TW200809391A - 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 has an excellent peeling property after exposure and development, will not be colored when subjected to baking, has good transmittance in the visible region, and can be used to form, after being thermally hardened, a protective layer having excellent chemical resistance. The thermosetting composition of the present invention comprises (A) an alkali soluble resin, (B) a compound having 2 or more ethylene unsaturated groups, and (C) a photopolymerization initiator. The ethylene unsaturated groups are contained in an amount of between 1 mmol/g and 5 mmol/g with respect to the total weight of the component (A) and the component (B). The exposure film formed by exposing at an optimum exposure amount and hardening the thermosetting composition for a protective film has a dissolving rate of 2.3 &mgr:m/min or below in a 0.4 wt.% of tetramethylammonium hydroxide solution (25 DEG C).

Description

200809391 IX. Description of the Invention: [Technical Field of the Invention] This is a thermal-curable composition for a protective film using light or heat, for example, for a printed wiring board or a liquid crystal display: , parts, plasma display, large-scale integrated circuit, thin = 褒, color coding, organic electroluminescence, etc.; film: two plates &amp; various electronic parts of the insulating coating formation is more useful hardening Sexual composition. Further, the present invention relates to a curable composition which is useful for a liquid crystal panel such as a liquid crystal display, which is useful for a second color filter, a black matrix, a protective layer, a rib portion, and a spacer, and is formed using the same. A cured product, and a liquid crystal display device having the same. [Prior Art] On a thin film transistor (tft, Thin iSt〇r) active matrix substrate used in a liquid crystal display device, between (4) a T array element and a transparent conductive film forming a pixel electrode, a m array element f is formed to protect Interlayer insulating film. Here, a contact hole for connecting the tantalum electrode of the TFH train and the wiring formed of the transparent conductive film is generally formed on the interlayer insulating film. Therefore, a photosensitive thermosetting composition is generally used as the material of the interlayer insulating film. Further, such a thermosetting composition used in the recycling, more specifically β as a positive 3L photosensitive composition, is known to contain a composition of an alkali-soluble resin and a 1'2-quinonediazide (for example, In the case of the negative-type thermosetting composition, a photopolymerizable composition is known (Example 312ΧΡ/Invention Manual (Supplement)/96-09/96119464, 200809391, for example, refer to Patent Document 2). For example, in the conventional positive photosensitive composition disclosed in Patent Document 1, for example, the following cases exist in the above-mentioned Japanese Patent Publication No. 2002-131899. That is, in the case of hard baking after exposure and development, the 1,2-quinonediazide is colored by thermal decomposition, and the visible light rate is lowered. In other respects, the photopolymerization composition disclosed in Patent Document 2 is not easy. There is still room for improvement as described above, but there is still room for improvement in consideration of the concept of "Following I.", that is, if the defect is detected after the exposure and development, the film is easily peeled and cured. Composition film There is a case where repair is possible (there is a case where the production cost of the product can be improved). The conventionally known negative photosensitive composition tends to be difficult to peel off. Further, in the use of the TFT active matrix substrate as described above, After the contact hole is formed, a cured film (a cured film having chemical resistance) which is resistant to various kinds of engraving liquids when the upper transparent conductive film is processed is known. It is conventionally difficult to cope with such peeling resistance. DISCLOSURE OF THE INVENTION An object of the present invention is to provide a thermosetting composition for a security film which is excellent in peelability after exposure and development. "Additionally, another object of the present invention is to provide a coloring-free, visible light-transmitting region during hard baking. A thermosetting composition for a protective film having a good rate. Further, another object of the present invention is to provide a 312XP/invention specification (supplement)/96-09/96119464 1 200809391 which can be formed after thermosetting. The protective film of the protective layer is made of a thermosetting composition. Further, another object of the present invention is to form a protective film by thermosetting [, a product formed by the object. A liquid crystal display device comprising the cured product as a protective film. The thermosetting composition for a protective film according to the present invention is characterized in that it contains (A) an alkali-soluble resin and (8) has two or more ethylenic properties. a composition of a saturated base, and (C) a photopolymerization initiator, wherein the content of the ethylenically unsaturated group is 丨mmolole/g or more based on the total weight of the component (A) and the component (B). The exposure film exposed and hardened at an optimum exposure amount of 5 mmol/g or less was dissolved in a 0.4 wt% aqueous solution of tetramethylammonium hydroxide (25% in a crucible) of 2.3 /zm/min or less. The cured product of the invention is formed using the thermosetting composition for the protective film. In the liquid crystal display device of the present invention, the cured product is provided as a protective film. [Embodiment] According to the present invention, it is possible to provide a thermosetting composition for a protective film which is excellent in peeling property after exposure and development. Further, it is possible 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, a thermosetting composition for a protective film which can form a protective layer excellent in chemical resistance after thermosetting is provided. Further, the cured product formed by the protective film thermosetting composition is a protective film having no coloration during hard baking and a light transmittance in a visible light region, so that the quality is high. - "The liquid crystal display device of the present invention uses a high-quality cured product, so the quality is described in detail in the following description of the embodiment of the present invention in terms of quality, 0, 312XP/invention specification (supplement)/9b 09/96119464 8 200809391. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention. [1] Thermosetting composition for protective film The thermosetting composition for a protective film of the present embodiment (hereinafter sometimes The term "thermally curable composition" is characterized in that it contains the following components (A) to (C), (A) an alkali-soluble resin, and (B) a compound having two or more ethylenically unsaturated groups. (C) The photopolymerization initiator, the content of the ethylenically unsaturated group (hereinafter, abbreviated as "ethylenically unsaturated group equivalent") is 1 based on the total weight of the above component (A) and component (B). a dissolution rate of an exposure film exposed to a minimum exposure amount of 5 mol%/g or less and 5 mmol/g or less and exposed to an optimum exposure amount in a 4 wt% aqueous solution of tetramethylammonium hydroxide (25 ° C) ( Hereinafter, it is sometimes abbreviated as "development dissolution rate") It is 2·3 //m/min or less. In addition, the dissolution rate of the thermosetting film obtained in the N-mercaptopyrrolidone (6(TC)) after exposure to the optimum exposure amount at 220t: baking treatment (hereinafter, sometimes abbreviated as "L" P dissolution rate ") is preferably 〇1 #2 minutes or less. Hereinafter, first, "ethylenically unsaturated group equivalent", "optimum exposure amount, "developing dissolution rate", and "Li P dissolution rate" are added. [Ethylene Unsaturated Group Equivalent] The ethylenically unsaturated group equivalent is calculated by the following formula: Ethylene 312XP per unit weight / invention specification (supplement) / 96-09/96119464 9 200809391 The greater the unsaturated group , the larger the value. <Relationship> Ethylene unsaturated group equivalent (mole/ §) = millimoles of unsaturated unsaturation in the composition / [weight of component (1) t (g) + component (8) Weight (g)] ~ The larger the value of the above ethylenically unsaturated group equivalent, the greater the polymerization density caused by exposure, and the more difficult (4) after development. On the other hand, if the ethylene dibasic group is § If the value is small, the polymerization density caused by the exposure will become small, so there is a deterioration in chemical resistance after hard baking. Further, there is a case where the film reduction phenomenon at the time of development increases, and the resolution and the shape of the pattern are deteriorated. The upper limit of the value of the ethylenically unsaturated group equivalent is 5 亳 mol / 2 or less, preferably 4.5 mmol. The ear/g or less is more preferably 4 mmol/g or less, and the lower limit is 1 mmol/g or more, preferably 15 mmol/g or more, more preferably 2 mmol/g or more. In addition, in the case where the chemical structure formula of the component (B) and the component (A) contain an ethylenically unsaturated group, the "mole number of the ethylenically unsaturated group in the composition" is based on The method of adding the monomer to the predicted chemical formula of the poly-person is calculated. In the present invention, as a method of adjusting the ethylenic unsaturated group equivalent to 1 to 5 mol/g, the following may be mentioned. 1) ~ 3) method. 1) The amount of the compound having two or more ethylenically unsaturated groups is adjusted. 2) When the soluble resin contains an ethylenically unsaturated group, adjust its content. 3) In the compound having two or more ethylenically unsaturated groups, the amount of the ethyl 312XP/___ (supplement)/96-09/96119464 10 200809391 dilute unsaturated group is decreased, and the molecular weight is increased. [Optimum Exposure Amount] This hot-hardening composition is applied to a glass substrate so that the dry film thickness is approximately * (4), and baked on a hot plate under conditions of 赃 and sec. . Thereafter, the lamp is exposed by (10) with a high-pressure mercury lamp. As the exposure conditions, the amount of exposure energy is in the range of 32 〇 mJ/cm 2 , and the exposure energy amount is set at intervals of each time for exposure. After the exposure, it was immersed in an aqueous solution of 4% by weight of tetramethylammonium hydroxide for 70 seconds, rinsed with pure water, and the film thickness of the remaining cured film (exposure film) was measured. The film thickness of the obtained exposed film was plotted with respect to the exposure amount. The minimum exposure amount within a range of 1% by volume of the exposure film when an exposure amount is 21/2 times the exposure amount is defined as the optimum exposure amount (mj/cm2). [Dynamic Dissolution Rate] The thermosetting composition of the present Example was applied onto a glass substrate, baked on a hot plate at 90 ° C for 90 seconds, and the dried film thickness was measured. Thereafter, exposure was performed by an illuminance of 3 〇 mW/cm 2 by a high pressure mercury lamp. The exposure amount is set to the above optimal exposure amount. After the exposure, the film was immersed in a 25-minute (replacement of 4% by weight of tetramethylammonium hydroxide aqueous solution for a fixed period of time (development), and then rinsed with pure water to measure the film thickness of the remaining exposed film. The difference between the dry film thickness after baking and the film thickness of the exposed film remaining after washing with pure water (#m) divided by the development time (minutes) is defined as the development dissolution rate. The greater the value of the speed, the more the chemical resistance after hard baking is 312XP/invention manual (supplement)/96-09/96119464 11 200809391, or the thinning and deterioration of the film during development. The large, resolution and pattern shape are below the above-mentioned clocks in the fine shape of the shell. It is preferably 2 or less, and more than 3.32 / min. There is no special position, usually _ (four) In the minute image = after r, the so-called "hard-baked" system is used to indicate the baking treatment after the exposure of the image. The thermosetting composition is sufficiently thermally hardened to obtain a thermosetting t film. In the Ming Dynasty, as a method of making the dissolution rate of the image reach 2 "... the slaves", the following i) to v) methods are mentioned. , Particularly preferably iv), v) method. The Fo 1 inch) to reduce the acid value of the alkali-soluble resin. Compound having two or more unsaturated heteroaryl group of B, the increase in the number of ethylenically unsaturated groups.

