thereafter, it was immersed in 0.4% by weight of tetramethyl gas = l =: t. The soaking time (seconds) at which the surface of the substrate is visualized by dissolving or peeling off the soluble resin or the like is defined as a break point. In the present embodiment, the break point is 15 seconds or longer, more preferably 3 () seconds or longer. = Bu is 1 Gsec or more'. Preferably, it is usually 1000 seconds or less. The upper limit of the film is not particularly limited. Here, if the acid value of the alkali-soluble resin, and the exposure obtained after the exposure, the thermosetting property is lowered, or the film shape is deteriorated, the film is thinned and enlarged, and the image is formed. The composition of the highly soluble resin, the brother. Further, in the case of such a solution 312XP/invention specification (supplement)/9_61, it is also easily dissolved in 200804976, and the chemical resistance of the photoresist film such as N-methylpyrrolidone is deteriorated. In the liquid, the heat hardening obtained after hard baking is in the embodiment, by taking the breakpoint value into the above-mentioned range

= A thermosetting film having a cured resin composition having a good acid value and having good chemical resistance and excellent chemical resistance can be obtained. The mouth of the city of Shikoku, the so-called "hard roast", indicates that the exposure is obvious. The heat-cured film of the present embodiment was obtained by the hard baking. Further, in the present embodiment, the baking treatment-curable composition which has been subjected to the image treatment is sufficiently thermally cured in the present embodiment, and is used as an alkali-soluble resin which realizes the aging, the mussels, and the long breakpoint. The method includes the following methods [a] to [c]. [a] A method of increasing the molecular weight of a resin [b] A method of using a compound having a hydrophobic substituent as a resin [C] A method of partially including a crosslinked structure or the like - wherein, in view of achieving good development The viewpoint is preferably the [b] method, and particularly preferably the [b] method. [Optimum exposure amount] The thermosetting composition of the present embodiment is applied onto a glass substrate so that the dry film thickness is approximately 4, and is carried out on a hot plate at 9 〇 and 9 〇•sec. bake. Thereafter, exposure was performed by a high pressure mercury lamp at an illuminance of 3 〇 m w / c m 2 . As the exposure conditions, the amount of exposure energy is in the range of i 〇 mj/cm 2 to 32 〇 mJ/cm 2 , and the exposure energy amount is set at intervals of each time for exposure. After exposure, 0.4% by weight of tetramethylammonium oxide 312XP/invention manual (supplement)/96-09/96119465 11 200804976 in water/cold solution for 7 seconds, rinsed with pure water, determined The film thickness of the remaining cured film (exposure film). The film thickness of the obtained exposed film was plotted with respect to the exposure amount. The optimum exposure amount (mj/cm2) is defined as the optimum exposure amount of the exposure film with an exposure amount of 21/2 times the exposure amount of 10% or less. [Polychloric acid dissolution rate] The thermosetting composition of the present embodiment is applied to a glass substrate so that the dry film thickness is approximately 4 # m, and is applied to a hot plate at 90 ° C for 90 ° C. Bake. Thereafter, exposure was performed by a high pressure mercury lamp at an illuminance of 3 〇 mW/cm 2 . The exposure amount is set to the above optimal exposure amount. After the exposure, the film was baked at 2201 for an hour in an oven to obtain a thermosetting film. The thermosetting film was immersed in 40% by weight of hydrochloric acid, and then rinsed with pure water to measure the film thickness of the remaining thermosetting film. The difference between the film thickness of the thermosetting film and the film thickness of the thermosetting film remaining after washing with the above pure water (Vm) is divided by the value of φ time (minute) soaked in 2% by weight of hydrochloric acid as hydrochloric acid dissolution. speed. The larger the value of the above-described hydrochloric acid dissolution rate, the lower the resistance to the etching liquid when wiring such as IT crucible is produced. The dissolution rate of the hydrochloric acid is usually preferably #m/min and more preferably 0.05 W minutes or less. In addition, the lower limit is not particularly limited. • 疋’ is usually 〇· 001 // m/min or more. In the present embodiment, the sheet is provided with a thermosetting composition for a protective film which can form a protective film which reduces the viscosity of the film (4), and the acid value and the break point of the component (1) contained in the thermosetting composition are respectively It is specified in a fixed range. 312XP/Invention Manual (Supplement)/96-09/96119465 12 200804976 Furthermore, the problem of the present embodiment (reducing viscosity) is not a problem generally known to the industry. Next, each component used in the thermosetting composition of the present embodiment will be described. In the thermosetting composition of the present embodiment, in addition to the essential components (A) to (c), the following components may be blended. (D) Thermal crosslinking agent (E) Other components • (F) Additives (G) Organic solvents Hereinafter, each component will be described. Further, in the present embodiment, the "r (meth)acrylic group" means "acrylic acid group and/or methacrylic acid group". The same applies to "(meth) acrylate" and "(meth) acryl thiol". In addition, the phrase "addition" before the monomer name means that both the monomer and the polymer thereof are contained, and the "(acid) anhydride" and "...acid (anhydride)" are acids and their self-text. Both of the anhydrides, "(poly)carboxylic acid", mean both a carboxylic acid and a polycarboxylic acid. In addition, the "total solid content" means the total amount of components of the photopolymerizable composition from which the solvent is removed. (A) Alkali-soluble resin As the alkali-soluble resin used in the present embodiment, the resin having an acid value and a breakpoint within the above range and soluble in an alkaline solvent is not particularly limited, and is preferably a A resin containing a carboxyl group or a hydroxyl group. As such a soluble resin, for example, 312XP/invention specification (supplement)/96-09/% 119465 13 200804976 (mercapto)acrylic acid, (meth) acrylate, maleic acid, vinyl acetate An epoxy resin containing an unsaturated group and a carboxyl group, such as s曰, 顺丁二二胺胺; • (mercapto)acrylic acid, (mercapto) acrylate, (methyl) acrylonitrile, (fluorene) propylene a vinyl-based resin containing a hydroxyl group or a carboxyl group, which contains a hydroxyl group or a carboxyl group, such as a amine, a maleic acid, a styrene, a vinyl acetate, a vinylidene chloride or a maleimide; and a polyamine; Polyester, polyether, polyurethane, polyvinyl butadiene, polyethylene glycol, polyvinylpyrrolidone, acetamidine cellulose, and the like. These may be used alone or in combination of two or more. Further, in view of the testability and image formation property, an epoxy resin containing an unsaturated group and a carboxyl group, and a vinyl group containing a carboxyl group are preferable. Further, in view of the peeling property after exposure and development, in the vinyl-containing resin containing a carboxyl group, it is preferred to use a fine resin containing a carboxyl group which does not contain an unsaturated group. (A-1) an epoxy resin containing an unsaturated group and a carboxyl group as an epoxy resin containing an unsaturated group and a carboxyl group, and may, for example, be a carboxylic acid addition product containing an unsaturated group of a cyclic oxy resin, further * A ring-containing resin containing an unsaturated group and a carboxyl group of a polyvalent carboxylic acid and/or an acid anhydride thereof. That is, it can be added to the epoxy group of (i) epoxy group by ester bond (-C00-) formed by (ii) a, a carboxyl group ring-opening addition of a fluorene-unsaturated monocarboxylic acid. Ethylene unsaturated bond, and hydroxy 312XP generated at this time / invention specification (supplement) / 96-09/96119465 14 200804976 ^: two (1) polybasic acid or its acid needle renegade. Hereinafter, the constituent components of the nucleating oxygen resin containing the mulch and (4) will be described. The following constitutions may be used alone or in combination of two or more. The ring used in the epoxy resin containing an unsaturated group and a fluorenyl group: a double bis epoxide used in an epoxy resin containing an unsaturated group and (iv): tT F epoxy resin, double-reduced epoxy resin, age-old acid: Polycyclic (four) fat, condensed and dicyclopentanyl polymerized epoxy resin. Among them, the viewpoint of the strength of the cured film is preferably (4) epoxy resin phenolic epoxy resin, polyepoxy resin of dicyclopentadiene, and glycidyl propyl acrylate. (meth)acrylic acid alkyl ester copolymer or the like / (Α 1 2) α, / 9 - unsaturated monoacids as the unsaturated monocarboxylic acid, for example, (meth)acrylic acid, butene I, cis-butyl Alkenedioic acid, fumaric acid, isaconic acid, citraconic acid, etc., •= and pentaerythritol tri(meth) acrylate succinic anhydride anhydride, pentaerythritol tris(decyl) acrylate tetrahydroortylene Dicarboxylic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (methyl) acrylate A tetrahydrophthalic anhydride adduct, a reaction product of (meth)acrylic acid and 2-4-caprolactone, and the like. Among them, (meth) propyl benzoic acid is preferred in view of sensitivity. (A-1 - 3) a polybasic acid or an anhydride thereof as a polyvalent carboxylic acid or an anhydride thereof, and examples thereof include succinic acid, maleic 312 oxime/invention specification (supplement)/96-09/96119465 15 200804976 acid, Ionic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-mercaptotetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid , 4-ethyltetraphthalic acid, hexamethylene phthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethyl Hexahydroortho-, phthalic acid, 4-ethylhexa-hexyl phthalic acid, and their anhydrides. Among them, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable in view of image reproducibility and development, and more preferably tetrahydrophthalic acid Anhydride. In the present embodiment, in view of improving the sensitivity, the resolution, and the adhesion to the substrate of the thermosetting composition, the epoxy resin containing an unsaturated group and a repellent group is preferably an epoxy resin. Phenolic novolac epoxy resin, double epoxy resin, hydroxy epoxy (resin) or nonylphenol novolac epoxy resin, α, /3-unsaturated monocarboxylic acid is (mercapto)acrylic acid, polycarboxylic acid or its anhydride For tetrahydrophthalic anhydride. Further, as the epoxy resin containing an unsaturated group and a carboxyl group, the acid value is preferably from 80 to 200 mg-KOH/g, more preferably from 85 to 180 mg-KOH/g. Further, the molecular weight of the epoxy resin containing an unsaturated group and a carboxyl group is usually 1,000 or more, preferably 1,500 or more, usually 40 or less, and the ruthenium is preferably 30 or less. More preferably 2 〇, 〇〇〇 below. • Especially in the case of an epoxy resin containing an unsaturated group and a carboxyl group having an acid value of 120 mg-KOH/g or more, a high value can be obtained by setting the value of the following formula (1) to 150 or more. A resin having a molecular weight and a long break point (the above method [a]) is preferred. ([weight average molecular weight] + 20000) / [acid price] (1) 312 talk instructions (supplement) / 96-09/96119465 16 200804976 The lower limit of the value of (1), more preferably 170 or more, Especially good. The upper limit of the formula (1) is preferably 400 or less, and particularly preferably 3 or less. When the value of the formula (1) is small, the resin having a high acid value will have a short break point, so that the presence of the thermosetting composition is high, and the solubility is also high, and the sensitivity and the adhesion are in the direction of the cow. Further, when the value of the formula (1) is large, it is easy to contain a gelled component having a high molecular weight, and there is a tendency that a development residue tends to occur. As a method of obtaining a high molecular weight epoxy resin containing an unsaturated group and a carboxyl group, a method of using a high molecular weight epoxy resin as the above epoxy resin can be mentioned. In addition, the molecular weight in the present embodiment is a weight average molecular weight (MW) in terms of polystyrene measured by gel permeation chromatography (GPC method) unless otherwise specified. The details of this measurement method are as follows. [Machine] HTC-8020 manufactured by Tosoh Co., Ltd. _ [Pipe column] GMHXL-N 30cmx2 from Tosoh Co., Ltd.

[Mobile phase] 1. 0 ml / min [column temperature] 40 ° C

[Solvent] THF (four-hydrogen nucleus stabilized by 丁基·〇3 wt% of butyl hydroxy benzene) . [Standard sample] polystyrene (PSt) standard sample [calibration line] 5 times [test] RI (inside the device) [Injection amount] 0.1% by weight 100 //L (samples in advance GL Science 312XP / invention manual (supplement) / 96-09/96119465 17 200804976 Co., Ltd. manufacturing layer (four) 13P riding filter,) The above-mentioned epoxy resin containing an unsaturated group and a silk in the deuterium can be synthesized by a conventionally known method. Specifically, the above-mentioned % oxygen resin may be dissolved in an organic solvent, and the above-mentioned α,/3-unsaturated monocarboxylic acid may be added to the mixture in the presence of a catalyst and a thermal polymerization inhibitor. Further, a polyvalent carboxylic acid or its anhydride is added to continue the reaction. Here, the organic solvent may, for example, be an organic solvent such as methyl ethyl ketone, cyclohexyl oxime, ethyl alcohol ethyl acetate or propylene glycol monomethyl ether acetate. — Further, as the catalyst, a tertiary amine such as triethylamine, benzyldiamine or tribenzylamine may be mentioned, or de-, 7-tetramethylammonium chloride or decyltriethylamine may be mentioned. a quaternary ammonium salt such as chlorination, female-based listening, tetrabutylammonium chloride, trimethyl-based ammonium chloride, 痞-甘#, and a phosphorus compound such as bis-phosphine, or Triphenyl records and other townships. Further, as the above-mentioned thermal polymerization inhibitor, hydroquinone phenol monomethyl ether, methyl p-diphenol or the like can be given. The amount of the unsaturated monomer _ is relative to the chemical equivalent of the epoxy resin, and can be generally set to 〇. 7-1 3 chemist = U~U chemical equivalent. Further, the temperature field at the time of the addition reaction may be 60 to 15 Torr, preferably 80 to Torr. Further, the amount of the polybasic acid or the acid liver thereof is usually set to 〇· K 2 chemical, preferably 0·2 to 1·1, based on the chemical equivalent amount generated in the above addition reaction. Chemical equivalent. In the case of the above-mentioned epoxy resin containing an unsaturated group and a silk, specific examples of the heavy unit are shown below. 312XP/Invention Manual (supplement)/96-09/96119465 18 200804976 [Chemical 1]

OCH^HCHr

Translation (? shouting bell

HCK)i [Chemical 2]

(R represents hydroxy or methyl) 19 312XP/Invention Manual (supplement)/96-09/96119465 200804976

The idea of using a compound having a hydrophobic substituent as a resin to obtain a high acid value and a long breakpoint of the tree wax (the above ^^^^^^^^^^^^^^^^^^^^^^^^^^^ a group of resins; a resin such as a condensed alicyclic group such as a Fuji, a bicyclopentylene, or an amantadine; and specifically 2' (A-1-υ is preferably a (four) secret epoxy resin, a (four) A cyclic epoxy resin, a polymerized epoxy resin of a phenol and a dicyclopentadiene. (Α 2) The vinyl group-containing resin containing a carboxyl group is, for example, a vinyl group-containing unsaturated carboxylic acid having a carboxyl group and ethylene. A copolymer of a base compound, etc. Examples of the unsaturated carboxylic acid include (mercapto)acrylic acid, crotonic acid, methacrylic acid, maleic acid, maleic anhydride, isaconic acid, citraconic acid, and the like. These may be used singly or in combination of two or more. Examples of the vinyl compound include styrene, α-methylstyrene, hydroxystyrene, and decyl decyl acrylate. Ethyl acrylate, propyl (meth) acrylate, (meth) propyl Butyl acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, oxindole (meth) acrylate Ester, (methyl) 3 UXP / invention specification (supplement) / 96-09/96119465 20 200804976 Acrylic acid via vinegar, (meth)acrylic acid epoxy propyl vinegar, (methyl) propyl acetonate vinegar, (meth)acrylic acid dicyclopentanacetic acid, (methyl)propionic acid 2_methyladamantane vinegar, (mercapto)acrylic acid 2-ethyl ruthenium vinegar, (methyl) acrylic acid vinegar, ( Methyl) dimethyl amide ethoxylate g, N_(methyl) propylene phthalocyanine, (meth) acrylonitrile, (meth) acrylamide, N-methyl hydrazide A copolymer of an amine, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminoethyl(decyl)acrylamide, and an ethylene compound such as ethylene acetate These may be used singly or in combination of two or more. Among them, '(fluorenyl) dicyclopentanyl acrylate provides a wide tolerance for development time and deterioration of imaging liquid. Preferred examples of such (indenyl) dicyclopentanyl acrylate include compounds exemplified in JP-A-2002-89533, for example, a dicyclopentadiene skeleton or a dicyclopentane. a base skeleton, a dicyclopentenyl skeleton, a (fluorenyl) acrylate of a dicyclopentenyloxyalkyl skeleton, etc. # In the above copolymer (vinyl group-containing resin containing a carboxyl group), in consideration of image shape, sensitivity, From the viewpoint of the strength of the cured film, a (meth) acrylate-(meth)acrylic acid copolymer is preferable, and more preferably, it contains ~go mol% (mercapto) acrylate, and 20 to 70 mol% (曱) Copolymer of acrylic acid. Particularly good % • Contains 50 to 75 mole % (mercapto) acrylate, 25 to 50 mole % (methyl). Acrylic copolymer. & Further, as the (meth) acrylate, an aryl (meth) acrylate such as benzyl (meth) acrylate, and an isobutyl (meth) acrylate or a dicyclopentyl (meth) acrylate are preferable. Ester, 2-methyladamantyl (meth)acrylate, (methyl) 312XP/Invention Manual (supplement)/96·09/96119465 200804976 Propylene Fee 2 Ethyl Crude Oil Vinegar Monocyclic (Methyl) Acrylic acid esters. Using a (meth) acrylate-(meth)acrylic acid copolymer having an alicyclic (meth)acrylic acid alkyl ester as a copolymer component as a component • a soluble resin, alicyclic (A) The base of the alkyl acrylate is preferably 10 mol% or more, more preferably 15 mol% or more, more preferably 60 mol% or less, still more preferably 50 mol% or less. Further, the acid value of the carboxyl group-containing vinyl resin is usually 80 to 25 Q mg to K0H/g, preferably 80 to 200 mg-KOH/g, more preferably 90 to 150 mg to KOH/g. Further, the molecular weight of the carboxyl group-containing vinyl resin is usually 1,000 or more, preferably 1,500 or more, more preferably 2 or more, and usually 10,000 or less, preferably Below 50,000, more preferably 3 〇, 〇〇〇 below, especially preferably below 20,000. In the case of using a carboxyl group-containing vinyl resin in the above range, the peeling property after development is good, which is preferable. In particular, in the case of a carboxyl group-containing vinyl fluorene resin having an acid value of 12 〇 mg-K 〇H/g or more, a high molecular weight can be obtained by setting the value of the following formula (1) to 15 Å or more. It is preferable to use a resin having a long break point (the above method [a ]). ([Weight average molecular weight] + 20000) / [Acid value] (1) • The lower limit of the value of the formula (1) is more preferably 170 or more, and particularly preferably 18 Å or more. # As the upper limit of the formula (1), it is preferably 400 or less, and particularly preferably 300 or less. (1) When the value of the formula is small, the resin having a high acid value will have a short break point, so that the alkali solubility as a thermosetting composition is also high, sensitivity and adhesion are 312XP/invention specification (supplement) /96-09/96119465 22 200804976 Down, tendency. Further, when the value of the formula (i) is large, it is easy to contain a gelled component having a high molecular weight, and there is a tendency that a development residue tends to occur. As a method of obtaining a high molecular weight ethylenic resin containing a slow group, a method of reducing the amount of the polymerization initiator in the polymerization reaction of the above vinyl compound can be mentioned. In view of obtaining a resin having a high acid value and a long breakpoint by using a compound having a hydrophobic substituent as a monomer component of a resin (the above-mentioned Lu [b] method), as a vinyl resin containing a carboxyl group, Preferably, it contains styrene such as styrene or α-mercaptostyrene; butyl (meth)acrylate, pentyl methacrylate, hexyl methacrylate, and dodecane (meth)acrylate a chain (mercapto)acrylic acid alkyl ester having a carbon number of 4 or more, such as a base ester or a 2-ethylhexyl (meth)acrylate; (meth)acrylic acid isotonate, (meth) propylene 1 ring Amyl, (mercapto) phthalic acid hydrazine fund, freshly burned vinegar, (ethyl) 2-ethyladamantyl acrylate, alicyclic (alkyl) acrylate, benzyl (meth) acrylate And the like as a resin of its copolymerization component. In the case of using an alkali-soluble resin in the present embodiment, a resin having a cross-linked structure (the above-mentioned [c] method) can be obtained by the following method. The epoxy resin containing an unsaturated group and a carboxyl group may, for example, be a method of separately heating the epoxy resin containing an unsaturated group and a carboxyl group in the presence of a polymerization initiator, or heating the unsaturated group and The carboxyl group epoxy resin and the #functional "2 | a mixture of compounds capable of containing an ethylenically unsaturated group, and partially form a crosslinked structure. A monofunctional or bifunctional ethylenically unsaturated group-containing compound used in the crosslinking of the epoxy group containing an unsaturated group and a carboxyl group in 312XP/invention specification (supplement)/96-09/96119465 23 200804976 Specific examples thereof include styrene, α-methylstyrene, hydroxystyrene, (fluorenyl) decyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Ester, amyl (mercapto) acrylate, hexyl (meth) acrylate, • dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxy decyl (meth) acrylate , (meth)acrylic acid hydroxyethyl ester, (mercapto)acrylic acid propyl propyl ester, (mercapto) isopropyl acrylate, (fluorenyl) dicyclopentanyl acrylate, (mercapto) acrylic acid 2-曱 fund Alkyl ester, 2-ethyl succinyl (meth) acrylate, benzyl (meth) acrylate, hydrazine (meth) acrylate, hydrazine-dimethylaminoethyl ester, hydrazine-(meth) propylene oxime Minoline, (meth)acrylonitrile, (meth)acrylamide, hydrazine-hydroxyindole (fluorenyl) propylene Amine, hydrazine, fluorenyl fluorenylamine, hydrazine, hydrazine-dimethylaminoethyl (meth) acrylamide, ethyl hydrazine, ethyl ketone Acrylic vinegar, diethylene glycol di(meth) acrylate, propylene glycol bis(indenyl) acrylate, trimethylolpropane bis(indenyl) acrylate, glycerol di(decyl) acrylate, pentaerythritol II (meth) acrylate, bis-A (meth) propionate, bis-a bis [oxyethyl (meth) acrylate], bisphenol A bis [epoxy propyl ether (Methyl) acrylate] and the like. The above-mentioned ruthenium-containing oxime-based resin may be a method in which a polyfunctional compound containing an ethylenically unsaturated group is used as a copolymerization component. • A polyfunctional ethylenically unsaturated group-containing compound which is a copolymerization component of the vinyl group-containing resin, and specific examples thereof include ethylene glycol bis(indenyl)acrylate and diethylene glycol. Di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, three 312XP/invention specification (supplement)/96-09/96119465 24 200804976 Hydroxyl group Propane tris(fluorenyl) acrylate, trimethylol propyl epoxicone, bis-(fluorenyl) propylene vinegar, propylene triacetate (meth) acrylate vinegar, glycerol Acrylate, glycerol propylene oxide addition tris(indenyl) acrylate* ester, pentaerythritol bis(indenyl) acrylate, quaternary tetraol tris(mercapto) propylene. acid ester, pentaerythritol tetra ( Methyl) acrylate, dipentaerythritol penta(indenyl) acrylate, dipentaerythritol hexa(indenyl) acrylate, bisphenol A bis(indenyl) acrylate, bisphenol A bis[oxyethyl (mercapto) Acrylate], bisphenol A bis [epoxypropyl ether (fluorenyl) acrylate], and the like. The polyfunctional ethylenically unsaturated group-containing compound having a crosslinked structure is preferably 5 mol% or less, more preferably 3 mol% or less, based on the copolymerization component. When the cross-linking structure is too large, the resin obtained as a result of the copolymerization tends to be gelled, and when the thermosetting composition is formed, it is difficult to dissolve in the following organic solvent or tend to cause development residue. The alkali-soluble resin in the present embodiment is preferably one which does not contain an aromatic group or a phenyl group which has no substituent or a substituent at a P (pair) position. In this case, there is a tendency that the protective film is discolored (red) due to heat treatment, and cracking due to heat is suppressed. Examples of such an alkali-soluble resin include a copolymer of -styrene or dicyclopentanyl (meth)acrylate; • a bisphenol A epoxy compound or an epoxy resin, or a substituent which may have a substituent Addition of an adduct compound containing an α, a monounsaturated carboxylic acid to an epoxy compound or an epoxy resin of a skeleton; and further adding a polycarboxylic acid and an acid liver thereof to the above adduct compound 312XP/Invention Manual (supplement)/96-09/96119465 25 200804976 Obtained compound. Further, the alkali-soluble resin in the present embodiment is preferably a component which does not contain any of an ethylenically unsaturated group or an epoxy group. That is, an alkali-soluble resin containing an ethylidene-unsaturated group or an epoxy group tends to have a decrease in storage stability of the composition, which is not preferable. Specific examples of the alkali-soluble resin containing no ethylenically unsaturated group or epoxy group include (A-2) a vinyl group-containing resin. More specifically, (alkyl) acrylate / (mercapto) acrylic copolymer, styrene / (alkyl) acrylate / (mercapto) acrylic copolymer, (mercapto) acrylic acid Hydroxyalkyl ester / alkyl (meth) acrylate / (mercapto) acrylic acid copolymer, styrene / hydroxyalkyl (meth) acrylate / alkyl (meth) acrylate / (mercapto) acrylic acid copolymer , (mercapto) acrylate acrylate/maleic acid copolymer, styrene/(mercapto)acrylic acid alkyl vinegar/maleic acid copolymer, (mercapto) hydroxyalkyl acrylate/( Methyl)alkyl acrylate/maleic acid copolymer, styrene/(mercapto)acrylic acid φ hydroxyalkyl ester/(mercapto)acrylic acid alkyl ester/maleic acid copolymer, and the like. Further, as the alkali-soluble resin, from the viewpoint of suppressing generation of gas in the case of heating the thermosetting composition of the present embodiment and improving heat resistance, it is preferable to satisfy the following relationship. [Relationship] V2/V32 1·3 (V2: weight content of an alkali-soluble resin having a molecular weight (M2) obtained by a GPC method using polystyrene as a standard substance to obtain a differential molecular weight distribution In the case of a curve, it corresponds to a molecular weight of 101/2 times the molecular weight (Ml) of the maximum peak value 312XP/invention specification (supplement)/96-09/96119465 26 200804976. V3 ·· has a maximum peak value The molecular weight (mi) is 1 〇-" 2 times the molecular weight (M3). The weight content of the soluble resin) • The differential molecular weight distribution curve is expressed in comparison with the soluble resin. The weight content of the soluble resin corresponding to the molecular weight of each molecular weight. Further, such a differential molecular weight distribution curve is measured by a GPC method using polystyrene as a standard material in the same manner as the above molecular weight measurement method. The V2/V3 value is usually ΐ3 or more, preferably 15 or more, more preferably 1.8 or more, and usually 1,000 or less, preferably 5 Å or less, more preferably 200 or less. By using such an alkali-soluble resin having a molecular weight distribution having a low molecular weight component, the image formability can be improved, the strength of the protective film can be increased, and the indium tin oxide (IT, indi(10)tin oxide) film on the protective layer can be suppressed. The generation of crack defects. Further, the alkali-soluble resin having the specific molecular weight distribution can be obtained, for example, by treating φ as follows, that is, by dissolving a commonly obtained soluble resin in the following organic solvent (such as isopropyl glycol monoacetic acid g). After the resin solution, the solvent of the soluble resin such as methanol is mixed, and the resin is precipitated and filtered, and the precipitated resin is filtered, for example, air-dried under the conditions of reduced pressure, 4 〇 ° C, and 12 hours. The content of the above-mentioned soluble resin in the thermosetting composition of the present embodiment is usually 5% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, based on the total solid content. Preferably, it is 7% by weight or less. If the amount of the soluble resin is too small, there is a case where the reproducibility of the surface shape of the image section 312XP/invention specification (supplement)/96-09/96119465 27 200804976 is lowered, and the heat resistance is lowered. The sensitivity is lowered and the imaging dissolution rate is lowered. (B) Compound having an ethylenically unsaturated group. A compound having an ethylenically unsaturated group used in the thermosetting composition of the present embodiment (hereinafter, abbreviated as "ethylenically unsaturated compound") It is a compound which has one or more ethylenically unsaturated bonds in a molecule. Further, the thermosetting composition of the present embodiment preferably contains a compound having two or more ethylenically unsaturated groups. Examples of the compound having one or more ethylenically unsaturated groups include unsaturated carboxylic acids such as (mercapto)acrylic acid, crotonic acid, methacrylic acid, maleic acid, isaconic acid, and citraconic acid, and Its alkyl ester, (mercapto) acrylonitrile, (meth) acrylamine, styrene and the like. In addition, examples of the compound having two or more ethylenically unsaturated bonds in the molecule include an ester of an unsaturated carboxylic acid and a polyhydroxy compound, and a phosphate containing a (fluorenyl) acryloxy group. Hydroxy acrylate compound • (meth)acrylic acid urethane with polyisocyanate compound, and (meth)acrylic acid or (meth)acrylic acid acetal compound and polyepoxide epoxy (methyl) Acrylates, etc. These may be used alone or in combination of two or more. • (B-1) an ester of an unsaturated acid and a polyalkyl group-ester (as an ester (meth) acrylate) Specifically, the following compounds can be exemplified. The reactant of the unsaturated carboxylic acid and the sugar alcohol, as the sugar alcohol, for example, ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol 312XP/invention specification (supplement)/ 96_〇9/96119465 28 200804976 Hydroxymethylpropane (addition number 2 to 14), propylene glycol, butanediol, hexanediol, calcined, propylene glycol, pentaerythritol, dipentaerythritol and the like. The reactant of the above-mentioned unsaturated hydrazine and the oxygen (tetra) adduct of a sugar alcohol: the same as the above. The alkylene oxide adduct is exemplified by an oxyethylene adduct or a propylene oxide adduct. The reaction product of the above unsaturated carboxylic acid and an alcohol amine: examples of the alcohol amines include diethanolamine, triethanolamine and the like. As the ester of the above unsaturated carboxylic acid and polyhydroxy compound, more specifically, the following compounds can be exemplified. ^ Ethylene glycol, (meth)acrylic acid vinegar, diethylene glycol di(meth) acrylate, propylene glycol bis(indenyl) acrylate, trishydroxypropyl propane bis(indenyl) acrylate, trimethylol Propane tris(fluorenyl) acrylate, trimethylol tert-propane ethylene oxide addition tris(indenyl) acrylate, glycerol di(decadienoic acid vinegar, glycerol tri(meth) acrylate , glycerol, propylene-acrylic acid addition of tris(indenyl) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol, tris(decyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol Methyl) acrylate, dipentaerythritol hexa(meth) acrylate, and the like, and the same crotonic acid, isocrotonic acid, cis-butyric acid, isaconate, citraconate, and the like. Further, examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include aromatic acids such as the above unsaturated carboxylic acid and p-diphenol, resorcin, pyrogallol, bisphenol F, and bisphenol A. Reactants of polyhydroxy compounds, or their ethylene oxide adducts Specifically, for example, bisphenol A bis(indenyl) acrylate, bisphenol A bis [oxyethyl (indenyl) acrylate], bisphenol 312XP / invention specification (supplement) / 96-09 /% 119465 29 200804976 A bis [epoxypropyl ether (mercapto) acrylate], etc. Further, examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include the above unsaturated carboxylic acid and tris(2-hydroxyl) a reaction product of a heteropolyhydroxyl compound such as ethyl)isocyanurate, specifically, for example, di(meth)acrylate of triethylidene)isocyanurate or tris(methyl) ) Propionate and the like. Further, the ester of the above-mentioned unsaturated tarenic acid and polyalkyl group-containing compound may, for example, be a reaction product of the above unsaturated carboxylic acid, polyvalent carboxylic acid or polyhydroxy compound. Specifically, for example, (mercapto)acrylic acid, condensate of phthalic acid and ethylene glycol, condensate of (mercapto)acrylic acid, maleic acid and diethylene glycol, (meth)acrylic acid a condensate of p-benzoic acid and pentaerythritol, a condensate of (mercapto)acrylic acid, adipic acid, butanediol and glycerin, and the like. (B-2) a phosphate containing a (meth) propylene decyloxy group as a phosphate ester containing a (fluorenyl) propylene fluorenyloxy group, and is a sulphonate compound containing a (fluorenyl) propylene fluorenyloxy group, There is no particular limitation, and φ is preferably represented by the following general formulae (la) to (Ic). [Chemical 3]