Hi) increases the amount of total solids relative to a compound having two or more ethylenically unsaturated groups. 1V) A soluble resin having an alicyclic group and/or an aryl group is used. v) A polymerization initiator which is less likely to cause polymerization failure due to oxygen (specific examples: mercapto phosphine oxide-based compounds, derivatives). [NMP dissolution rate] The thermosetting composition of the present embodiment was applied onto a glass substrate so that the dried film thickness was approximately 4 /zm, and baked on a hot plate at 9 Torr for 9 sec. . Thereafter, exposure was performed by a high pressure mercury lamp at an illumination of 3 〇 mW/cm 2 312 XP / invention specification (supplement) / 96-09/96119464 12 200809391. The exposure amount is set to the above optimal exposure amount. After the exposure, it was further baked at 220 t for 1 hour in an oven to obtain a thermosetting film. The thermosetting film was immersed in 6 (TC&quot; base material (4) for 2 minutes, and then rinsed with pure water to measure the film thickness of the remaining thermosetting film. The film thickness of the above-mentioned thermosetting film was purely used as described above. The difference in film thickness (/zm) of the thermosetting film remaining after water rinsing is divided by the N-methyl material. The value of the ketone soaking time (minutes) is defined as the hydrazine dissolution rate. The hardening property of the thermosetting film after hard baking is worse. As the dissolution rate of the above-mentioned radish, it is usually preferably 〇1 minute or less, more preferably 0.08 //m/min or less, and particularly preferably 〇〇6. In addition, the lower limit is not particularly limited, and is usually 〇·'min or more. As means for making the NMP bathing speed reach 〇·ι or less, in addition to the above-described developing solution dissolution rate means i) to v), The following means vi), vii) 〇vi) increase the amount of thermal crosslinker. Vii) increasing the amount of crosslinker (epoxy group, -n(CH2〇r)2 group) in the molecule of the thermal crosslinker. In order to provide a thermosetting composition for a film which is excellent in peeling property after exposure and development, the ethylenically unsaturated group equivalent and the image dissolution rate of the thermosetting composition are respectively It is specified in a fixed range. Further, the subject of the present embodiment (improving the peelability) is not a problem generally known to the industry. 312 Χ / Invention Manual (Supplement) / 96-09/96119464 13 200809391 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 above-mentioned essential components, the following components may be blended. (D) Thermal crosslinking agent (E) Other components (F) Additives (G) Organic solvents The following is a description of each component. Further, in the present embodiment, the "(fluorenyl)acrylic group" means "acrylic group and/or mercaptoacryl group". The same applies to "(mercapto) acrylate" and "(mercapto) acrylonitrile". In addition, the addition of "polymerization" to the monomer name means that both the monomer and the polymer thereof are contained, and "(acid) anhydride" and "...acid (anhydride)" mean both a ruthenium acid and an anhydride thereof. The term "(poly)carboxylic acid" means 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. (Α) Alkali-Soluble Resin The linearly soluble resin used in the present invention is a resin which is soluble in the test solvent, and is not particularly useful, and preferably contains a resin of a county or a base. As such an alkali-soluble resin, soil contains unsaturated groups such as methyl acrylate, (meth) acrylate, maleic acid, vinyl acetate, and cis-butyl iranimide, and (d) Epoxy tree 312XP / invention specification (supplement) /%-09/96119464 14 200809391 fat; (meth)acrylic acid, (mercapto) acrylate, (meth)acrylonitrile, (mercapto) acrylamide, a vinyl-based resin containing a hydroxyl group or a carboxyl group, which contains a hydroxyl group or a carboxyl group, such as maleic acid, styrene, vinyl acetate, vinylidene chloride or maleimide; and polyamine, polyester, Polyether, polyurethane, polyvinyl butyric acid, polyvinyl alcohol, polyvinylpyrrolidone, acetaminophen, and the like. These may be used alone or in combination of two or more. Further, in view of alkali developability and image formability, 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 resin containing a carboxyl group, it is preferred to use a vinyl resin containing a carboxyl group without containing an unsaturated group. (A-1) An epoxy resin containing an unsaturated group and a carboxyl group, and an epoxy resin containing an unsaturated group and a carboxyl group, and further, for example, a carboxylic acid adduct containing an α-unsaturated group of an epoxy resin An epoxy resin containing an unsaturated group and a carboxyl group added to a poly-τ carboxylic acid and/or an acid anhydride thereof. That is, an ester bond (-C00-) formed by ring-opening addition of a carboxyl group of (i) an α,/5-unsaturated monocarboxylic acid to (i) an epoxy group of an epoxy resin Further, an ethylenically unsaturated bond is added, and at this time, a hydroxyl group is added to (iii) a carboxyl group of a polyvalent carboxylic acid or an anhydride thereof. Hereinafter, the constituent components of the epoxy resin having an unsaturated group and a carboxyl group will be described. The following 312XP/invention specification (supplement)/96-09/96119464 15 200809391: the knife can be used alone or in combination. Mix two or more types. Oxygen resin-1) The ring used in the epoxy resin containing an unsaturated group contig is used in an epoxy resin containing an unsaturated group and a carboxyl group. Double (four) epoxy resin,: • 裒 树 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂Among them, considering the strength of the high-hardening film, it is preferred to look for the epoxy resin (4) epoxy resin, bismuth and dicyclopentadiene polymer epoxy resin, and its acrylic acid epoxy propyl 3 a copolymer of acrylic acid or the like. Soil (Α~1-2) α,/5-unsaturated monoacid as the α,/3-unsaturated monocarboxylic acid, for example, (meth)acrylic acid, crotonic acid, maleic acid, Fumaric acid, isaconic acid, citraconic acid, etc., and pentaerythritol tri(meth)acrylate succinic anhydride adduct, pentaerythritol tris(meth)acrylate tetrahydrophthalic anhydride adduct, two Pentaerythritol penta(indenyl) acrylate succinic anhydride adduct, dipentaerythritol penta(methyl) acrylate phthalic anhydride adduct, dipentaerythritol penta(meth) acrylate tetrahydrophthalic anhydride An adduct, a reaction product of (meth)acrylic acid and 2-caprolactone, and the like. Among them, (meth)acrylic acid is preferred in view of sensitivity. (A-1 - 3) Polycarboxylic acid or its anhydride as a polyvalent carboxylic acid or its anhydride, for example, succinic acid, maleic acid, isaconic acid, phthalic acid, tetrahydrophthalic acid , 3-mercaptotetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic 312XP/invention specification (supplement)/96·09/96119464 16 200809391 formic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methyl hexahydrophthalic acid, 4-mercapto hexamethylene phthalate, 3-ethyl hexa- phthalate Hyperthyroidism, 4-ethylhexahydro-ortho-carboxylic acid, and their acid sulphate. Among them, from the viewpoint of image reproducibility and development, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferred, and tetradecylene is more preferred. 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 carboxyl group is preferably an epoxy resin. Phenolic novolac epoxy resin, biguanide epoxy resin, hydroxyindole epoxy (resin) or indophenol novolac epoxy 9 resin, α,/5-unsaturated monocarboxylic acid is (meth)acrylic acid, polycarboxylic acid Or its anhydride is tetrahydrophthalic anhydride. Further, the epoxy resin containing an unsaturated group and a carboxyl group is preferably an acid value of from 2 Å to 200 mg-KOH/g, more preferably from 30 to 18 Å. In addition, the "acid value" in the present embodiment is a value measured in accordance with JIS-κ〇〇7〇 (reference grease test method). 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 4 Å, 〇〇〇 or less, preferably 30,000 or less, and more preferably 2〇, 〇〇〇 below. Further, 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). The details of this measurement method are as follows. [Mode] Tosoh Co., Ltd. hlc — 8020 312XP / invention manual (supplement) / 96-09/96119464 17 200809391

[Pipe column] GMHXL manufactured by Tosoh Co., Ltd. — N 30cmx2 [Mobile phase]1 · 0 m 1 /min [column temperature] 40°C

[Solvent] THF (tetrahydrofuran stabilized with 0.03 wt% butylhydroxytoluene) [Standard sample] Polystyrene (PSt) standard sample [Check line] 5 times [Detection] RI (in-device) [Injection amount] 0.1% by weight of 1 〇〇 (the sample is previously filtered by GL Chromatography Disc 13P manufactured by GL·Science Co., Ltd.) The above-mentioned epoxy resin containing an unsaturated group and a carboxyl group in the present embodiment can be obtained by a conventionally known method. synthesis. Specifically, a method in which the above-mentioned epoxy resin is dissolved in an organic solvent and the above-mentioned α, fluorene-unsaturated monocarboxylic acid is added in the presence of a catalyst and a thermal inhibitor can be used. The reaction is carried out, and a polycarboxylic acid or an anhydride thereof is further added to continue the reaction. Here, examples of the organic solvent include organic solvents such as methyl ethyl ketone, cyclohexene self-identification, ethyl-ethyl acetate, and propylene glycol monoacetic acid vinegar. Further, examples of the catalyst include tertiary amines such as triethylamine, dimethylamine, and sulfhydrylamine, or tetramethylammonium chloride, methyl-hydrazine, tetraethyl ammonium, and tetra Butyl ammonium chloride, trimethylbenzyl: a graded salt or a triphenyl lining compound, or a phenyl group, etc.: hydroquinone, p-benzene, and, as the above thermal polymerization Inhibitors such as diphenol monoterpene ether, methyl hydroquinone, and the like. 312ΧΡ/Invention specification (supplement)/%-〇9/96119464 18 200809391 The amount of the above α,/5-unsaturated monocarboxylic acid is usually set to 1 equivalent of the epoxy group of the resin. It is preferably 0.9 to U chemical equivalent. Further, the addition reaction 3 temperature is usually set to 60 to 150 ° C, preferably 80 to 1203⁄4. Further, the compounding amount of the polyvalent carboxylic acid or its anhydride is usually 〇.丨~12: stoichiometric, preferably 0.2 to 1.1 chemistry, based on the chemical equivalent of the hydroxyl group formed in the above-mentioned addition anti-deer&quot; equivalent. The oxy-resin will be exemplified as a specific example of the above-mentioned ring unit containing the oxime group and the carboxyl group. [Chemical 1] 312XP / invention manual (supplement) / 96-09/96119464 19 200809391

HOO0

OOC

J h2c_2oocch=c?h2 GHsH— Ηοόα OCH2CHCH2〇OCCH^CH2 ch2 och2chch2^—

20 book (supplement)/96-09/96119464 200809391 [Chemical 2]

(A-2) A vinyl-based resin containing a carboxyl group. The carboxyl group-containing vinyl resin of the present embodiment is, for example, a copolymer of an unsaturated carboxylic acid and a vinyl compound. Examples of the unsaturated carboxylic acid include (meth)acrylic acid, butyric acid, butane maleic acid, maleic anhydride, isaconic acid, and citraconic acid. It can be used alone or in combination of two or more. Further, 'the vinyl compound may, for example, be styrene, m phenethyl hydrazine, styrene styrene, (fluorenyl) acrylate, (fluorenyl) propyl acetonitrile or (meth) acrylate propyl s. (Mercapto) butyl acrylate, (mercapto) acrylic acid vinegar, (mercapto) hexyl acrylate, (meth) acrylate 12 kiln, 312XP / invention manual (supplement) / 96-09 /96119464 200809391 2-ethylhexyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid Rice ester, dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate, N,N-didecylaminoethyl (meth)acrylate, N-(methyl)propene porphyrin, ( Acrylonitrile, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N, N-dimethyl (decyl) acrylamide, N, N-dimethylamine A copolymer of a vinyl group (meth) acrylamide, a vinyl compound such as vinyl acetate, or the like. These may be used alone or in combination of two or more. Among them, dicyclopentanyl (meth)acrylate is preferred in that it provides a wide latitude for development time and deterioration of developing solution. Examples of such a dicyclopentanyl (meth)acrylate include compounds exemplified in JP-A-2002-89533, for example, a dicyclopentadiene skeleton, a dicyclopentyl skeleton, and a bicyclic ring. A pentenyl skeleton, a (meth)acrylic acid of a dicyclopentenyloxyalkyl skeleton, or the like. In the above-mentioned composite material (vinyl group-containing resin having a carboxyl group), a (meth) acrylate-(meth)acrylic acid copolymer is preferable in view of image shape, sensitivity, and cured film strength, among which Preferably, it comprises a copolymer of 30 to 80 mole % (meth) acrylate and 20 to 70 mole % (meth) acrylic acid. Particularly preferred is a copolymer comprising 50 to 75 mol% of (meth) acrylate and 25 to 5 mol% of (meth)acrylic acid. Further, the acid value of the carboxyl group-containing vinyl resin is usually from 3 〇 to 250 mg to K0H/g, preferably from 50 to 2 〇〇 mg_K 〇 H/g, more preferably from 7 〇 to 150 mg-KOH. /g. Further, the molecular weight of the carboxyl group-containing vinyl resin is usually 312XP/invention specification (supplement)/96-09/96119464 200809391 corpse. The above is preferably U00 or more, more preferably 2, _ is 00 or less, preferably 5 Å or less, and particularly preferably 20 or less. In the case of using the R 1 resin of the upstream R 1 and the ethylene resin of the R, it is preferable that the reproducibility after the development of the image is good. The alkali-soluble resin in the present embodiment is preferably one which does not contain a family ring or which contains an unsubstituted or phenyl group having a silky group at the p (pair) position. In this case, there is a tendency that the protective film is discolored (i-red) due to heat treatment, and cracking due to heat is suppressed. As such a soluble resin, for example, a copolymer of styrene or bis-cyclopentyl acrylate may be mentioned; in the case of a double-type epoxy compound or epoxy resin, or an S skeleton which may have a substituent; An addition compound obtained by adding a carboxylic acid containing a cold-unsaturated group to an epoxy compound or an epoxy resin; and further adding a polycarboxylic acid 70 and an acid anhydride thereof to the above-mentioned adduct compound 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. In other words, an alkali-soluble resin containing an ethylarene-unsaturated group or an epoxy group tends to have a low 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 vinyl group-containing resin having a carboxyl group. More specifically, an alkyl (meth)acrylate / (mercapto) acrylic copolymer, a styrene / alkyl (meth) acrylate / (mercapto) acrylic copolymer, (mercapto) acrylic acid Hydroxyalkyl ester / alkyl (meth) acrylate 312 ΧΡ / invention specification (supplement) / 96-09/96119464 23 200809391 / (mercapto) acrylic copolymer, styrene / (meth) hydroxyalkyl acrylate /(fluorenyl)propionic acid calcination base / (mercapto) acrylic acid copolymer, (mercapto) alkyl acrylate / maleic acid copolymer, styrene / (mercapto) acrylic acid Alkyl ester/maleic acid copolymer, hydroxyalkyl (meth) acrylate / (fluorenyl) alkyl acrylate / maleic acid copolymer, styrene / hydroxyalkyl (meth) acrylate Ester / (alkyl) acrylate / 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, the molecular weight corresponding to the molecular weight (Ml) of the maximum peak value is 1 〇 1/2 times the molecular weight V3 ·· The molecular weight (M3) having a molecular weight (M1) corresponding to the maximum peak value of lo-w times The weight content of the alkali-soluble resin is a weight-containing content of the alkali-soluble resin corresponding to the molecular weight of each molecular weight contained in the alkali-soluble resin. Further, such a differential molecular weight distribution curve is measured by a GPC method using polystyrene as a standard substance in the same manner as the above molecular weight measurement method. The V2/V3 value is usually 13 or more, preferably 15 or more, more preferably 1.8 or more 'usually one shoulder or less, preferably _ or less, 312XP/invention specification (supplement)/96-09/96119464 0/t 200809391 Better than 200 or less. By using such a soluble resin having a low molecular weight component with a small amount of t-sub-distribution, image formability can be improved, and the strength of the protective amine can be increased to 'inhibit the indium tin oxide on the protective layer. ) The generation of crack defects in the film. Further, the above-mentioned specific molecular weight distribution-soluble resin can be known, for example, by dissolving a commonly obtained soluble resin in an organic solvent (such as isopropyl glycol monoacetic acid vinegar or the like) to prepare a resin. After the solution, it is mixed with a poor solvent of the soluble resin such as A*, and the resin is precipitated and the resin which has been decanted, for example, under reduced pressure, 4 Torr. 〇, 12 hours of conditions to make it dry. The content of the alkali-soluble resin in the thermosetting composition of the present embodiment is usually 5% by weight or more based on the total solid content, more preferably 10% by weight or more, and usually 8% by weight or less. It is preferably Μ% by weight or less. When the amount of the alkali-soluble resin is too small, the reproducibility of the image cross-sectional shape may be deteriorated, and the heat resistance may be lowered. If the amount is too large, the sensitivity may be lowered and the development dissolution rate may be lowered. (Β) Compound having an ethylenically unsaturated group The compound having an ethylenically unsaturated group used in the thermosetting composition of the present embodiment (hereinafter sometimes abbreviated as "ethylenically unsaturated compound") is represented by A compound having one or more ethylenically unsaturated bonds in the molecule. Examples of the compound having one or more ethylenically unsaturated groups include unsaturated carboxylic acids such as (meth)acrylic acid, crotonic acid, isobutyric acid, maleic acid, isaconic acid, and citraconic acid. And its alkyl esters, (meth)acrylonitrile, 312 ΧΡ / invention instructions (supplement) / 96-09/96119464 25 200809391 (methyl) acrylamide, styrene and the like. In addition, examples of the compound having two or more ethylenically unsaturated bonds in the molecule include esters of an unsaturated carboxylic acid and a polyhydroxy compound, and phosphates containing a (meth)acryloxy group, (methyl) Ethylene methacrylate compound and polyisocyanate compound (meth) acrylate urethane, and (mercapto) acrylate or (meth) hydroxy acrylate compound and polyepoxy epoxy (meth) propylene Acid esters, etc. The crucible may be used alone or in combination of two or more. (B-1) an ester of an unsaturated carboxylic acid and a polyhydroxy compound as an ester of an unsaturated carboxylic acid and a polyhydroxy compound (hereinafter, abbreviated as "ester (meth) acrylate)", specifically, it can be exemplified The following compounds. The reaction product of the unsaturated carboxylic acid and the sugar alcohol: examples of the sugar alcohol include ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene (addition number 2 to 14), and propylene glycol. Butylene glycol, hexanediol, trishydroxypropylpropane, propylene glycol, pentaerythritol, dipentaerythritol and the like. The reaction product of the above unsaturated carboxylic acid and the alkylene oxide adduct of the sugar alcohol: the sugar alcohol is the same as described above. The alkylene oxide adduct may, for example, be an ethylene oxide 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 and triethanolamine. As the ester of the above unsaturated carboxylic acid and polyhydroxy compound, more specifically, the following compounds can be exemplified. ^ Ethylene glycol di(meth)acrylate, diethylene glycol--leaf-IT-based acrylate, propylene glycol bis(indenyl) acrylate, trimethylolpropane bis(methylamide) 3ΠΧΡ/invention specification ( Supplement)/96·〇9/96119464 26 200809391 Acrylate, Trimethylolpropane Tri(meth)acrylate, Trimethylolpropylene Epoxy Ethylene Addition Tris(indenyl)acrylate, C3 Alcohol bis(mercapto) acrylate, glycerol tri(meth) acrylate, glycerol propylene oxide addition tris(decyl) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri ( Methyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta(indenyl) acrylate, dipentaerythritol hexa(meth) acrylate, etc., and the same crotonate, isocrotate, cis. Adipic acid ester, isaconic acid vinegar, and fluconazole g. Further, examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include an aromatic acid such as the above unsaturated carboxylic acid and hydroquinone, resorcin, pyrogallol, bisphenol F, and bisphenol A. A reactant of a polyhydroxy compound or an epoxy ethylene bromide adduct thereof. Specifically, for example, it is a bis-A (A) acryl vinegar, a bisphenol A bis [oxy-extended ethyl (fluorenyl) acrylate], a double A-double [a bad propyl propyl (meth) acrylate Cool] and so on. Further, examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include a reaction product of the above-mentioned unsaturated carboxylic acid and a heterocyclic polyhydroxy compound such as tris(2-hydroxyethyl)isocyanuric acid vinegar. Specifically, for example, di(meth)acrylate, tris(indenyl)propionate or the like of tris(2-hydroxyethyl)isocyanurate. Further, examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include the above-mentioned unsaturated carboxylic acid, polybasic acid, and a reaction with a polyhydroxy compound. Specifically, for example, (mercapto)acrylic acid, a condensate of phthalic acid and ethylene glycol, (mercapto)acrylic acid, a condensate of maleic acid and diethylene glycol, (mercapto)acrylic acid, Condensate of terephthalic acid and pentaerythritol, 312XP / invention specification (supplement) / 96-09/96119464 200809391 (meth)acrylic acid, adipic acid, condensate of butanediol and glycerol, and the like. (B-2) a carboxylate containing a (meth)acryloxy group as a phosphate containing a (meth)acrylomethoxy group, and a phosphate compound containing a (meth)acryloxy group, There is no particular limitation, and among them, those represented by the following general formulae (la) to (Ic) are preferred. [化3] R10 Ο Η2〇=〇—〇-^CH2