m

m) • cm η 312XP / invention manual (supplement) / 96 · 〇 9/96119465 200804976 (in the formula (la), (lb) and (Ic), R1. represents a hydrogen atom or a methyl group, p and p' are An integer of 1 to 25, q is 1, 2, or 3.) Here, preferably p and p are 1 to 1 Å, especially 1 to 4, respectively. Specific examples of such a compound include (meth) acryloxyethoxyethyl phosphate, bis[(meth) propylene methoxyethyl] phosphate, and (meth) propylene oxime. Ethoxyethylene glycol phosphate or the like, which may be used singly or as a mixture. (B-3) A hydroxy ester of a (meth) acrylate and a poly(isocyanate) compound of a fluorenyl (meth) acrylate, and a hydroxy group of (meth) acrylate, for example, a hydroxy group of (mercapto) acrylate A (hydroxy) hydroxy acrylate compound such as a methyl ester, a hydroxyethyl (meth) acrylate or a tris(hydroxy) ethane tri(meth) acrylate. Further, examples of the polyisocyanate compound include aliphatic polyisocyanates such as dihexyl isocyanate and 1,8-diisocyanate isocyanate decyl octyl; and cyclohexane diisocyanate and dinonylcyclohexane. An alicyclic polyisocyanate such as a diisocyanate, a 4, 4-decylene bis(cyclohexyl isocyanate), an isophorone diisocyanate or a bicycloheptane triisocyanate; 4' 4 a phenyl group of diisocyanate, 2 An aromatic polyisocyanate such as an isocyanate phenyl) thiolate; or a heterocyclic polyisocyanate such as isocyanurate; or a method disclosed in JP-A-2002-261 Allophanate modified polyisocyanurate; isomeric isocyanate compound. 312ΧΡ/发明发明(补件)/96-09/96119465 31 200804976 As a (meth)acrylic acid ester compound and a polyisocyanate compound (mercapto)acrylic acid urethane, preferably containing the above ureidocarboxylic acid The (meth)acrylic acid urethanes of modified polyisocyanurate are modified. The (mercapto)acrylic acid amine oxime esters containing the allophanate-modified polyisocyanurate have low viscosity, excellent solubility in a solvent, and are suitable for photohardening and/or thermal hardening. The adhesion to the substrate and the improvement in film strength are effective, and are preferable in this respect. As the above-mentioned (meth)acrylic acid amide phthalate head in the present embodiment, a commercially available one can be used. Specifically, for example, Shin-Nakamura Chemical Corporation

Manufactured under the trade names "U - 4HA", "Μ- 306A", "UA-MC340H", "M ~ Birthday 34〇11", "1161^8", 3&761411] &0311, with ureido formic acid The ester skeleton compound "AGROR4060" and the like. The (meth)propionate urethane in the present embodiment is preferably one or more in a single molecule, and preferably has six or more (preferably six or more, more preferably eight or more). Amino phthalate linkages [[---C0-0-], and 4 or more (preferably 6 or more, more preferably 8 or more) (mercapto) propylene-based compounds. This compound can be obtained, for example, by reacting the following compound (i) with a compound of the following (ii). (1) A compound containing four or more urethane bonds in one molecule. For example, a compound containing four or more kinds of a base group and a diisocyanate in one molecule such as pentaerythritol or polyglycerol may be mentioned. a compound obtained by reacting a diisocyanate compound such as an ester, a trimethyl hexamethylene diisocyanate, an isophora with a diisocyanate or a decyl diisocyanate; (i-1); 312XP/invention specification (supplement)/96 -09/96119465 32 200804976 Alternatively, a compound containing two or more hydroxyl groups in one molecule such as ethylene glycol

"DURANATE24A-100" manufactured by Cheng Industrial Co., Ltd., "DURANATE 22A-75PX", "DURAMTE 21S-75E", "DURAMTE 18H-70β" and other biuret type, and "MRAMTE P-301-75E" a compound (i-2) obtained by reacting a compound containing three or more isocyanate groups in an amidine molecule such as "DURANATE Ε-402-9GT" or an "adduct type" such as "DURANATE Ε - 405 - 80Τ"; A compound (i-3) obtained by polymerizing or copolymerizing ethyl isocyanate (mercapto) acrylate or the like. A commercially available product can be used as the compound, and for example, "DURANATE ME20-100" manufactured by Asahi Kasei Kogyo Co., Ltd. can be used. (ii) A compound containing four or more (meth) acryloxy groups in one molecule, for example, pentaerythritol di(meth)acrylate, dipentaerythritol triterpene (mercapto) acrylate, dipentaerythritol tetra(fluorenyl) A compound containing one or more hydroxyl groups and two or more, preferably three or more (fluorenyl) acryloxy groups in one molecule, such as acrylate, dipentaerythritol penta (meth)acrylic acid vinegar, or dipentaerythritol hexaacrylate vinegar. • Here, as the molecular weight of the compound of the above (i), it is preferably 500 to 200, 〇〇〇, particularly preferably 1,000 to 1,50,000. Further, the molecular weight of the above (meth)acrylic acid urethane is preferably 6 Å to 150, 0 Å. Further, 'such (meth) propionate amino phthalic acid vinegar, for example, by making the compound of the above (i) and the compound of the above (ii) in benzene or ethyl acetate 312XP / invention instructions ()) /96-09/96119465 33 200804976 and other organic solvents in 10~15 (rc reaction 5 minutes ~ 3: and". In this case 'preferably to make the former isoniaric acid; The ratio is 1/10~10", if necessary, use a catalyst such as n-butyltin laurate. Instead, use a base-based propylene or a (meth)acrylic acid acetal compound and an epoxy compound + latex compound. (Mercapto) acrylates As the polyepoxy compound, for example, (poly)ethylene glycol polyepoxypropyl fluorene, (poly)propylene glycol polyepoxypropyl scaly, (4) butane diol polyepoxy propylene Base scale, (poly) pentanediol polyepoxypropyl group, (poly) neopentyl glycol polyepoxypropyl ether, (poly) hexanediol polyepoxypropyl ether, (9) trimethyl methacrylate Polyepoxypropyl (tetra), (poly) glycerol polyepoxypropyl, (poly) sorbitol polyepoxypropyl ether and other aliphatic polyepoxide; phenolic phenolic polyepoxide, bromine Phenolic phenolic polyepoxy compound, (0, 1, P-) anthraquinone phenolic polyepoxy compound, bisphenol A poly ring & bisbis bisphenol F polyepoxy compound and other aromatic polyepoxide; sorbose Polycyclic epoxy oxime esters such as polyglycidyl ether of alcohol anhydride, triepoxypropyl isocyanurate, triepoxypropyl tris(2-diethylethyl) isocyanurate; Epoxy compound. The epoxy (meth) acrylate which is a reaction product of a (meth)acrylic acid or a (hydroxy) hydroxy acrylate compound and a polycyclo compound, may be exemplified by such a polyepoxy compound. a reaction product of acrylic acid or the above-mentioned hydroxy ester (meth) acrylate compound, etc. (Β-5) Other ethylenically unsaturated compound 312ΧΡ/Invention specification (supplement)/96-09/96119465 34 200804976 As other ethylenicity Examples of the saturated compound include, in addition to the above, (meth) acrylamide such as ethyl bis(indenyl) acrylamide; allyl esters such as diallyl phthalate; and phthalic acid. a compound containing a vinyl group such as divinyl carboxylate; an ether containing phosphorus pentasulfide or the like The ethylenically unsaturated compound of an ether bond sulfide becomes a thioether bond, whereby crosslinking rate of ascension of a thioether bond-containing compounds.