m ί10 ο H2C;占如2,,“0〇^〇} 卿仏卿嶋^_〇—|^)3»qm 〇c) (in the formulas (la), (lb) and (Ic), hydrogen An atom or a fluorenyl group, p and P' are integers of 1 to 25, and q is 1, 2, or 3.) Here, p and p are preferably 1 to 1 Å, especially 1 to 4. Specific examples of such a compound include (mercapto) acryloxyethyl phosphate, bis[(indenyl) propylene methoxyethyl] phosphate, and (meth) propylene oxy ethoxylate. Alcohol phosphates, etc., which can be used alone, and can also be used as a mixture. (B-3) (mercapto) hydroxy acrylate compound and polyisocyanate compound (meth) acrylate as Examples of the (mercapto) acrylic acid ester ester compound include (mercapto) propylene L vinegar, (mercapto) propylene: acid by acetonitrile, tetramethylene sulfonate tri(meth) acrylate, and the like ( Methyl methacrylate hydroxy ester compound. 312Xp/invention specification (supplement)/96-09/96119464 28 200809391 Further, as the polyisocyanate compound, for example, hexamethylene diisocyanate; [8-II] Aliphatic polyisocyanate such as isocyanate 4-isocyanate methyl octane; hexane hexane diisocyanate, dimethylcyclohexane diisocyanate, 4, 4-mercaptobis(cyclohexyl isocyanate), isophorone diisocyanate , an alicyclic polyisocyanate such as bicycloheptane triisocyanate; 4 ' 4 an aromatic polyisocyanate such as a mesogenic monoisocyanate or a tris(isocyanate phenyl) thioxanate; a heterocyclic ring such as isocyanurate Polyisocyanate modified by the method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2,260,261, the ketone phthalate modified polyisocyanuric acid vinegar; polyisocyanate compound as a (meth)acrylic acid a (meth)acrylic acid urethane of a hydroxyester compound and a polyisocyanate compound, preferably a (meth)acrylic acid amide phthalate containing the above ureido phthalate modified polyisocyanurate The (mercapto)acrylic acid amide phthalate containing allophanate-modified polyisocyanurate has low viscosity, excellent solubility in a solvent, and is compatible with a substrate due to photohardening and/or thermal hardening. In the present embodiment, the above-mentioned (meth)acrylic acid carboxylic acid hydrazine can be used as a commercial product. Specific examples include, for example, Shin-Nakamura Chemical Co., Ltd. The company's trade name is "U-4HA", "UA- 306A", UA-MC340H, "m-MC340H", "U6LPA", and the compound "AGROR4060", which has an allophanate skeleton manufactured by Bayerin Japan. 312XP/Invention Manual (Supplement)/96-09/96119464 29 200809391 - The above-mentioned (fluorenyl) acrylamide ruthenic acid in the present embodiment is preferably contained in a ruthenium molecule in view of sensitivity. 4 or more (more than 6 or more, more preferably 8 or more) amino phthalate linkages [-NH-C0-0-], and 4 or more (preferably 6 or more, more preferably 8 or more) a compound of (meth) propylene oxime. 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 hydroxyl groups in one molecule such as pentaerythritol or polyglycerol, and dihexyl diisocyanate, a compound (i-1) obtained by reacting a diisocyanate compound such as tridecyl hexamethylene diisocyanate, isophorone diisocyanate or toluene diisocyanate; or two or more hydroxyl groups in one molecule such as ethylene glycol Compound and Asahi

"DURANATE24A-100" manufactured by Cheng Industrial Co., Ltd., "DURANATE 22A-75PX", "DURANATE 21S-75E", "DURANATE 18H-70B" and other biuret type, and "DURANATE P-301-75E", a compound (i-2) obtained by reacting a compound having three or more isocyanate groups in one molecule such as an adduct type, such as r DURANATE E~ 402-90Tj - 13⁄4 r DURANATE E-405-80T j; A compound (i-3) obtained by polymerization or copolymerization of an isocyanate (ethyl) acrylate or the like. A commercially available product can be used as the compound, and for example, "DURANATE ME20-1" manufactured by Asahi Kasei Kogyo Co., Ltd. 312XP / Invention Manual (Supplement) / 96-09/96119464 30 200809391 can be cited. (ii) A compound containing four or more (fluorenyl) acryloxy groups in one molecule, for example, pentaerythritol bis(indenyl) acrylate, dipentaerythritol tris(decyl) acrylate, dipentaerythritol tetra(indenyl) A compound containing one or more hydroxyl groups and two or more, preferably three or more (meth) acryloxy groups in the fluorene molecule such as acrylate, dipentaerythritol penta (meth) acrylate or dipentaerythritol hexaacrylate. Here, the molecular weight of the compound (i) is preferably from 5 Å to 200,000, particularly preferably. Further, the molecular weight of the above (mercapto) acrylamide phthalate is preferably 6 Å to 15 Å. Further, such a (mercapto) acrylamide phthalate may be, for example, a compound of the above U) and a compound of the above (Π) in an organic solvent such as toluene or ethyl acetate at 10 to 15 ( Rc is produced by a method of about 5 minutes to about 3 hours. In this case, it is preferred that the molar ratio of the former isocyanate group to the latter is 1/1 G to 1 G/1, and if necessary, Catalyst such as n-butyltin laurate (B 4) Epoxy (meth) acrylate as (meth)acrylic acid or (hydroxy) hydroxy acrylate compound and polyepoxy compound As a polyepoxide, for example A polyepoxy compound (poly)ethylene glycol polyepoxypropyl group, (poly)propylene glycol polyepoxypropyl bond, (poly)butyl alcohol polyepoxypropyl group, (poly) ) pentylene glycol polyepoxypropyl group, (poly) neo-diol polyepoxypropyl fluorene, (poly)hexane diol polyepoxypropyl bond, (poly) dimethicone polyepoxy Propyl _, (poly) glycerol polyepoxypropyl bond, (poly) sorbitol polyepoxypropyl ether and other aliphatic polyepoxide; 312XP / hair Ming manual (supplement) /96-09/96119464 αι 200809391 % oxygen compound, evolutionary age poly-epoxy compound, (Ο-, Ρ) A-7, such as acid polyepoxide, double age An aromatic polyepoxide such as polyepoxide, bis-F polynuclear oxygen compound; xylitol anhydride ♦ epoxypropyl ether, triepoxypropyl isocyanurate, iso-man Heterocyclic polyepoxide such as propyl tris(2-hydroxyethyl) ester. &quot;Reactivate epoxy for $(meth)acrylic acid or hydroxyester (meth)acrylate compound and polycyclohexene complex The (meth)acrylic acid vinegar may be a reaction product of such a poly% hydrazine compound with (meth) octaenoic acid or the above (meth) hydroxy acrylate compound. (B-5) Other ethylenic unsaturation Examples of the other ethylenically unsaturated compound include, in addition to the above, (meth)acrylic acid amines such as sulphate and (meth)propionamide; and propyl propyl esters such as diallyl phthalate. a vinyl group-containing s species such as phthalic acid divinyl ester or the like, and an ether bond-containing ethylene by ruthenium pentasulfide or the like;

A compound containing a thioether bond which is vulcanized with an ether bond of a compound to form a thioether bond, thereby increasing the crosslinking speed. Further, for example, a decane coupling agent containing an isocyanuric acid group or a mercapto group is disclosed as disclosed in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. a methyl acrylate compound and a sol of a particle size of 5 to 30 rnn [e.g., 'isopropyl alcohol dispersed organic oxime = gum ("IPA_ST" manufactured by Seiko Chemical Co., Ltd.), methyl ethyl ketone dispersed organic sol (Nissan) "rMEK-ST" manufactured by Chemical Co., Ltd.), sulfhydryl-isobutyl hydrazine and dispersed organic sol ("MIBK~ manufactured by Nissan Chemical Co., Ltd."