Further, a polyfunctional (meth) acrylate compound having a particle diameter of 5 to 30 nm is used, for example, in a decane coupling agent containing an isocyanate group or a fluorenyl group as disclosed in JP-A No. 3,164,407 and JP-A-9-100111.矽Sol [for example, isopropyl alcohol-dispersed organic sol (IPA-ST from Nissan Chemical A), methyl ethyl ketone-dispersed organic sol ("MEK_ST" manufactured by Seiko Chemical Co., Ltd.), methylation The butyl ketone disperses the compound which is bonded to the organic stone sol ("SST" manufactured by Nissan Chemical Co., Ltd.). This compound is a compound which is obtained by reacting a stagnation sol with an ethylenically unsaturated compound via a zebra calciner to enhance the strength and heat resistance of the cured product. Further, as another ethylenically unsaturated compound, those known from the Japanese Patent Laid-Open Publication No. 2005-165294 can also be used. They may be used alone or in combination of two or more. In the present embodiment, it is preferable that the polyunsaturated compound contains a compound containing two or more ethylenically unsaturated groups in the molecule. A vinegar (methyl) acetophenone oxime, a (meth) propyl oxy phthalate or a (meth) acetoacetic acid (IV), more preferably vinegar (meth) acrylate From the purpose of the vinegar (A 312Xp / invention manual (supplement) / 96-09/96119465 35 200804976 base) acrylates, particularly preferred for bisphenol A di (meth) acrylate, double age A double [ An aromatic polyhydroxy compound such as oxyethyl (meth) acrylate vinegar, bis (a epoxidized propyl ether) or an ethylene oxide adduct thereof Further, in the ethylenically unsaturated compound of the present embodiment, the protective film may be inhibited from containing no aromatic ring or containing a substituent or a phenyl group having a substituent at the p (pair) position. It is preferable to heat-treat and discolor (red), and as such an ethylenically unsaturated compound, for example, An aliphatic polyfunctional (fluorenyl) acrylate, a bisphenol A or a (mercapto) acrylate compound having a hydrazine skeleton, etc. The ethylenically unsaturated portion of the thermosetting composition of the present embodiment The content of the compound is usually 1% by weight or more, preferably 20% by weight or more, and usually 7% by weight or less, preferably 60% by weight or less based on the total solid content. If it has an ethylenically unsaturated group When the amount of the compound is too small, the moisture tends to decrease, and the development speed of the image is lowered. If the amount is too large, the reproducibility of the image cross-sectional shape is likely to be lowered and the photoresist film is thinned. The component (B) in the present embodiment. In the case of a compound having two ethylenically unsaturated groups, the ratio of the compound having two ethylenically unsaturated groups to the total weight of the above component (A) and the above component (b) is usually 丨〇重•里More preferably, it is 20% by weight or more, and the upper limit is usually 7% by weight, preferably 60% by weight or less. If the content of the compound containing two ethylenically unsaturated groups is too large, there is resistance. chemical On the other hand, if the amount is too small, there is a case where the peeling property is lowered. In addition, 'at least a part of the use contains three or more ethylenically unsaturated groups 312XP/invention specification (supplement)/96_〇9/96119465 36. Compound of 200804976 In the case of the component (B) in the present embodiment, the content of the compound containing three or more ethylenically unsaturated groups is usually 1 part by weight based on 1 part by weight of the soluble resin of the (Α) component. 1% by weight or less, more preferably 60 parts by weight or less, more preferably 55 parts by weight or less. • The content of the compound containing three or more ethylenically unsaturated groups in the component (Β) relative to the total of the (Β) component The weight is 1 part by weight, usually 8 parts by weight or less, preferably 60 parts by weight or less, more preferably 55 parts by weight or less. The ratio of the compound containing three or more ethylenically unsaturated groups to the total weight of the above-mentioned component (spring) and the above component (Β) is usually 6% by weight or less, preferably 50% by weight. /. Hereinafter, it is more preferably 40% by weight or less, and the lower limit is usually 5% by weight or more. By using a compound containing three or more ethylenically unsaturated groups, the effect of the hardness of the cured film is increased. However, if the content is too large, the peeling property after exposure is liable to be lowered. The blending ratio of the component (Β) to the component (Α) is usually 15 parts by weight or less, preferably 120 parts by weight or less, more preferably 120 parts by weight or less, based on the blending ratio of the component (Β) to the component (Α). It is 11 parts by weight or less, usually 50 parts by weight or more, preferably 70 parts by weight or more, and more preferably 8 parts by weight or more. (C) Photopolymerization initiator - Any known one can be used as the photopolymerization initiator to be used in the thermosetting composition of the present embodiment, and it can be produced by ultraviolet light to visible light. Unsaturated radical polymerization of free radicals. Specific examples of the polymerization initiator which can be used in the present embodiment are listed below. 312ΧΡ/Invention Manual (supplement)/96-09/96119465 37 200804976 2 (4A"It^t,6-bis(trichloromethyl) are all three wells, (曱乳基奈基)-4, 6-double (trichloroindenyl) are all three, 2 (4-ethoxynaphthyl)-4,6-bis(trichloroindenyl) are all three, 2_(4_ethoxyl Base)-4,6-bis(trichloroindenyl):::Speaking of halogens ^ " ^ J-opened temple halogenated thiolated trimorphine derivatives. (n) i-substituted thiolated bismuth Azole derivatives, 2_(o-phenyl)_4b disaccharide salon dimer, 2-(o-chlorophenyl)-4,5-bis(3,monomethoxy miso dimer, 2-( O-fluorophenyl)_4,5-diphenyl-saliva dimer, = o-methylphenyl)-4, 5-diphenylimidyl dimer, 2_(o-methoxyphenyl)-4 , imidazole derivatives such as 5-diphenylimidazole dimer. (111) Benzoin, benzoin isobutyl ether, benzoin isopropyl ether and other benzoin, benzoin alkyl ethers. (iv) 2-曱Anthracene derivatives such as quinone, 2-ethyl hydrazine, 2-tert-butyl hydrazine, and chloropurine. (v) Benzofluorenone derivatives. (VI) Diphenyl fluorenone, Michelin Ketone, 2 曱Dibenzophenone, 3-mercaptobisbenzophenone, 4-methylbenzophenone, 2-chlorodibenzophenone, 4-bromobenzophenone, 2-mercaptopurine, etc. Benzoquinone derivative (vii) 2, 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxyl —2-N-Phenylphenylacetone, Bu. Hydroxy 1- 1-mercaptoethyl-(p-isopropylphenyl)one, 1-hydroxy-1 (p-dodecylphenyl) ketone, 2- Acetophenone derivatives such as methyl-(4'methylthio)phenyl)_2-carbolinyl-l-propanoid 1, 1,1,1-trichloromethyl-(p-butylphenyl) ketone . (viii). Thioxanthone, 2-ethyl oxime ketone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2, 4-dimercaptothioxanthone, 2, 4-diethyl 312XP /Instruction of the Invention (Supplement)/96-09/96119465 38 200804976 A benzoate derivative such as a thioxanthone or a 2,4-diisopropylthioxanthene (ix)-monomethylaminobenzoic acid group. _ equivalent anthracene derivative. Ethyl ester, p-diethylaminobenzoic acid, ethyl (X) 9-phenyl--(p-methoxy phenyl group, etc. μ derivative. (xi) 9, l〇-monomethyl benzophene Morphine and other derivatives.

(XII) bis(3⁄4-pentadienyl)titanium dichloride, bis(cyclopentadienyl)diphenyltitanium, bis(d-pentadienyl)-di(2,3,4,5,6 — Pentafluorobenzene+yl)chin, bis(cyclopentadienyldi(2,3,5,6-read benzene+yl)titanium, bis(cyclopentadienyl)-di(2,4,6-tri Fluorobenzene 4-yl) titanium, bis(cyclopentadienyl)-2,6-bis(fluorophenyl-1-yl)titanium, bis(cyclopentadienyl)-2,4-di(fluorobenzene 1 -based) titanium, bis(methylcyclopentadienyl)-di(2,3,4,5,β-pentafluorophenyl-1-yl)titanium, bis(methylcyclopentadienyl)-two (2,6-difluorobenzene-i-yl) Titanium, bis(%pentadienyl)-2,6-di-fluoro-3-(pylin-1-yl)-benzene-1-yl titanium An equivalent of a titanocene derivative. (xiii) 2-Mercapto-1[4-(methylthio)phenyl]-2-hydroxyindolinyl-j-propanone ketone, benzyl-dimethylamino-1 -(4-Phenylphenyl)-1-butanone, 2-benzyl-2-didecylamino-1-(4-monophenylphenyl)-4-butanone, benzoquinone4- Monomethylaminoethyl ester, tetradecylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, benzene Acid 2-ethylhexyl-1,4-tetramethylammonium ester, 2, 5-bis(4-diethylaminobenzylidene) • Cyclohexanone, 7-Diethylamino-3 -(4-Diethylaminobenzimidyl)-α-aminoalkylphenone-based compound such as coumarin or 4-(diethylamino)chalcone. (xiv) 2, 4, 6 - fluorenyl phosphine oxide system such as trimethyl benzhydryl-diphenyl-phosphine oxide, bis(2,4,6-trimercaptobenzylidene)-phenylphosphine oxide, etc. ()) / 96 · 〇 9 / 9619465 39 200804976 compound. One (XV) 1 '2 ~ Xin Erqi, Bu [4 - (phenylthio) phenyl]-2- (purine - benzoquinone), Ethyl ketone, oxime 9-ethyl-6-(2-methylbenzhydryl)-9H-isoxazole_3_yl]-1-(0-acetic acid monthly loss) () Japanese Patent Laid-Open No. 20-8068 , special open 2001 — -3^ 2005— 305=报,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The agents may be used singly or in combination of several kinds. As group 2 / °, Japanese Patent Publication No. Sho 53-128G2, JP-A-279-249, JP-A-2-4 Publication, Publication No. special two sides or 6- Laid-Open Patent Publication No. Fine disclosed in the other

A combination of initiators. The photopolymerization initiator which is the thermosetting composition of the butyl I Α ^; 5V for the total solid content, usually ο.1% by weight or more, preferably ILb is more than 1%, μ 通 吊 吊 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ( ( ( ( ( ( ( ( ( ( ( ( ( )decline. = is the compounding ratio of * (G) to the component (8), and the amount of the component (6) is usually 2 parts by weight or less, preferably 2 parts by weight or less with respect to 100 parts by weight, usually less than or equal to Q1 parts by weight.