J J 312XP / invention manual (supplement) / 96-09/96119464 32 200809391 etc. This compound is a compound which reacts a ruthenium sol with an ethylenically unsaturated compound via a decane coupling agent to impart strength and heat resistance to 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. These may be used alone or in combination of two or more. In the present embodiment, the ethylenically unsaturated compound is preferably a compound containing 2: an ethylenically unsaturated group in the molecule, in view of polymerizability and crosslinkability. Among the hydrazines, preferred are acenaphthyl (meth) acrylates having a (meth) propylene oxime urethane ester or a (meth) acrylate urethane, more preferably an ester (A) Base) acrylates. Among the ester (meth) acrylates, particularly preferred are bisphenol quinone di(meth) acrylate, bisphenol quinone bis[oxyethyl (meth) acrylate], bisphenol quinone [ethylene acrylate] An aromatic polyhydroxy compound such as an ether (meth) acrylate] or a reaction product with the epoxy Ethylene adduct. Further, in the ethylenically unsaturated compound of the present embodiment, those which do not contain an aromatic ring or which contain an unsubstituted or phenyl group having a substituent at the p (pair) position can suppress discoloration of the protective film by heat treatment. Red), so 1 is good. Examples of such an ethylenically unsaturated compound include an aliphatic polyfunctional (fluorenyl) acrylate, a bisphenol oxime or a (meth) acrylate compound having a ruthenium skeleton polyol. The content of the ethylenically unsaturated compound in the thermosetting composition of the present embodiment is usually 1% by weight or more, preferably 20% by weight or more, and usually 70% by weight or less based on the total solid content. Preferably, it is 312XP/invention specification (supplement)/96-09/96119464 33 200809391 60% by weight or less. When the amount of the compound having an ethylenically unsaturated group is too small, the moisture tends to decrease and the development rate 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. In the case where the component (B) in the present embodiment contains a compound having two ethylenically unsaturated groups, the compound having two ethylenically unsaturated groups accounts for the total of the above component (A) and the above component (B). The ratio by weight is usually 1% by weight or more, preferably 20% by weight or more, and the upper limit is usually 7% by weight or less, preferably 60% by weight or less. When the compound containing two ethylenically unsaturated groups contains too much ruthenium, the chemical property may be lowered. On the other hand, if the amount is too small, the peeling property may be lowered. In addition, when a compound containing three or more ethylenically unsaturated groups is used as the component (B) in the present embodiment, the content of the compound containing three or more ethylenically unsaturated groups is relative to (A). The alkali-soluble resin of the component is usually 丨〇〇 by weight or less, 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 (B) is usually 8 parts by weight or less, preferably 60 parts by weight or less based on 1 part by weight based on the total weight of the component (B). More preferably, it is 55 parts by weight or less. The ratio of the compound containing three or more ethylenically unsaturated groups to the total weight of the component (A) and the component (B) is usually 6% by weight or less, preferably 50% by weight or less, more preferably 40% by weight. Below %, the lower limit is usually 5% by weight or more. By using a compound containing three or more ethylenically unsaturated groups, the effect of increasing the hardness of the cured film can be exhibited. However, if the content is too large, it is easy to introduce 312XP/Invention Manual (Supplement)/96-09/96119464 34 200809391 The peeling property after exposure decreased. The compounding ratio of the component (8) to the component (1) is usually 15 parts by weight or less, preferably 120 parts by weight or less, more preferably (four) 11 parts by weight or less, usually 50%, based on 100 parts by weight of the component (A). The weight portion or more is preferably 70 parts by weight or more, more preferably 8 parts by weight or more. (C) Photopolymerization initiator The photopolymerization initiator used in the thermosetting composition of the present embodiment may be any known one, and it may be produced by ultraviolet light to ultraviolet light. Unsaturated radical polymerization of free radicals. Specific examples of the polymerization initiator which can be used in the present embodiment are listed below. (1) 2-(4-methoxyphenyl)- 4,6-bis(trimethylsulfonyl)-tri-morphine, 2-(4-methoxynaphthyl)-4,6-bis(trichloro) Methyl)-tri-morphine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-tris-s-zine, 2-(4-ethoxycarbonylnaphthyl)-4, 6-bis(trichloroindenyl) is a trihalogenated derivative such as tribasin. (ii) a halogenated thiolated soxadiazole derivative, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis ( 3,-methoxyphenyl) saponin dimer, 2-(o-fluorophenyl)-4,5-diphenyl-salt dimer, 2-(o-indenyl)-4, 5 a diphenyl-taste dimer, a 2-(o-methoxyphenyl)-4, 5-diphenyl miso dimer, and the like. (i i i ) benzoin, benzoin, benzoin isobutyl ether, benzoin, isopropyl ether and other benzoin, benzoin alkyl ether. (i v) an anthracene derivative such as 2-mercaptopurine, 2-ethylhydrazine, 2-tert-butylphosphonium or 1-carboquinone. 312XP/Invention Manual (supplement)/96-09/96119464 35 200809391 (V) Benzofluorenone derivatives. (vi) benzophenone, mischoketone, 2-methyldibenzophenone, 3-methylbenzophenone, 4-methyldibenzoyl ijg, 2-chlorodibenzopyrene, 4 - A benzophenone derivative such as a dibenzoyl hole or a 2-carboxybenzophenone. (V11) 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxynucleohexyl phenyl ketone, α-hydroxy-2-methylbenzene Acetone, hydroxy-1-methylethyl-(p-isopropylphenyl)one, hydroxy-indole-(p-dodecylphenyl)one, 2-methyl-(4, one (a) Acetophenone derivatives such as thio)phenyl)-2-hydroxyindolyl-p-acetone, 1,1,1-dichloromethyl-(p-butylphenyl) ketone. &amp;111) thioxanthone (1; 1 ^ 1:1101 ^), 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl Thiophenone derivatives such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone. (1 Χ) a paraben derivative such as p-dimethylaminobenzoic acid ethyl ester or p-diethylaminobenzoic acid ethyl ester. (Χ) 9-phenyl. Acridine derivatives such as acridine and 9-(p-methoxyphenyl)acridine. (χι) 9' 10-dimethylbenzophenone and other timid derivatives. (XII) bis(3⁄4-pentadienyl)titanium dichloride, bis(cyclopentadienyl)diphenyltitanium tetra, bis(cyclopentadienyl)-di(2,3, 4, 5, 6 _ pentafluorobenzene + yl) chin, bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluorobenzene+yl)titanium, bis(cyclopentadienyl)-di(2,4 ,6-trifluorobenzene-1-yl)titanium, bis(cyclopentadienyl)_2,6-bis(fluorophenyl-l-yl)titanium, bis(cyclopentadienyl)_2,4_di(fluorine Benzene-1-yl) Titanium, bis(methylcyclopentadienyl)_di. ,^-pentafluorobenzene+yl) chin/diylcyclopentanyl)-di(2,6-di-fluorophenyl-bu)titanium, bis(cyclopentadienyl)-2,6- II (Bilin_Bujib Benzene+Based Titanium, etc. 312XP/Invention Manual (Supplement)/96-09/96119464 36 200809391 Titanocene derivative. (xiii) 2 - Mercapto-1 [4-(sulfuric acid) Phenyl] phenyl]- 1-2 aryl-based; [-acetone, 2-&gt;yl-2-indenylamino]; [mono(4-monophenyl) phenyl, 2-benzyl) -2-Didecylamino-1-(4-indolylphenyl)-;[1-butanone, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate Ester, 4-diethylaminophenyl phenyl g, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylamino benzoate, 2, 5_bis (4) -diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino) α-Aminoalkylphenone compound such as chalcone. (xiv) 2, 4, 6-dimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-tri F-benzene) A mercapto phosphine oxide compound such as mercapto)-phenylphosphine oxide. (XV) 1,2-octanedione, 1-mono[4-(phenylthio)phenyl]-2-(anthracene-benzoic acid), ethyl ketone, 1-[9-ethyl-6-( 2-Methylbenzylidene)-911-carbazole-3-yl]-1 - (0-acetic acid monthly loss) (xvi) Japanese Patent Laid-Open No. 2〇〇〇_8〇〇68, special opening Represented by the compounds disclosed in the specification of Japanese Patent Application No. 2005-305074, the disclosure of which is incorporated herein by reference. The above-mentioned photopolymerization initiators are used singly or in combination of a plurality of them. Examples of the combination include Japanese Patent Publication No. Sho 53-128-2, and No. 1-279903. Kaiping No. 2 - 4_ Bulletin = 4 - 164902 or special (Kaiping 6_75373, etc.: combination of initiators. U not 312XP / invention manual (supplement) / 96-09/96119464 37 200809391 The photopolymerization initiator contained in the thermosetting composition of the shape is usually 〇·1% by weight or more, preferably 5%·5% by weight or more, usually 40% by weight based on the total solid content. Take Preferably, it is 30% by weight = lower. When the amount of the right photopolymerization initiator is too small, the sensitivity is likely to be lowered, and if the right amount is too large, the scum (developing solubility) is likely to be lowered. As the component (C), The compounding ratio of the component.) is usually not more than 1 part by weight, more preferably 1 part by weight or less, and usually more than 丨·丨 by weight, based on the compounding amount of the component (B). It is 5· 5 parts by weight or more. (D) Thermal crosslinking agent The thermosetting composition of the present embodiment may contain a thermal crosslinking agent for the purpose of improving the heat resistance and chemical resistance of the film after thermosetting. ^, for ..., the father knows 1 丨, and if it is a cross-linking reaction by hard-baked image after the image is formed by exposure and development, a well-known person can be used. Specifically, the following may be used in the case of the above materials (four), or two or more kinds may be used in combination. (D-丨) a compound containing an epoxy group in the molecule as a compound containing an epoxy group in the molecule used in the present embodiment, such as a reaction of a monohydroxy compound or a polyhydroxy compound with a surface alcohol; The ether compound, the (poly) (tetra) compound and the polyepoxypropyl styrene compound obtained by the reaction, and the (poly) epoxypropylamine compound obtained by reacting the (poly) aminating component are converted from a low knives. It is a compound of a molecular weight. _ (D-1~1) Polyepoxypropyl ether compound 312XP/Invention manual (supplement)/96-09/96119464 38 200809391 A propyl ether compound, for example, a bicyclolified tertyl ether of polyethylene glycol Type oxime resin, bis(4-hydroxyphenyl)-epoxy resin, epoxy resin, 雔Μ ς not 丞 ^ one % 虱 propyl ether type

Also known as F 裱 丙基 propyl ether type epoxy resin, bisphenol A -% milk propylene _ type epoxy resin, tetramethyl bis bis ace syl ether epoxy resin, epoxy '&quot; Oxygen material ^milk B said addition of double A bis-epoxy propyl scale epoxy 2: two base g-type epoxy resin, two-peep base swelling base oxygen type ring, double a A / acid _ Oxygen wax, _ / cresol novolac epoxy resin. ... 衣 衣 曰 曰 曰 曰 曰 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣Milk: base ether resin, which can be exemplified by double s epoxy resin, smashing m: epoxy resin, three epoxy resin, hydrated epoxy resin of aged and dicyclopentene, and epoxy resin . A phenol resin such as a resin such as 5% hydrazine or the like, which is a phenol resin such as a compound such as a resin or a compound such as a compound such as a compound or a compound such as a compound such as a compound or a compound such as a compound such as a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or a compound or (D 1 2 ) Polyepoxypropyl vinegar compound The propyl group-containing compound may, for example, be a hexa-% oxypropyl ester type epoxy resin or an adjacent type epoxy resin. - 夂 one % 虱 propyl ester (D - 1 - 3) polyepoxypropylamine compound as polyepoxypropylamine compound methane - gas generation system I, for example, bis (4-amino group) Phenyl)

One of the T-alkanes is a propyl propylamine type epoxy resin, and the linoleum type epoxy resin is used. "Cyanide knocking three epoxy propylene 312XP / invention manual (supplement) / 96-09/96119464 39 200809391 (D-1 - 4) Others, as other examples, for example, one can be made alone or in combination More than the above (fluorenyl) propylene acrylate, α-ethyl acrylate propyl propyl ester, α-n-propyl acrylate propyl propyl ester, α-n-butyl acrylate propyl propyl ester, ( Mercapto) acrylic acid _3, 4-epoxybutyl acrylate, 4,5-epoxypentyl (meth) acrylate, -6,7-epoxyheptyl acrylate, α-ethyl acrylate 6. A polymer obtained by reacting an epoxy group such as a (meth) acrylate such as epoxy heptyl ester, or a (meth) acrylate having an epoxy group. The polymer of the other copolymerization monomer of 7 % by mole, preferably U to 60 % by mole. Examples of the monomer for copolymerization include (mercapto)acrylic acid and methyl (meth)acrylate. , ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl f-methyl)acrylate, phenyl (meth)acrylate, Ethyl cyclohexyl methacrylate, dicyclopentanyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, (meth) acrylate (meth) acrylate (meth) acrylate, and An styrene, α-fluorenyl styrene, p-nonyl styrene, vinyl naphthalene or the like, and a sulphur-based compound. As a (fluorenyl) acrylate having an epoxy group, it is preferably enumerated (A) Further, preferred examples of the copolymerization monomer include dicyclopentanyl (meth)acrylate, styrene, and α-methylstyrene. When the epoxy compound is a resin (there is In the case of the epoxy resin, it is not particularly limited as long as the protective film material (thermosetting composition) of the present embodiment can be uniformly applied in a solution state, and the coating is formed according to the formation. The thickness of the film, the coating conditions, the purpose, etc. are appropriately selected from the 312 ΧΡ/invention specification (supplement)/96·09/96119464 40 200809391. As the molecular weight, it is usually suitably in the range of 2 〇 3 〇〇, 〇〇 0, preferably 3, _1 1 〇〇 〜 50,000. In addition, the epoxy group used in the epoxy compound or epoxy used in the present embodiment is usually a 1-epoxy group, and is intended to be connected to θ or impart flexibility. Can also be used: 3 qualitative illusion, epoxy cyclohexyl. '3^-based (oxe-butane) is an epoxy compound of the present embodiment, which does not contain an aromatic product == or a phenyl group having a substituent at the (p-) position. Color change (red) 2 ring = compound, for example, a bis-epoxy compound and an epoxy oxime; an epoxy compound having a first skeleton which may have a substituent, and an epoxy ruthenium (A) A copolymer of a glycidyl acrylate such as the above. The thermosetting composition of the present embodiment has a shape = 1: weight = lower oxygen = ^ 3 〇 by weight or less, and usually a compound having a weight of (10) - The opening of the mouth m ° contains the epoxy in the molecule, which tends to cause the thermosetting composition solution" and the peeling property after exposure and development to decrease. U contains the heat-crosslinkable compound: == a nitrogen-thermally crosslinkable compound, a compound of the same, or a snail-modified compound thereof, or a urinary 3UXP/invention specification (winning V96 face 6119464 41 200809391 specific and a ' as a fumarin effect on melamine Examples of the compound or the alkyl modified product are exemplified by Cytec lndustHes.

Cyme1" 〇 main book trademark) 300, 301, 303, 350, 736, 738, 370 771, 325, 327, 703, 7G1, 266, 267, 285, 232, / 114 272, 254, 2G2, 1156, 1158 "Nkalac" (registered trademark) E-2151, MW-100LM, MX-750LM, etc. In addition, examples of the compound which causes fumarin to act on phenyl melamine or an alkyl carbaryl thereof include "Cymel" (registered trademark) ii23, ι 25, 1128 and the like. In addition, "Cymel" (registered trademark) 117 〇, 11 η, 11, U72, "Nikalac" (registered trademark) Μχ-27, as an example of the compound which is used to act on the brown sulphate of the sulphate. ()Wait. In addition, as an example of a compound which causes fumarin to act on urea or an alkyl modified substance, r UFR" (registered trademark) 65, 300, "Nikalac" (registered trademark) Μχ _ manufactured by Cy1: ec industries, etc. In the (D) thermal crosslinking agent in the present embodiment, a compound having a -N(CH2〇R)2 group (wherein R represents a burnt group or a hydrogen atom) is preferable. Particularly preferred is a compound which causes formalin to act on urea or melamine or a burn-in thereof. In the case where the thermosetting composition of the present embodiment contains a nitrogen-containing heat-crosslinkable compound as the (9) thermal crosslinking agent, the content of the nitrogen-containing heat-crosslinkable compound as a thermosetting composition is relative to the total The solid content is usually 4% by weight or less, preferably 30% by weight or less, more preferably 2% by weight to 312XP/Invention specification (supplement)/96-09/96119464 42 200809391 I Residue == crosslinkable compound If the amount is too large, it will easily lead to a decrease in the rate of the rafting and a decrease in resolution. Among them, as the thermal crosslinking agent (D), a compound which is a particularly preferable compound is a compound of a molecular group, that is, a 2 group (a formula, R represents a thio group or a hydrogen atom), and it is particularly preferable to make a formalin A compound of urea or melamine or a burn-in thereof. (E) Other components (E-1) Adhesive auxiliary agent For the purpose of improving the adhesion to the substrate, an adhesive agent can be formulated in the deuterated composition of the present embodiment. As the adhesion promoter, for example, a decane coupling agent can be mentioned. More specifically, for example, trimethoxy benzoic acid, r methacryloxypropyl trimethoxy decane, vinyl triethoxy decane, ethylene trimethoxy decane, R_epoxypropyloxypropyltrimethoxycarbazide, 7-isocyanatopropyltriethoxy(tetra), (3, cyclohexyl)ethyltrimethoxydecane, and the like. These coupling agents can be used alone or in combination. In addition, the decane coupling agent not only functions as an adhesion aid, but also has a moderate heat to the protective film during heat treatment (4) (thermal fluidity) ), improve the function of flatness. The decane coupling agent to be blended for such a purpose is, for example, a material coupling agent having an epoxy group. More specifically, for example, I exemplifies r-glycidoxypropylmethoxymethyl, 3 _(3 s epoxycyclohexyl)ethyltrimethoxy oxysulfide, and the like. 312XP/Invention Manual (Supplement)/96-09/96119464 43 200809391 In the case of using an adhesion aid, 'as the above-mentioned adhesion aid, the total solid content relative to the thermosetting composition is usually 〇· 1% by weight or more, usually 20% by weight or less, preferably 10% by weight or less. (E-2) Surfactant The thermosetting composition of the present embodiment is intended to enhance the coating property of the coating liquid of the composition and the developability of the thermosetting composition layer, and may also contain non- An ionic, anionic or cationic amphoteric surfactant, or a surfactant such as a fluorine-based or polyfluorene-based surfactant. Examples of the nonionic surfactant include polyoxyethylene oxides, oxypropylene propylene oxides, polyoxyethylene benzene bonds, polyoxyethylene alkyl esters, and polyoxygenates. Ethylene fatty acid esters, glycerol esters = acid esters, oxyethylene glycerol fatty acid vinegars, pentaerythritol fatty acids, polyoxyethylene pentaerythritol fatty acids (IV), sorbitol liver fatty acid esters, oxyethylene sorbose Alkyd fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like. Further, as the above-mentioned anionic surfactant, for example, alkyl alkanoate, alkyl benzene salt, alkyl sulfonate, polyoxyethylene alkyl decanoic acid Salts, alkyl sulfates, alkyl sulfates, high-grade yeast sulfates, aliphatic alcohol sulfates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl phenyl ether sulfates Class, alkyl phosphate salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphate special polymer interface activity. Among these, the special-high score is preferably a polyoxyethylene surfactant such as "Emulgen Teng;; Emulgen A60" manufactured by Kao Corporation. 312XP/Invention Manual (Supplement)/96-09/96119464 44 200809391 Z-based surfactants are more preferably special poly-philic polymer interface surfactants J 0, t is such an anionic surfactant' can be used For example, "Emal 10" ^ 'alkylnaphthalene sulfonate manufactured by Yamagata and Bovine Chemical Co., Ltd. can be used as a commercial product, for example, it is not a 1NB manufactured by Kao Co., Ltd. L"# 'Special polymer-based surfactants are exemplified by the flower 2:%&quot;, "1...8" and "-" as the above-mentioned cationic surfactant, which can be cited as a quaternary salt: derivative Species, amine salts, etc., in addition, as an amphoteric interface, 4 can be used to test the compounds, imidazolium salts, imidazolines, = base = etc. The salt is more preferably a hard fat-didimethyl (four) class. As a city #, for example, the amine amine king company 劐铁夕 "^ + · 〇yt bovine, Acetamin 24", etc., quaternary ammonium salt "Quartamin 2 servant" made by Niu Yuhua Wang Co., Ltd.