More than 1 part. J (D) Thermal Crosslinking Agent 312XP / Invention Specification (Supplement) / 96-09/96119465 200804976 The thermosetting composition of the present embodiment is intended to enhance the heat and the chemical properties of the film after heat curing. It may also contain a thermal crosslinking agent. / As a thermal crosslinking agent, a known one can be used if it is a hard-baked reaction after image formation by a Hunan exposure/development image. In addition, the following may be mentioned, and these may be used alone or in combination of two or more. (D-1) A compound containing an epoxy group in the molecule as a molecule used in the present embodiment, having a combination of epoxy groups = such as μ, a mono- or a compound of the formula (4) and an epichlorohydrin are reacted ( a poly(epoxypropyl) bond compound, a (poly) acid compound, a polyepoxypropyl vinegar compound obtained by the reaction, and a (poly) amine compound I and a surface gas alcohol (poly) The glycidylamine molecular weight is converted to a compound of a high molecular weight species.物寺自自低(D 1 -1) polyepoxypropyl hydrazine compound as polyepoxypropyl ether compound', for example, polyethylene glycol oxypropyl epoxide type epoxy resin, double (4_ Diphenyl epoxide = epoxy resin, bis(3,5-dimethylphenyl) di-type epoxy resin, bisphenol oxime-俨 gas system

-Production... Ether type epoxy resin, bisphenol A, % 虱 propyl ether type epoxy resin, tetradecyl bisphenol A bis epoxy resin, epoxy Ethylene sulphur addition double hop A epoxide彻 It is said that: fat, di-based base-stretched oxy group type ΐ and - Α / aldehyde phenolic type epoxy resin, phenol cresol novolac type epoxy resin. In addition, the polyepoxypropyl bond is included in the polyepoxypropyl (tetra) compound. _Invention Manual Axis/96 Juju 961 earned 41 200804976 As a polyepoxypropyl over the tree, the epoxy tree hired, a aging road epoxy tree wax, two production, oxygen resin, the convergence of the two women Epoxy resin, bismuth and naphthalene ester, bismuth and bicyclic epoxy resin. A τ' s phenolic resin such as oxo resin, 亥 等 et al (ΛΚ) nucleus oxypropyl ether compound conjugate, etc., reacted with the remaining radicals to introduce a few bases, and the acidification (D-1 - 2) The polyglycidyl ester compound as a base vinegar compound is exemplified by a hexahydrophthalic acid type epoxy resin. One of the oxime propyl esters (D-1 - 3) polyepoxypropylamine compound as a polyepoxypropylamine compound, for example, the methane-produced bismuth (4-amino group) Phenyl): a lactopropylamine type epoxy resin, an m-amino acid type epoxy resin of iso-cyanuric acid, or the like. One of the 虱 虱 (D-1 - 4) other appeals to another 'as other examples, for example, can be made alone - (methyl) propyl acetoate epoxy propyl vine ... ethyl acrylate; = : 酉 ... -Polypropyl propyl acrylate, butyl butyl acrylate, (mercapto) acrylic acid _3,4 epoxide butyl vinegar, (meth) acrylic acid. , f-epoxypentyl ester, (mercapto)acrylic acid-6,7-epoxyheptyl ester, α-ethyl•acrylic acid-6,7-epoxyheptane vinegar, etc. A polymer formed by the reaction of acid. Alternatively, polymerization of another copolymerizable monomer having a (meth) acrylate having an epoxy group and containing usually 10 to 7 mol%, preferably '" 15 to 60 mol%; Things. 312 ΧΡ / Invention Manual (Supplement) / 96-09/96119465 42 200804976 Examples of the monomer for copolymerization include (meth)acrylic acid, methyl (meth)acrylate, and ethyl (meth)acrylate. Methyl)butyl acrylate, (meth)acrylic acid 2-ethylhexyl ester, phenyl (meth) acrylate, (mercapto) propylene-I cyclohexanyl, (meth) acrylate dicyclopentane Esters, esters of (cyclo)acrylic acid such as dicyclopentyl (meth) acrylate, oxyethyl acrylate, (meth) isopropyl acrylate, and styrene, α-mercapto styrene, p-nonyl styrene A vinyl aromatic compound such as vinyl naphthalene.

As the (meth) acrylate having an epoxy group, a (meth)acrylic acid propyl propyl ester is preferred. Further, preferred monomers for copolymerization include (cyclo)acrylic acid dicyclopentanyl ester, styrene, and α-mercaptostyrene. In the case where the epoxy compound is a resin (sometimes abbreviated as "epoxy resin"), as a preferred molecular weight, if the protective film material (thermosetting composition) of the present embodiment can be uniformly applied in a solution state, It is not particularly limited, and is suitably selected depending on the thickness of the formed coating film, the coating conditions, the purpose, and the like. As its molecular weight, it is usually suitably in the range of 2, 〇S to 300,000, preferably 3, _~1 〇〇, _, more preferably ‘, _ ～ 50, 〇〇〇. Further, the epoxy group used in the epoxy compound or epoxy resin used in the present embodiment is usually an epoxy group for improving stability over time, and for the purpose of being used. (oxetan), 4, 3-epoxycyclohexyl. Further, the epoxy compound of the present embodiment does not contain an aromatic ring: or contains a non-substituted or a base having a substituent at the P (pair) position, and is used to suppress discoloration of the protective film by heat treatment. Red ^ as 312Xp / invention specification (supplement) / 96-09/96119465 heart 200804976 Such an epoxy compound, for example, may be a bisphenol A type epoxy compound and an epoxy resin, and a first skeleton which may have a substituent An epoxy compound, an epoxy resin, a copolymer of epoxypropyl (meth)acrylate, etc. • The thermosetting composition of the present embodiment contains a compound having an epoxy group in the molecule as (D) heat exchange In the case of a crosslinking agent, the content of the epoxy group-containing compound in the 7-knife in the thermosetting composition is usually 60% by weight or less, preferably 5% by weight or less, more preferably 5% by weight or less, based on the total solid content. 30% by weight or less, usually j% by weight or more. If the content of the compound containing an epoxy group in the molecule is too large, the storage of the thermosetting composition solution is likely to decrease, and after exposure and development Stripping (D-2) Nitrogen-containing heat-crosslinkable compound As the nitrogen-containing heat-crosslinkable compound used in the present embodiment, fumarin is allowed to act on melamine, benzotrimeric amine, and glyphosate. Or a compound of urea or an alkyl modified compound thereof. Specifically, as a compound for causing fumarin to act on melamine or an alkylene-modified substance, "Cyme1" manufactured by Cytec Industries Co., Ltd. (registered) Trademarks) 300, 3, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, =, 238, 1141, 272, 254, 202, 1156, 1158 "Nlkalac" (registered trademark) E_2i5l, MW-100LM, MX.-750LM, etc. of Sanhe Chemical Co., Ltd. / Other 'as an example of a compound that causes formalin to act on phenyl melamine or its alkyl modified shellfish 'Cymel' (registered trademark) 1123, 1125, 1128, etc. 〇 312XP / Invention Description _ Supplement) / 96-09/96119465 44 200804976 In addition, as a compound that causes formalin to act on glycoluril or its alkyl group Examples of modified substances can be cited as "Cymel (registered trademark) 1170, 1171, 1174, 1172, "Nikalac" (registered trademark) Mx_27 (), etc. In addition, as an example of a compound which causes fumarin to act on urea or an alkyl modified substance, "UFR" (registered by the registrar) 65, 300, "Nikalac" (registered trademark) ΜΧ _29 制造 manufactured by Cytec Industries, Inc. Wait. As the (8) thermal crosslinking agent in the ninth aspect of the present invention, it is preferable that the ruthenium is a compound containing a ruthenium (2) group (wherein R represents a burnt group or a hydrogen atom). It is particularly preferred to have fumarin acting on the alkyl modified product of urea or melamine. When the thermosetting composition of the present embodiment contains the nitrogen-containing heat-crosslinkable compound as the (8) thermal crosslinking agent, the content of the thermally crosslinkable compound as the thermosetting composition is relative to the total solid content. The fraction is usually 篁 下 ' 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳decline. Among them, as a heat-crossing (8), a particularly good compound may be a group of -N(CH2〇R) 2 groups (wherein 'R represents a burnt group or a hydrogen atom), each of which is particularly good for the effect of formalin. In urea oxime or its alkyl modification. N-money compound (Ε) Other ingredients (Ε-1) Adhesive Additive For the purpose of improving the adhesion to the substrate, an adhesive agent can be formulated in the composition. For the heat-hardening of the U form, as the auxiliaries, for example, 312XP/invention specification (supplement)/9(10)/96119465^200804976 decane coupling agent can be mentioned. More specifically, for example, trimethoxy sulphur-based benzoic acid, decyl acryloxypropyltrimethoxy oxysulfide, vinyl triethoxy fluorene, vinyl trimethoxy Cyclohexane, r-glycidoxypropyltrimethoxyoxylinane, isocyanatopropyltriethoxylate, cyclohexyl)ethyltrimethoxydecane, and the like. ‘Yuping, I’m a couple,’ I’m alone, or I’m mixing them.

In addition, the decane coupling agent not only functions as an adhesion aid, but also imparts moderate heat fusion to the protective film during heat treatment (the function of heat flow is improved to flatness and flatness is 1) The coupling agent may, for example, be a linear compound having an epoxy group, for example, γ is exemplified by r-glycidoxypropylmethoxy decane, 々_(3,4-epoxy). % hexyl) ethyltrimethoxy hydride calcined, etc. In the case of using an adhesion aid, the total amount of the solidification component as the above-mentioned adhesion promoter is usually 〇1% by weight or more based on the total amount of the thermosetting composition. Usually, it is 20% by weight or less, preferably 1% by weight or less. (E-2) Surfactant The thermosetting composition of the present embodiment is used to improve the coating property of the coating liquid of the composition and heat hardening. For the purpose of developing the composition layer, etc., it may contain a nonionic, anionic or cationic amphoteric surfactant, or a surfactant such as fluoroquinone or polysecondic oxygen. For example, polyoxyethylene alkyl test, polyoxygen Alkene polyoxypropylene alkyl _, polyoxyethylene alkyl benzene bond 46 312 ΧΡ / invention instructions (supplement) / 96-09/96119465 200804976 class, polyoxyethylene alkyl esters, polyoxyethylene fatty acid vinegar, C III Alcohol fat = 酉文知, polyoxyethylene glycerol fatty acid g, pentaerythritol fatty acid = class, polyoxyethylene pentaerythritol fatty acid ester, sorbitan fatty acid vinegar, polyoxyethylene sorbitan fatty acid A vinegar, a sorbitan fatty acid vinegar, a polyoxyethylene sorbitan fatty acid ester, etc. As such a commercial item, polyoxyethylene such as "Emulgeni 〇:p" and "Emulgen A60" manufactured by Kao Co., Ltd. It is a surfactant and the like.

Further, examples of the anionic surfactant include a burnt acid salt, a burnt benzene (10) salt, a silk naphthalene yarn, a polyoxyethylene ketone ether hydrochloride, and a burnt sulfate. Pyridyl sulfate g-type salts, higher alcohol sulfate sulfates, aliphatic alcohol sulfates, polyoxyethylenes, sulfonium sulfonium oxyethylene alkyl phenyl ether sulfates, alkyl phosphates Classes, ^Oxygenene-based sulphur-based phosphates, polyoxyethylene-based benzene-phosphates, special polymer surfactants, and the like. Among these, a special high molecular surfactant is preferred, and a special polycarboxylic acid type polymer interfacial activity is preferred.

As such an anionic surfactant, a commercially available product can be used. For example, the sulfuric acid ester salt can be exemplified by "E rib 丄 1 〇" manufactured by Kao Co., Ltd., and the alkylnaphthalene sulfonate can be exemplified. "Pe1 ex NB L"# manufactured by Kao Co., Ltd. 'The special surfactant-based surfactants are "H. Qing coffee 1 L - 18" manufactured by Hana Co., Ltd., "H 〇 〇 〇 〇 L - 1 〇〇" and so on. Further, 'the above-mentioned cationic surfactants include quaternary salt, class derivatives, amine salts, and the like, and are used as an amphoteric interface 47 312XP/invention specification (supplement)/96·〇9 /96119465 200804976 !·生宾'J' can be cited as a beet test compound, a salt of a salt, a miso salt, a ϋ ^^ member #肖, etc., preferably a quaternary ammonium salt Preferably, it is a stearin trimethylammonium salt. As a commercial product, for example, "Acetamin 24" manufactured by Kao Co., Ltd., etc., and four grades of salt, etc., can be cited as "Quartamin 24p" and "Quartamin" manufactured by Kao Co., Ltd. 86W" and so on. On the other hand, as the fluorine-based surfactant, a compound having a fluorine-based group or a gas-extended group at at least any of a terminal, a main chain and a side chain is preferred. • Specifically, for example, u, 2, 2-tetrafluorooctyl hydrazine as “tetrafluoropropyl” ether, 1,1,2, 2-tetrafluorooctyl hexyl ether, octylene glycol Di(M,2,2-tetrafluorobutyl)ether, hexanediol bis(nm3-hexafluoropentyl)ether octylpropanol-(1,1,2,2-tetrafluorobutyl)ether, Hexanediol mono(M,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecylsulfonate, 1' 1' 2, 2, 8, 8, 9, 9, 10, 10 - decafluorododecane, ll 2, 2, 3, 3 - hexafluorodecane, and the like. • As such a commercial product, "BMM 1", "ΒΜ-11", manufactured by BM Chemie, "Megaface F142D" made by Dainippon Ink Chemical Industry Co., Ltd., " Megaface F172", "Megaface FI 73", "Megaface FI 83", "Megaface F470", "Megaface, F475", rFC43〇 manufactured by Sumitomo 3M Co., Ltd., and "DFX" manufactured by NE〇s Co., Ltd. ~ 18" and so on. In addition, examples of the polyfluorene-based surfactant include "T〇ray Si η c〇ne DC3pA" manufactured by T〇ray Silicone Co., Ltd., the same SH7PA", "same DC11PA", and "same SH21PA". "Same as SH28PA", 31 invention manual (supplement)/96-09/96119465 48 200804976 "Same as SH29PA", "same as SH30PA", "same as SH8400", "TSF-4440" manufactured by Toshiba Si 1 icone Co., Ltd. , "TSF-4300", "TSF-4445", "TSF-444(4)(5)(6)(7)6", "TSF-4460", "TSF-4452", manufactured by Sil icone Co., Ltd. "KP341", "BYK323" and "BYK330" manufactured by BYK Chemie. Among these surfactants, a fluorine-based surfactant and a polyfluorene-based surfactant are preferable in view of the uniformity of the coating film thickness. The surfactant may be a combination of two or more kinds, and examples thereof include a polyfluorene-based surfactant/a surfactant, a polyoxo-based surfactant/a special-polymer surfactant, and a fluorine-based interfacial activity. Combination of agent/special polymer surfactant. Among them, a polyfluorene-based surfactant/fluorine-based surfactant is preferred.