Quartamin 86W" and so on. On the other hand, as the surfactant, it is preferred to have a compound having a burnt group or a gas (tetra) group at the terminal, the main chain and the side chain. Specifically, for example, U,2,2-tetra-I-octyl αι, 2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctylhexyl ether, and octylene Alcohol (Μ 2:2-tetrafluorobutyl) hydrazine, hexane ethylene glycol di ai, 2, 2, 3, 3_q - earth ether, octanediol diai, 2,2-tetrafluorobutyl) ether, Propylene glycol di(1'1'2'2,3,3-hexafluoropentyl)ether, sodium perfluorododecylsulfonate, L U'2, 8'8'9'9, 10, 10-10 Fluorodedodecane, J, i, 2, 2, 3, 3 hexafluoride 312XP / invention specification (supplement) / 96-09/96119464 45 200809391 decane and the like. As such commercial products, "BM - 1 000", "BM-1100" manufactured by BM Chemie, "Mega face F142D" manufactured by Dainippon Ink Chemical Industry Co., Ltd., and "Megaface F172" are available. "Mega face • FI 73", "Mega face FI 83", "Mega face F470", "Megaface F475", "FC430" manufactured by Sumitomo 3M Co., Ltd., "DFX-18" manufactured by NEOS Co., Ltd. Wait. In addition, examples of the polyfluorene-based surfactant include "Tor ay Si 1 i cone DC3PA" manufactured by Toray Si 1 i cone Co., Ltd., "same as SH7PA", "same DC11PA", and "same SH21PA". "Same as SH28PA", "Same 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”, “KP341” manufactured by Silicone, Inc., “BYK323” and “BYK330” manufactured by BYK Chemie And other commercial products. 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/fluorine-based surfactant, a polyfluorene-based surfactant, a special polymer-based surfactant, and a fluorine-based surfactant. /Special polymer interface Λ Combination of active agents, etc. Among them, a polyfluorene-based surfactant/fluorine-based surfactant is preferred. In the combination of the polyoxo-based surfactant/fluorine-based surfactant, Example 312ΧΡ/Invention Manual (Supplement)/96-09/96119464 46 200809391, such as "TSF4460" / NE0S manufactured by GE Toshiba Silicone Co., Ltd. "DFX-18" manufactured by the company, "Βγκ-300" manufactured by BYKChemie Co., Ltd. or "ΒΥΚ-330" / "ς * 393" manufactured by Seimi Chemical Co., Ltd., "KP340" manufactured by Shin-Etsu Shiki Gum Co., Ltd. / Greater Japan Ink Company, manufactured "F-478" or "F-475", "SH7PA" manufactured by Toray Si 1 icone, "DS-401" manufactured by DAIKIN, and "1^77" manufactured by Unicar Corporation of Japan / Sumitomo 3 elbow company "之4430" and so on. In the case where 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, more preferably 1 to 5, based on the total solid content. weight%. (E-3) Hardener In order to shorten the time in the curing condition or change the set temperature, the thermosetting composition of the present embodiment may additionally contain a curing agent, and different curing conditions may be appropriately selected depending on the manufacturing steps of the respective elements. . 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, a polyvalent carboxylic acid (anhydride), a polymer containing a polyvalent carboxylic acid (anhydride), and a thermal acid generator. , an amine compound, a polyamine compound, a quinone carboxylic acid, and the like. Particularly, in the case where the above epoxy group-containing compound is used as the thermal crosslinking agent, a thermosetting agent is preferably used. (E-3 - 1) benzoic acid-based compound as a benzoic acid-based compound, which may be represented by a benzoic acid or a benzoic acid having a benzene ring = position = a position, a halogen group, a halogen group, a thiol group, and a benzoic acid group. , Hyun-based, aryl, propyl and other substituents. Among them, it is preferably /, there is a hardened food for the epoxy resin t &gt;, the moon b force is more than the south of the base as a substituent 312 Χ & </ gt> / invention manual (supplement) / 96-09/96119464 47 200809391 special &lt; Soil is a base with more than 2 bases. As such a benzoic acid compound, for example, 3,4, tribasic benzoic acid, 2,5-dibenzyl benzamidine H2'6-dihydroxybenzoic acid, 3,4-dihydroxyl group Benzoic acid, 2,4,6-trihydroxylcarboxylic acid, and the like. CE-3-2) Polycarboxylic acid (anhydride) As the polyvalent acid (anhydride), for example, monomethylbiscycloheptylene dicarboxylic anhydride, hexahydrophthalic anhydride, tetrahydroortylene-benzoquinone- An alicyclic polycarboxylic acid (anhydride) such as phthalic anhydride, dialkyltetrahydrophthalic anhydride or methylcyclohexene dihydrolevulin; stupid-anthracene anhydride, meta-dicarboxylic anhydride, pyromellitic anhydride, Diphenyl fluorenone: aromatic polybasic anhydride such as carboxylic acid ketone, benzophenone tetracarboxylic acid sulfonate; alicyclic benzoic acid, maleic acid, cyclopentane tetracarboxylic acid, etc. A hydrolyzate of an aromatic acid anhydride or the like. Among these, trimellitic acid (anhydride) and phthalic anhydride are preferred. (E-3-3) Polymer containing a polyvalent carboxylic acid (anhydride) As a polymer containing a polyvalent carboxylic acid (anhydride), a polycarboxylic acid (anhydride) such as maleic acid (anhydride) and an intramolecular molecule are mentioned. A polymer containing a compound of one or more ethylenically unsaturated bonds, or a partial half-ester modified polymer of a polycarboxylic acid (anhydride) portion of such a polymer. Examples of the compound containing one or more ethylenically unsaturated bonds in the molecule include (meth)acrylic acid, an alkyl ester thereof, (meth)acrylonitrile, (meth)acrylamide, styrene, and the like. (Poly) an olefin such as a substituent such as an alkoxy group or an alkyl group. 12XP/Inventive Manual (Supplement)/96-09/96119464 48 200809391 As a polymer containing a polycarboxylic acid (anhydride), the octopus in the bean can be considered as if and the strength of the cured film. A copolymer of an olefin having a substituent such as an alkoxy group or an alkyl group. 〆, (E-3-4) thermal acid generator as a thermal acid generator, for example, an aromatic diazonium salt, a di-salt, a monophenyl sulfonium salt, a tri-propyl propyl salt, a tri-propyl propyl sulphate Salts, etc. = salt compounds, sulfonates, halogen compounds, and the like. Specific examples of the aromatic diazonium salt include diazonium chlorobenzene hexafluorophosphate, = methylamine * benzohexa acid salt, naphthyl hexafluorophosphate diazonium, monomethylaminonaphthyltetra Fluoroborate diazonium salt, and the like. In addition, 'as a base lock salt, can be cited - poor basin Bu # ^ Benji four mouse borate bismuth, dibasic hexahydrate bismuth citrate, diphenyl hexafluorophosphate ^,,, a ten-gram one base Difluoromethanesulfonic acid", 4, 4 - di-dibutyl-diphenyldifluoromethane * lack of soil - 匕 匕 T 页 页 錤, 4, 4, - di butyl butyl - two Phenyl tetrafluoroborate, 4, 4,--zan-^ fluoroquinone ruthenium phthalate, etc. - Di-dibutyl-diphenyl hexanthene, as a soap phenyl salt, which can be exemplified by ^ ^ ^ ^卞--p-Phenylmethylmethyl® ^^^7丞/, 锑 锑 对, p-ethoxylated benzyl hexamethyl hexafluoroantimonate 苄, benzyl _, lower, fmrr, 丞 丞 hydroxy Phenylmethyl hexafluoroantimonic acid I, a compound represented by the following formula (H), etc., a phenyl sulfonium salt type, etc.. 1 &amp; 卞丞 [4] m