In the combination of the polyoxo-based surfactant/fluorine-based surfactant, for example, "TSF4460" manufactured by GE Toshiba Silicone Co., Ltd. / "DFX-18" manufactured by NEOS Corporation, and "BYK" manufactured by BYK Chemie Co., Ltd.

- "300" or "BYK-330" / "S-393" manufactured by Seimi Chemical Co., Ltd., "讣340" manufactured by Shin-Etsu Chemical Co., Ltd. / "F-478" or "F-475" manufactured by Dainippon Ink Co., Ltd. "8117?1" / - 11 manufactured by ay Si 1 icone, "〇3-401" manufactured by the company, "11-77" manufactured by the company "L-77" manufactured by the company / "FC4430 manufactured by Sumitomo 3M" When the thermosetting composition of the present embodiment contains a surfactant, the content ratio of the surfactant in the thermosetting composition is preferably 10% by weight or less based on the total solid content, and more preferably 1 to 5 wt%. 312XP/invention specification (supplement)/96·09/96119465 49 200804976 (E-3) The time in the short hardening condition of the hardener or the change of the temperature, the present embodiment = the curable composition may additionally The hardening agent is contained, and various hardening conditions can be appropriately selected according to the coating step of each element. 1. The curing agent is not particularly limited as long as it does not impair the desired function, and examples thereof include a benzoic acid compound and many Domain acid (anhydride), containing more: carboxy oxime: anhydride) Compound 'thermal acid generating agent, an amine compound, a polyamine compound (iv) block t you like. In particular, in the case where the above epoxy group-containing compound is used as the thermal crosslinking agent, a thermosetting agent is preferably used. CE-3-1) benzoic acid-based compound as a benzoic acid-based compound, which may have a hydroxyl group, a halogen group, an alkyl group, a fluorenyl group at the 2- to 6-position of the benzene ring of benzoic acid or benzoic acid. Substituents such as 醯j, alkoxy, aryl', _propyl. Among them, a hydroxyl group having a higher curing ability to epoxy resin is preferably used as the substituent 2 as having two or more base groups. Examples of such a benzoic acid compound h include 3,4,5-trihydroxybenzoic acid, 2,5-dihydroxybenzoquinone-2,6-monohydroxybenzoic acid, and 3,4-dihydroxyl. Benzoic acid, 2, 4, 6-trihydroxybenzoic acid, and the like. Α〜3—2) Polycarboxylic acid (anhydride) Examples of the polyvalent carboxylic acid (anhydride) include monodecyl bis heptene phthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic acid. An alicyclic polycarboxylic acid (anhydride) such as an acid anhydride, a trialkyltetrahydrophthalic anhydride or a nonylcyclohexene dicarboxylic anhydride; a sulphuric acid anhydride, a trimellitic anhydride, a pyromellitic anhydride, Diphenyl hydrazine M2XP / invention manual (supplement) / 96-09/96119465 5 〇 200804976 :: 竣::: aromatic polycarboxylic anhydride such as benzophenone tetracarboxylic anhydride; glass anhydride. Benzoic acid, cis-butyl a hydrolyzate γΛ of an alicyclic aromatic acid anhydride such as adipic acid or cyclopentamethylene tetraacid. Among the 'isoindoles, preferred are trimellitic acid (anhydride), phthalic acid, and an acid anhydride. (Ε — 3—3) A polymer containing a polybasic citric acid (anhydride) as a yttrium containing a polycarboxylic acid (anhydride), which may be exemplified by maleic acid (anhydride) The carboxylic acid (anhydride) fish in the molecule will be right ^ ^ 八, the knife in the inner 3 has more than one polymer of the ethylenically unsaturated bond of the polymer, 哎 切 匕 匕 A A A 此种 此种 此种Acid (anhydride) A partial half ester modified polymer such as a port P. /乍: a compound containing one or more ethylenically unsaturated bonds in the molecule, such as oxan (f-based) acrylic acid, and its alkyl group, (meth) propyl group, (meth) acrylamide, Styrene, an olefin having a (poly)alkyl group, and the like. It is preferred to use a polymer which contains a polycarboxylic acid (anhydride) as a polymer, and a viewpoint of the strength of the cured film. It is preferably a copolymer of an olefin having a substituent such as a cis-succinic anhydride and a di-light-alkoxy group or an alkyl group. . "Let ^ + ^ (E - 3 - 4 ) a thermal acid generator as a thermal acid generator, and examples thereof include an aromatic diazonium salt, a di-salt salt, a monophenylphosphonium salt, a triallyl sulfonium salt, and = One side of the soil... Also / 归石石西盐等夂录德

Salt compounds, acid esters, self-priming compounds, and the like. Q As a specific example, = scented diazonium salt can be exemplified by chlorinated hexa-a • heavy solitude, 7 methylamino ί hexahydrate diazonium salt, naphthyl hexafluorophosphate diazonium salt, dinonylamine Naphthyl tetra-I acid diazo salt and the like. — 312ΧΡ/Invention Manual (Supplement)/96-09/96119465 51 200804976 In addition, as the diaryl lock salt, bismuth diphenyltetrafluoroborate, bismuth diphenyl hexafluoroantimonate, diphenyl six Bismuth fluorophosphate, bismuth diphenyltrifluorosulfonate, ruthenium 4,4'-di-t-butyl-diphenyltrifluoromethanesulfonate, 4,4'-di-di-tert-butyl-diphenyl Bismuth tetrafluoroborate, 4,4'-di-t-butyl-diphenylhexafluorophosphate, and the like. Further, examples of the monophenylphosphonium salt include benzyl-p-hydroxyphenylsulfonyl hexafluorophosphate, bishydroxyp-hydroxydifluorenyl hexafluoroantimonate, and p-ethoxycarbonylphenyldifluoride. Hydrazine fluoroantimonate, benzyl-p-hydroxyphenyl decyl hexafluoroantimonate Φ 锍, a monophenylphosphonium salt type such as a compound represented by the following formula (Π), or a benzylphenyl phosphonium salt type. In the formula, Z represents a phenyl group. Further, examples of the triallyl sulfonium salt include triphenyltetrafluoroborate, ruthenium triphenyl hexafluorophosphate, ruthenium triphenyl hexafluoroantimonate, and tris(p-chlorophenyl)tetrafluoroboric acid. Anthraquinone, tris(p-chlorophenyl)phosphonium hexafluorophosphate, tris(p-chlorophenyl)phosphonium hexafluoroantimonate, bismuth 4-tert-butyltriphenylhexafluorophosphate, and the like. As the triallyl selenium salt, selenium triallyl tetrafluoroborate, triene, propyl hexafluorophosphate, triallyl hexafluoroantimonate, bis(chlorophenyl)phenyl four In the case of bismuth bismuth, bis(chlorophenyl) phenyl hexahydrate, bismuth (chlorophenyl) phenyl hexafluoroantimonate or the like. Examples of the sulfonate include benzoic acid benzoate, p-nitrobenzyl-9, 10-ethoxyindole-2-sulfonate, 2-nitrobenzylsulfonate, 312XP. /Invention Manual (Supplement)/96-09/96119465 52 200804976 2,6-Dinitrobenzyl sulfonate sulfonate. '2,4-dinitrobenzyl-based sulfonate-as a self-supplement compound', 2-chloro-2-phenylacetophenone, 2, _^chloroacetophenone, 2'4'6 -Tris(trichloromethyl)-trientrine, 2_(p-methoxymethanthyl)-4,6-bis(trichloromethyl) are all three, 2-phenyl-4, 6: chloromethyl ) all three, 2-(p-methoxyphenyl)_4,6_bis (three gas ^ two:: two oxime:: ': methoxy t and -2- (4-fluoro-based) - ^-trichloroethane, bis-i, (decyl)-2,2,2-trichloroethanol, bis-2-(4-methoxyphenyl hydrazine: > ethane, etc., one Among these thermal acid generators, a monophenylphosphonium salt type or a benzylphenylsulfonium salt type is preferred in view of light transmittance and strength of the cured film. Further (E-3-5) amine compound Examples of the amine compound include ethylenediamine, 1,3-diaminopropane, anthracene, 4-diaminobutane, hexamethylenediamine, _ 2,5-dimethylamethylenediamine, and piperidine. , pyrrolidine, triethylenediamine, trimethylhexamethylenediamine, dinonylcyclohexylamine, tetramethylguanidine, triethanolamine, N,n,-dimethylpipenine, dicyandiamide, or a derivative thereof ; DBU (1,8-diaza double) (5,4,0) undecene-d, DBU is an aliphatic amine such as tetraphenyl-borate (primary, secondary, tertiary); soil. m-phenylenediamine, diaminodiphenylnonane , diaminodiphenyl milling, diaminodiethyl decane, benzyl dimethylamine, dinonylamino phenol, 2-(diamine dimethyl fluorenyl) phenol, 2 , 4,6-tris(didecylaminomethyl)phenol, pyridine, acridine, DBU (1,8-diazabicyclo(5,4,0)undecene_n, 2,4b 312XP /Invention Manual (Supplement)/96-09/90119465 53 200804976 Aromatic amines such as tris-ethylhexyl acid salt of tris(dimethylaminomethyl)phenol (primary, secondary, tertiary); 2-methylimidazole, 2-ethyl-4-mercaptoimidazole, 2-ethyl-4-methylimidazole, .2-undecylimidazole, 2-pyridinylimidazole, 2-phenyl Imidazole, 1-benzyl.-2-methylimidazole, 1-cyanoethyl-2-hydrazinoimidazole, 1-cyanoethyl-2-ethyl-4-mercapto miso, 1-cyano Benzyl-2-indenylpyrrolidine, 1-cyanoethyl-2-indole-burning sulphur-salt-p-benzoic acid ester, 2-methyl mirbium-isocyanurate, 2-phenylimidazolium·isocyanurate, 2,4-diamine _ -6-[2-mercaptoimidazolyl-(1)]-ethyl-distributive, 2,4-diamino-6-[2-ethyl-saltyl-(1)]-B Base-average three-speaking, 2,4-diamino-6-[2~11-alkyl-based succinyl-(1)]-ethyl-all-seven, 2-phenyl-4,5-dihydroxy Mercaptoimidazole, 2-phenyl-4-methyl-5-hydroxydecyl imidazole, 1-ranylethyl-2-phenyl-4,5-di(cyanoethoxymethylpyrene Salic compound; diethylenetriamine, imine bispropylamine, bis(hexamethylene)triamine, and the like. Among these, from the viewpoint of the strength of the cured film, dicyandiamide and DBU-based tetraphenylborate are preferred. (Ε - 3 - 6) Polyamine compound As the polyamine compound, for example, triethyltetramine, tetraethylidene pentaamine, pentaethylhexamine, dinonylaminopropylamine, and Ethylaminopropylamine, aminoethylpiperidine, menthanediamine, isofluorodiamine, bis(4-amino-3-indolylcyclohexyl)oxime, diaminodicyclohexyl An aliphatic polyamine such as an amine, ν, ν-didecylcyclohexylamine, an aromatic polyamine such as a strepamine, a benzodiazepine, a xylylenediamine derivative or a monoamine amine dimer. Among these, preferably 312 χΡ / invention specification (supplement) / 96-09/96119465 54 200804976 is N,N-didecylcyclohexylamine. CE-3-7) Block carboxylic acid as the block carboxylic acid, for example, the above (poly) carboxylic acid and the tick acid containing the polymer are disclosed by Japanese Patent Laid-Open No. Hei No. Hei No. Hei. In the method disclosed in, for example, JP-A-2004-339332, the method disclosed in JP-A-2004-339333, etc., is added to a block acid or the like of ethylene ether. Among the above-mentioned curing agents, the polymer containing a polyvalent carboxylic acid (anhydride), a rust salt compound, a block carboxylic acid compound, and a benzoic acid compound have good curing activity, and can obtain high hardness and adhesion to a support. The sex aspect is better. More specifically, maleic anhydride and a polyoxypropylene group having a carbon number of 丨 to another alkyl group, a carbon number of 丨 15 or a polyethylene oxypropylene group having a carbon number of 1 to 15 may be mentioned. a polycarboxylic acid copolymer of at least one vinyl compound selected from the group consisting of ethylene, butene, or a propylene compound and styrene; • inclusion of an adduct of trimellitic acid or maleic acid and ethyl vinyl ether a carboxylic acid compound; a benzoin compound such as 2,5-dihydroxybenzoic acid or 3,4,5-trihydroxybenzoic acid; a base group-p-hydroxyphenylmethyl hexafluorophosphate, p-hydroxyphenyl group Mercapto hexafluoroantimonate rust, p-ethoxylated phenyldifluorenyl hexafluoroantimonate, a pair of Ik-based fluorenyl hexafluoro acid recording mirrors, the above formula (positive) a monophenylphosphonium salt such as a compound or a monophenylphosphonium salt such as a benzylphenylphosphonium salt. These hardeners may be used alone or in combination of two or more. 312XP/Invention Manual (Supplement)/96-09/96119465 55 200804976 As a hardener, the polycarboxylic acid copolymer and the benzoic acid compound are excellent in adhesion to the support, and The hardness is improved. In particular, the benzoic acid (tetra) compound is excellent in thermosetting property and high in light transmittance, and is preferred because it has a low effect of discoloration. In the case where the thermosetting composition of the present embodiment contains a curing agent, the content of the curing agent in the thermosetting composition is usually 0.05% by weight or more, preferably 〇1. The weight % is 2% or less, preferably 1% by weight or less. If the amount of the hardener is too small, it tends to cause a decrease in the viscosity and hardness of the support body, and on the contrary, it tends to cause an increase in the weight loss. (F) Additives in the thermosetting composition, in addition to the above-mentioned components to carry various additives, for example, the ortho-based di-p-benzoic acid, p-methoxy group, 2, 6-two may have a substituent. The ratio of the third butyl group to the age of the solid is the ratio of the total amount of the compound to the total opening: 1% by volume or less, preferably 2% by weight or less. In the same manner, a plasticizer such as dioctyl phthalate ortho-diphenyl phthalate or a tri-f-phenyl phenyl phosphate is contained in an amount of 40% by weight or less, preferably 20% by weight or less. - 夂 〆 Furthermore, in the thermosetting property of the present embodiment, a polymerization accelerator is added. As the polymerization, it is considered to be a '4' vr_ ^ # 〇 Μ Μ Μ 4 4 4 4 4 4 Μ 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四暴本 opened imidazole, 2-mercapto benzoxazole, 3 312XP / invention manual (supplement) / 96-09/96119465 56 200804976 sparse base 1,2,4 - three squat, 2 - squid-4 (3H) - hydrazine, /3-mercaptocil, ethylene glycol dithiopropionate, trishydroxypropyl propane trithiopropionate, pentaerythritol tetrathiopropionate, etc. Compounds, polyfunctional thiol compounds such as hexanediol, trishydroxypropyl propane trithiogluconate, pentaerythritol tetrathiopropionate, hydrazine, hydrazine-dialkylamino benzoate, hydrazine- An amino acid having an aromatic ring or a derivative thereof, such as a phenylglycine or a derivative thereof such as an ammonium salt or a sodium salt, a phenylalanine acid, or a salt such as an ammonium or a sodium salt or a derivative such as an ester. In the case of adding a polymerization accelerator to the thermosetting composition of the present embodiment, the content ratio thereof is preferably 20% by weight or less, more preferably 1 to 10% by weight based on the total solid content. Further, in the thermosetting composition of the present embodiment, an ultraviolet absorber may be added as needed. The ultraviolet absorber is added for the purpose of controlling the thermosetting composition of the present embodiment formed on the substrate by absorbing the specific wavelength of the light source used for the exposure by the ultraviolet absorber. The rate of photohardening at the time of film exposure. By adding an ultraviolet absorber, it is possible to obtain an effect of improving the pattern shape after exposure and development, or eliminating the residue remaining in the non-exposed portion after development. As the ultraviolet absorber, for example, a compound having an absorption maximum between 250 nm and 400 nm can be used. More specifically, for example, Sumisoapl30 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORBIO, EVERSORB11, EVERSORB12 (made by Taiwan Yongguang Chemical Industry Co., Ltd.), Tomisoap800 (manufactured by API Corporation), SEESORBIOO, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, 312XP /Invention Manual (Supplement)/96-09/96119465 57 200804976 Dibenzophenone compound such as SEESORB106, SEESORB107, SEES0RB151 (Shipro Chemical System);

Sumisoap200, Sumisoap250, Sumisoap300, . Sumisoap340, Sumisoap350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by Seongbuk Chemical Industry Co., Ltd.), TINUVIN PS, TINUVIN99 - 2, TINUVIN109, TINUVIN384 - 2, TINUYIN900 ^ TINUYIN928 ^ TINUYIN1130 (manufactured by Ciba Specialty Chemicals), EVERSORB70, EVERS0RB71, EVERS0RB72, Φ EVERS0RB73, EVERS0RB74, EVERS0RB75, EVERS0RB76, EVERS0RB234, EVERS0RB77, EVERS0RB78, EVERSORB80, EVERS0RB8K Taiwan Yongguang Chemical Industry Co., Ltd., TomisoaplOO, Tomisoap600 (manufactured by API Corporation), SEESORB701, Benzene triazole compounds such as SEESORB702, SEESORB706, SEESORB704, SEESORB706, SEESORB707, SEES0RB709 (Shipro Chemical); 0 Sumisoap400 (manufactured by Sumitomo Chemical Co., Ltd.), phenyl phthalate compounds such as phenyl salicylate; TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477DW A hydroxyphenyl β-three well compound such as TINUVIN479 (manufactured by Ciba Specialty Chemicals). Among them, a benzotriazole compound and a hydroxyphenyl tributary compound are preferred, and a benzotriazine compound is particularly preferred. In the case where the ultraviolet absorber is added, as a blending ratio, the total solid content of the thermosetting composition is usually 〇.〇1% by weight 312ΧΡ/invention specification (supplement)/96-09/96119465 58 200804976 If it is 10% by weight, if it is difficult to be excessive, it is 15% by weight or less, preferably 5% by weight or more. When the blending ratio of the ultraviolet absorber is less than the range, the effect of improving the shape of the pattern and/or eliminating the occurrence of the residue is likely to cause a decrease in sensitivity and/or a decrease in the residual film ratio. (G) Organic solvent Each of the above components is usually obtained by using an organic solvent. It is preferable that the weight is "fine", and the organic solvent is not particularly limited as long as it can dissolve, disperse, and operate the above components. Specifically, for example, it can be sirolius, ethyl cyanosine, butyl cyanidin, diethylene glycol mono-niobium, (one: early acid: propylene glycol diacetate, propylene glycol single A shouted acetic acid vinegar (hereinafter, there is a % between "PGMAc"), methyl ethyl _, J ketone, cyclohexanone, toluene, chloroform, dichloromethane, acetic acid ethyl t-lactic acid methyl vinegar, lactic acid , propionic acid 3 -methoxymethyl -, propionic acid 3 - ethoxy acetoacetate, propylene glycol monomethyl sulphate, methanol, ethanol, propanol, butanol, tetrahydrofuran, ethylene glycol dimethyl ether, acetic acid The oxybutyl ketone, s〇ivess oxime, carbitol, etc. As the above-mentioned organic solvent, it is preferably in the range of 1 〇〇 to 2 ,, more preferably in the range of 120 to 17 〇 ° C. The organic solvent may be used singly or in combination of two or more. As a combination of the organic solvents to be used in combination, for example, pgmac may be mixed with diethylene glycol dimethyl ether, methoxyacetic acid Tg, Μ· And one or more organic solvents selected from carbitol. In the above mixed solvent, from diethylene glycol dimethyl scale, methoxy butyl acetate 312 ΧΡ / ^ 0 ^ | ^ 0^^(^{φ)/96.〇9/96119465 59 200804976 The ratio of the organic solvent selected from the ester, Solvesso, and carbitol is usually 1% by weight or more, preferably 3, based on the PGMAc. 〇% by weight or more, usually 80% by weight or less, preferably 7% by weight or less. In the mixed solvent, the mixed solvent of PGMAc and methoxybutyl acrylate induces a moderate degree of the coating film in the coating and drying step. The fluidity is preferred in order to flatten the unevenness of the substrate. [2] Method of Forming Protective Film Next, a method of forming a protective film of the thermosetting composition of the present embodiment will be described. [2 - 1 ] The coating step is performed on the substrate on which the TFT array is formed, and the thermosetting composition of the present embodiment is coated with a rotating H or a ring-shaped (four) coating [curtain coater, die coater, coater). Coating by a coating device such as a sprayer. The coating thickness of the thermosetting composition is usually 〇. 5~5 # m. [2 ~ 2 ] The drying step removes (drys) the volatile component from the coating film. Form a dry coating film. Dry, vacuum drying, heating plate, Infrared oven, convection oven, etc. The preferred drying conditions are temperature 4G~15 (rc, drying for 60 minutes. [2 - 3] Exposure and development steps. Place a mask on the dried coating film of the thermosetting composition layer. == Line image exposure. After exposure, use the image to remove the degree of unexposed: 2 = Su Wei: Yes, after exposure, before the image is enhanced, there are (4) post-exposure post-baking. For baking, use 312XP/invention manual (supplement)/96-09/96119465 6〇200804976 heating plate, infrared oven, convection oven, etc. After exposure, the bar is 40~l50t, and the drying time is 1〇~6〇 minutes. It is generally required that the image obtained after development requires 2 () (four) wideness. In addition, in order to achieve high enamel quality, the tendency of the fine line reproducibility of the spring, the ground again: high = want = degree as the cross-sectional shape of the fine line image after development, non-image and image The rectangular shape with a clear contrast has a wide imaging range, such as development time, development time of the liquid, physical stimulation, and the like, and is therefore preferable. , wood / 乍 is the light source used in the exposure step of the dry coating film, heart lamp, tungsten wire lamp, high pressure mercury lamp, ultra high pressure mercury lamp 2: tooth: lamp, medium pressure mercury lamp, low pressure mercury lamp, etc. or argon ion mine laZer&gt ;Y^- Aluminura Lr excimer laser, nitrogen laser and other laser sources. In the case of light with a special wavelength, a filter can also be used. ^The solvent used in the development process is not particularly limited as long as it has the ability to dissolve the uncured portion of the t-film, and the above-mentioned environmental pollution, harmfulness to the human body, and fire hazard are considered. Sexually, it is an Asian-African organic solvent, and an alkaline imaging solution is used. Examples of such an inspectable developing solution include inorganic compounds such as sodium carbonate, sodium carbonate, carbonic acid unsalted, potassium hydrogencarbonate, sodium sulphate, potassium oxalate, sodium oxychloride, and hydrogen secret potassium. Or an aqueous solution of an organic test compound such as diethanolamine, triethylamine, triethanolamine or tetramethylammonium hydroxide. :: Alkaline imaging solution may also contain surfactant, water-soluble 'machine solvent, wetting agent, low molecular compound with trans- or slow acid group 312XP / invention manual (supplement) / 96-09/96119465 61 200804976 Scum and other changes have been made. In particular, since the surfactant has a large amount of developability, resolution, and good effect, it is preferably added. As the surfactant used in the developing solution, an anionic surfactant interface material of an acid group or a benzoic acid group is exemplified. ~ There are four cations of the base, there is no particular limitation on the method of imaging treatment, usually 1 () ~ 5 generations

The development temperature of f is 15 to 45 ° C is performed by methods such as immersion development, stirring development, highlight imaging, scanning imaging, and ultrasonic imaging. [2 - 4] Heat treatment step - The thermosetting composition film which forms an image by the exposure/development step is then subjected to a heat treatment (hard baking) step to form a cured product (thermosetting film). Further, after development, the full exposure may be performed before hard baking for the purpose of suppressing the occurrence of degassing during hard baking. In the case of full exposure before hard baking, the light source uses ultraviolet light or visible light, for example, xenon lamp, tooth lamp, tungsten lamp, high pressure mercury k, super pressure mercury lamp, metal halide lamp, medium voltage Mercury lamps, low-pressure mercury lamps and other light sources or argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers and other laser sources. In addition, a hard plate, an infrared oven, a convection oven, or the like can be used for hard baking. The hard baking conditions are usually in the range of 100 to 250 ° C and the drying time is in the range of 30 seconds to 90 minutes. [3] Liquid crystal display device (panel) Next, the manufacturing method of the liquid crystal display device (panel) of the present embodiment is described by adding 312XP/inventive book (supplement)/96-09/96119465 62 200804976. The liquid crystal display device of this embodiment is generally provided with a TFT active matrix substrate. s First, the cured material is formed on the substrate on which the TFT element array is formed as a protective film, and an I τ film is formed thereon, and an I τ ο ο ο ο . And the liquid crystal display device of the present invention can be formed by bonding the TFT active matrix substrate and the opposite substrate to form a liquid crystal single-cell, injecting liquid crystal into the formed liquid crystal cell, and then connecting the opposite direction. electrode. As the counter substrate, a color filter substrate having an alignment film is generally used. As the alignment film, a resin film such as polyimide or the like is preferable. The formation of the alignment film is usually carried out by a gravure printing method and/or a flexographic printing method, and the thickness y of the alignment film is several tens nm. After the hardening treatment of the alignment film by hot calcination, the surface treatment is carried out by irradiation of ultraviolet rays or treatment of the alignment cloth, and processing is performed to adjust the surface state of the liquid crystal. Further, a protective film similar to the above may be formed on the alignment film. The bonding gap between the TFT active matrix substrate and the counter substrate is generally selected in the range of 2 (four) or more and 8 (four) or less depending on the use of the liquid crystal display device. After bonding to the counter substrate, the portion other than the liquid crystal injection port is sealed by a sealing material such as an epoxy resin. • As such a sealing material, it is usually used to cure by UV irradiation and/or heating. After the peripheral sealed liquid crystal cell is cut into the panel unit, the vacuum chamber is decompressed, and the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal chamber is leaked, and the liquid crystal single 312XP/invention specification can be supplemented. Piece) /96-09/96119465 ^ 200804976 Inject liquid crystal into the element. The degree of decompression in the soil as the liquid unit is usually 1χ1〇_2 Pa or more, preferably lxl (T3Pa or more, usually lxl (r7pa or less, preferably ΐχΐ〇·6 Pa or less). The liquid crystal cell is preferably heated at the time of pressing, and is usually more than the above, preferably 5 Å or more, usually 100 C or less, preferably in the range of go ° c or less. The heating holding condition is usually in the range of 10 minutes or more and 60 minutes or less. Thereafter, the liquid crystal cell is immersed in the liquid crystal. The liquid crystal unit is injected into the liquid phase to cure the uv hardening resin to seal the liquid crystal injection port. Further, the liquid crystal display device (panel) is not particularly limited, and any known liquid crystal such as an aromatic system, an aliphatic system or a polycyclic compound can be used. Any one of lyotropic liquid crystal and thermotropic liquid crystal can be used. Any of the thermotropic liquid crystals may be a nematic liquid crystal, a smectic liquid crystal, or a cholesteric liquid crystal. [Embodiment] Next, the present embodiment will be described more specifically by way of examples and comparative examples, as long as This embodiment does not take off The following is not limited to the following examples. The constituent components of the thermosetting composition used in the following examples and comparative examples are as follows: (A) Alkali-soluble resin 312XP/invention specification (complement) Piece)/96-09/96119465 200804976 [Chemical 5]

PI: Acid value: 110 mg-KOH/g Mw : 7, 400 ([weight average molecular weight] + 20000) / [acid price]: 249

Acid value: 106 mg-KOH/g Mw ·· 17, 100 ([weight average molecular weight] + 20000) / [acid price]: 350

Acid value: 115 mg-KOH/g Mw : 14,000 ([weight average molecular weight] + 20000] / [acid price] · 296 65 312XP / invention manual (supplement) / 96-09/96119465 200804976 pm

p:c|:r= 10:30:60 acid value·· 33 mg-KOH/g Mw : 8, 200 ([weight average molecular weight] + 20000) / [acid price]: 855 [chemical 6]

Acid value: 130 mg-KOH/g Mw : 45,000 ([weight average molecular weight + 20000] / [acid price]: 500 PS:

Acid value: 259 mg-KOH/g Mw : 42,800 66 312XP/invention specification (supplement)/96-09/96119465 200804976 ([weight average molecular weight] + 20000) / [acid price]: 242

Acid value: 85 mg-KOH/g Mw : 8,300 ([weight average molecular weight] + 20000) / [acid value]·· 333 (B) Compound having an ethylenically unsaturated group [Chemical 7]

/=\ 9^3/===\ 〇 QH 03⁄4 -OH Q

Gongrongshe Chemical Epoxy Ester 3000M 10 M2:

CHa B %n 笤 2·0

Kyoeisha Chemicals Light Ester BP-2EM 312ΧΡ/Invention Manual (supplement)/96·09/96119465 67 200804976 瞧 Nippon Chemical Co., Ltd.

M4: Ο

OH

OH Ο

Gongrongshe Chemical Epoxy Ester 3000A (C) Photopolymerization Starter [Chem. 8]

H^CS

Irpaacure 907, manufactured by Ciba Specialty Chemicals

312XP/Invention Manual (supplement)/96-09/96119465 68 200804976

Irjacure OXE02 (D) Thermal Crosslinker by Ciba Specialty Chemicals χι: Η: CH2OGH3 CH2〇CH3

Nikalac MWIOOLM X2-made by Sanwa Chemical Co., Ltd.

Nippon Chemical Co., Ltd. NC-3000 (E) Other components S1: Fluorine-based surfactant. F475 (F) additive manufactured by Dainippon Ink Co., Ltd. Y1: polymerization accelerator. 2-mercaptobenzimidazole Y2 ··UV absorber. Has the following formula. [化10]

TIBAVIN384-2 312XP / invention manual (supplement) /96-09/96119465 69 200804976 (G) organic solvent PGMAc: propylene glycol monoterpene ether acetate, another alkali-soluble resin used, thermal hardening The composition of the composition and its exposed film and thermosetting film are as follows. - [Acid value] The alkali-soluble resin was measured in accordance with JIS-K0070 (standard oil test method). [Breakpoint] Lu will test the soluble resin on a substrate having a diameter of 4 μm as a dry film thickness, and bake at 9 ° C for 9 seconds on a hot plate. Thereafter, it was bubbled in an aqueous solution of 0.4% by weight of tetramethylammonium hydroxide at 25 °C. The immersion time (sec) at which the surface of the ruthenium substrate was visualized by dissolving or stripping the alkali-soluble resin was taken as a break point. [20% by weight of hydrochloric acid dissolution rate] The thermosetting film obtained by the formation of the above-mentioned thermosetting film was immersed in φ 20% by weight hydrochloric acid at 4 (rc for 2 minutes, and then rinsed with pure water. The film thickness difference (Mm) is divided by the soaking time (2 〇 minutes) as the 20% by weight hydrochloric acid dissolution rate (μιη/min) after hard baking. [Adhesiveness] *Coated in (4) Color filter manufactured by the subsidiary The glass plate for the light sheet was "ΑΝ100". On the glass substrate, a coating film having a dry film thickness of 4 " was obtained by drying on a hot plate at 9 (TC for 90 seconds). The adhesion of the film surface was evaluated on the basis of the following criteria. 〇: No adhesion, no finger marks when pressed by a finger. X: Adhesive, with a finger pressing to form a mark. 312XP/Invention Manual (Repair)/96-09/96119465 70 200804976 [Best exposure] 0 According to [Resolving property] The image of the thermosetting film observed by an optical microscope is as described in the above embodiment. The minimum line width ((10)) of the resolution obtained in the order of formation of the above-mentioned thermosetting film is taken as the analysis [ Pattern shape]

亍...The line pattern of the 20 (10) line width of the pancreas was evaluated on the basis of the following criteria. Hunting this A: good rectangularity, no skirt B · good rectangularity, but a little skirt C: poor rectangularity, or no resolution [residue] ~ observed by optical microscopy in the order of formation of the above-mentioned thermosetting film The blank pattern of the 30mi line width of the thermosetting film of the waiter is evaluated below for the residue of the blank portion. A. No residue B · Only the residue C is found in the peripheral portion of the photoresist. · Residue is also found in the center of the blank portion. [Releasability] The thermosetting film obtained in the order of formation of the above-mentioned thermosetting film is combined with the glass substrate. N-methylpyrrolidone in 6 〇. 〇 Soak for a few minutes and evaluate on the basis of the following criteria. 312XP/Invention Manual (Supplement)/96-09/96119465 71 200804976 〇: There is no thermosetting film remaining on the substrate. X··There is a thermosetting film remaining on the substrate. [Chemical resistance] The thermosetting film obtained in the order of formation of the above-mentioned thermosetting film was immersed in 20% by weight of hydrochloric acid at 4 (TC for 20 minutes, and evaluated according to the following criteria. 〇. Even by optical microscope The surface observation was carried out, and no pores or surface collapses (concavities and convexities) were observed. X. Observation of the surface by an optical microscope revealed that the pores or the surface were wrinkled (concave and convex). Or, by visual observation, white turbidity was observed. Light rate] A cured film was obtained in accordance with the order of formation of the above-mentioned thermosetting film, except that the mask was not used, and the light transmittance of the cured film was measured by a spectrophotometer UV3100PC manufactured by Shimadzu Corporation to obtain a wavelength of 6 〇.最小(10) The minimum transmittance (%) in the range of ~400 nm. [Examples 1 to 7, Comparative Examples 1 to 2] Lu was prepared by the preparation shown in Table 1 to prepare a thermosetting composition. The curable composition was applied to a glass plate "AN100" glass substrate for color filters manufactured by Asahi Glass Co., Ltd., and dried on a hot plate at 9 (TC for 90 seconds to obtain a coating film having a dry film thickness of 4. After self-coating film The side is exposed through a reticle with a line width of 10 #m to 50, using a 3 kW high-pressure mercury lamp. As an exposure, the image illuminance measured by an illuminance meter with a wavelength of 365 nm is ^ mW/cm. The exposure amount of the above optimal exposure amount is set. Next, a 0.4% by weight aqueous solution of tetramethylammonium hydroxide is used as the 312XP/invention specification (supplement)/96-09/96119465 200804976 image liquid at 25 ° C. The substrate was immersed in a developing solution for 70 seconds to carry out development, and further rinsed with pure water to obtain an exposed film, which was obtained by heating the obtained exposed film in a convection oven at 2200 ° C for 1 hour. A thermosetting film was obtained. Various evaluations were performed on the above thermosetting composition, exposed film, and thermosetting film. The results are shown in Table 1.

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Iff rodent (vΜΦΙ) s inch 61196/60-96/ip}®)_s?is distillate e 200804976 According to the results of Table 1, the thermosetting film formed by the thermosetting composition of the present embodiment is It is not only excellent in peelability, chemical resistance, light transmittance, pattern shape, and crushing property, but also a low-curing thermosetting film. In particular, in Example 5 in which a UV absorber was used in combination, a thermosetting film in which a pattern-like shape and a residue characteristic were present was obtained. The thermosetting film which consists of the thermosetting composition of the comparative example 1 has the acid value of the component (A) below the predetermined value, and is a thermosetting film which is bad in adhesiveness, and the peeling property and chemical-resistant property are also bad. . The thermosetting film formed of the thermosetting composition of Comparative Example 2 has a breakage point of a predetermined value or less. Therefore, it is a thermosetting film having poor chemical resistance and poor resolution. (Industrial Applicability) According to the present invention, for example, the following thermosetting composition for a protective film can be formed, and it is not colored during hard baking, and the light transmittance in the visible light region is good, and the viscosity of the coating film is further lowered. Therefore, defects can be reduced, and chemical resistance after heat hardening is also excellent. Further, in this way, it is possible to provide a high-quality liquid crystal display device with a high degree of industrial availability in the field of a film-hardening residue and a liquid crystal display. Dry = Bu, Ming' provides, for example, a solder resist film or a solder resist film in a printed wiring board, a liquid crystal display, a large-scale integrated circuit, a thin transistor, a half coat, a color calender, an organic electroluminescence, or the like. . Further, a thermosetting composition suitable for use as, for example, a liquid crystal, which is suitable for use as a color line, a black matrix, a helper, and a 312 ΧΡ / invention specification (supplement) / 96 〇 9/96119465 75 200804976 is provided. Therefore, the industrial availability in this field is extremely south. Furthermore, this application is based on the patent application filed on May 31, 2006 (Patent No. 2006-152051), the Japanese patent application filed on July 28, 2006 (patent 2006-206555), and 2007. This patent application (Patent 2007-134317) filed on May 21, the entire disclosure of which is incorporated by reference.

312XP/Invention Manual (supplement)/96-09/96119465 76

Claims (1)

200804976 X. Patent application garden: 1. A thermosetting composition for a protective film, which comprises the components (A) to (C): (A) a soluble resin, (β) a compound of an ethylenically unsaturated group, (C) a photopolymerization initiator, an acid value of the above component (Α) of 8 〇mg_K〇H/g or more, and the resin of the above (a) film thickness of 1 (four) The membrane is in a 4% by weight tetramethyl gas oxidized saddle aqueous solution (25. The breaking point in the crucible is 1 sec. or more. The thermosetting composition for a protective film according to claim 1 of the patent scope 'the above The component (8) is a component containing a chemical substance having two ethylenically unsaturated groups, and the compound having two ethylenically unsaturated groups accounts for the total weight of the above component (Α) and the above component (Β). The ratio of the protective film of the first aspect of the invention is a thermosetting composition. The above component (Α) is a component having no ethylenically unsaturated group and an epoxy group. For example, the protective film of patent application 帛1 has a thermosetting composition =, wherein after exposure with the optimum exposure amount Bake treatment under 22〇〇c i: a thermosetting film obtained from time to time, in 20% by weight of hydrochloric acid (4 〇. The dissolution rate in 〇 is 〇·1 M m/min or less. 5·If applying for a patent The thermosetting composition for a protective film of the range 帛1, further comprising the following components: (D) a thermal crosslinking agent. A description of the invention (supplement)/96-09/96119465 77 200804976 6. The cured product is characterized in that it is formed by using a thermosetting composition of the coating film of the first item of the patent scope. ” A liquid crystal display device characterized by having a cured product of the sixth scope of the patent application. As a protective film. 312XP/Invention Manual (supplement)/96-09/96119465 78 200804976 VII. Designation of representative drawings: (1) The representative representative of the case is: None (2) Simple description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 312XP/Invention Manual (supplement)/96-09/96119465 5