[3-CH2-2 SWV wherein 'Z' represents a phenyl group. 312XP/Inventive Manual (supplement)/96·〇9/96119464 49 200809391 Further = 'As a triallyl salt, there are triphenyl tetrakis-depleted acid, melon, diphenylphosphonium hexafluorophosphate , triphenylphosphonium hexafluoroantimonate, tris(p-chlorobenzene tert-tetrafluoroboron, di(p-chlorophenyl)phosphonium hexafluorophosphate, tris(p-chlorophenyl) hexafluoroantimonate, 4_ Tert-butyltriphenylphosphonium hexafluorophosphate, etc. As the "mercaptopropyl sulfonium salt", there are exemplified triallyl tetrafluoride tetrahydrate, trispropyl hexaphosphate, phosphate trichloride, triallyl hexafluoroantimony Acid code, bis(chlorophenyl)phenyltetrakis(tetra)phosphonate, bis(chlorophenyl)phenylhexafluoroantimonate, phenylhexafluoroantimonate selenium, etc. l Milky violence) For example, a toluene core benzoin vinegar, a thiol group M0-ethoxy ken-2- oleic acid vinegar, a 2 - cis-based toluene sulphuric acid vinegar, a 2: 6-dinitronodal toluene Sulfonic acid vinegar, 2, [dinitro-benzyl sulfonate vinegar vinegar, etc. A = halogen compound can be exemplified by 2-chloro-2-phenylacetophenone, 2, 2, 4, chloroethyl acetophenone 2, 4, 6-di(trichloromethyl) [(p-methoxystyryl)-4,6-bis(trichloromethyl)-tri-morphine, 2-phenyl-7,6-bis(trichloromethyl)-tri-morphine, 2~(pair Methoxyphenyl)-4,6-bis(trismethyl) diazide, 2-(4'-methoxyl-naphthyl)- 4,6-bis(trichloromethyl)-three :, double, trichloroethane, bis (4-chlorophenyl)-2'2'2-trichloroethanol, bis-2_(4-methoxyphenyl)-ditriethane, and the like. — Among these thermal acid generators, the viewpoint of light transmittance and cured film strength is preferably 'monophenyl salt type, or? Base phenyl salt type. (E - 3 - 5) Amine compound as an amine compound, for example, 3 UXP / invention specification (supplement) / 96-09/96119464 200809391 ethylenediamine, 1,3-diaminopropane, hydrazine, 4 - diaminobutane, hexamethylenediamine, 2,5-monodecylhexamethylenediamine, brittle bite, u ratio slightly oxime, triethylenediamine, tridecyl hexanediamine, dinonylcyclohexylamine, four Mercaptopurine, triethanolamine, N,N, dimethyl dimethyl ketone, bis-amine, or derivatives thereof; DBU (1,8-diazabicyclo(5, 4, 0) undecene-1 ), DBU is a tetraphenyl stone salt temple aliphatic amine (primary, secondary, tertiary); m-diamine, diaminodiphenylnonane, diaminodiphenylguanidine, diamine-based Ethyl diphenyl oxime, benzyl diamine, dimethylamino-p-dioxene, 2-(diamine dimethyl phenol), 2, 4, 6-tris(didecylamino fluorene Phenol, pyridine, acridine, DBU (1, 8-diazabicyclo(5, 4, 0) undecene-1), 2, 4, 6-di(monodecylaminomethyl) Aromatic amines such as 2-ethylhexyl acid salt (primary, secondary, tertiary); 2-mercaptopurine, 2-ethyl-4-methylweijun, 2-ethyl-4 - Methyl imipenone, 2-Η 基 咪 咪 、, 2-17 烧 基 咪 、, 2 phenyl phenyl saliva, 1-phenyl-2-mercaptopurine, 1-cyanoethyl-2 - thiophene, 1-cyanoethyl 2-ethyl-4-mercaptoimidazole, cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -11 Base sputum • trimellitic acid S, 2 - fluorenyl σ 镔 镔 · isocyanurate, 2-phenylimidazolium · isocyanurate, 2, diamino-6-[2 - mercapto imidazolyl-(1)]-ethyl-all three tillage, 2,4~diamino-6-[2-ethylimidazolyl-(1)]-ethyl-all three tillage, 2, 4~Diamino- 6 - [2-Η-烧基口米11 坐基-(1)]-ethyl-dimorphine, 2-phenylamino-4, 5-dihydroxydecyl imidazole, 2- Phenyl-4-methyl-5-pyridinyl imidazole; [Imidazole compound such as [cyanoethyl-2-phenyl-4,5-di(cyanoethoxyindenyl)imidazole; 312ΧΡ/ Disclosure of the Invention (Repair)/96-09/96119464 51 200809391 Monoethylenediamine, imine bispropylamine, bis(hexamethylene)triamine, and the like. Among these, from the viewpoint of the strength of the cured film, dicyandiamide or DBU-based tetraphenylborate is preferred. (E-3-6) Polyamine compound As the polyamine compound, for example, triethyltetramine, tetraethylamamine, pentaethylhexamine, dimercaptopropylamine, and diethyl Aminopropylamine, N-Aminoethylpipene, menthanediamine, isofluorodiamine, bis(4-amino-3-indolylcyclohexyl)decane, diaminodicyclohexylamine An aliphatic polyamine such as N,N-dimethylcyclohexylamine, an aromatic polyamine such as isophthalamide, benzodiazepine, xylylenediamine derivative or xylylenediamine terpolymer. Among these, N,N-dimethylcyclohexylamine is preferred. (E-3 - 7), as a block carboxylic acid, for example, the above-mentioned (poly) carboxylic acid and a carboxylic acid containing the polymer of the same are disclosed in Japanese Laid-Open Patent Publication No. Hei-4-218561. A block carboxylic acid of ethylene ether or the like is added by a method disclosed in JP-A-2003-336333, JP-A-2004-339333, and the like. Among the above-mentioned curing agents, the polymer containing a polybasic acid (Xuan), an iron salt compound, a block carboxylic acid compound, and a benzoic acid compound have good activity in hardening reaction to obtain high hardness and adhesion of the #support. The aspect is better. More specifically, it can be exemplified by: maleic anhydride and polyethylene oxypropylene having a carbon number of 丨 to other alkyl groups, a carbon number of 1 to U, a polypropylene oxypropylene group or a carbon number of 15 a polycarboxylic acid copolymer of a vinyl compound selected from the group consisting of at least one selected from the group consisting of butyl, butene, or a propylene compound and styrene, 312XP/invention specification (supplement)/96-09/96119464 52 200809391; a carboxylic acid compound of decanoic acid or an addition of maleic acid and ethyl vinyl ether; a benzoic acid compound such as 2' 5-dihydroxybenzoic acid or 3,4,5-trihydroxybenzoic acid; - p-Hydroxyphenyl sulfonium hexafluorophosphate, bismuth p-hydroxyphenyl dimethyl hexafluoroantimonate, p-ethoxycarbonyl phenyl dimercapto hexafluoroantimonate, ", base t to benzene A monophenylphosphonium salt such as a hydrazine methyl hexafluoroantimonate or a compound represented by the above formula (n), or a monophenylphosphonium salt such as a benzylphenyl phosphonium salt. These hardeners may be used singly or in combination of two or more. In the case of the curing agent, the polycarboxylic acid copolymer and the benzoic acid compound are excellent in adhesion to the support, and the monoterpene salt is excellent in hardness improvement. The benzoic acid-based compound is preferred because it has excellent thermosetting properties, high light transmittance, and low discoloration due to heat. 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 5% by weight or more based on the total solid content. The weight % or more is usually 20% by weight or less, preferably 10% by weight or less. If the amount of the hardener is too small, the adhesion to the support and the hardness are likely to be lowered. On the contrary, too much right is likely to cause an increase in the weight loss. (F) Additive In the thermosetting composition of the present embodiment, various additives may be blended in addition to the above components, for example, an o-hydroxy 2312XP/invention specification (supplement)/96-09/96119464 which may have a substituent. 53 200809391 Thermal polymerization inhibitors such as benzophenone, hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol. The blending ratio of the compounds is usually 5% by weight or less, preferably 2% by weight or less based on the total solid content. Further, it is also possible to contain, in a ratio of 40% by weight or less, preferably 2% by weight or less, of plasticity such as dioctyl phthalate, bis(dodecyl) phthalate or tricresyl squarate. Agent. Further, in the thermosetting composition of the present embodiment, a polymerization accelerator may be added as needed. Specific examples of the polymerization accelerator include an ester of an amino acid such as N-styl glycine or a bipolar ion compound thereof, a sulfhydryl benzoxazole, and a 2-bulk benzimidazole. 2-Weiylbenzoxazole, 3-diyl-1,2,4-dijun, 2-sulfo-4(3H)-喧嗤琳,々-sulfenyl naphthalene, ethylene glycol disulfide a compound containing a mercapto group such as a propionate, a trimethylolpropane trithiopropionate or a pentaerythritol tetrathiopropionate, hexanediol or trimethyl methacrylate dithioglucoside a poly-B thiol compound such as pentaerythritol tetrathiopropionate, N,N-dialkylamino benzoate, n-phenylglycine or a derivative thereof such as an ammonium salt or a sodium salt An amino acid having an aromatic ring or a derivative thereof, such as a propylalanine or a salt such as a salt or an ester thereof such as a sodium salt or a derivative thereof. In the case of adding a polymerization accelerator to the thermosetting composition of the present embodiment, the content ratio thereof is preferably 2% by weight or less based on the total solid content, more preferably 1 to 10% by weight.

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 absorbing the light source Z 312XP/invention specification (supplement)/96-09/96119464 54 200809391 specific wavelength used for the exposure by the ultraviolet absorber, thereby controlling The photohardening speed at the time of exposing the film of the thermosetting composition of this embodiment formed on the substrate. 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,

Sumisoapl 30 (manufactured by Sumitomo Chemical Co., Ltd.), EVERS0RB10, EVERS0RB1, EVERS0RB12 (made by Taiwan Yongguang Chemical Industry Co., Ltd.), Tomisoap800 (manufactured by API Corporation), SEESORBIOO, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEES0RB151 (Shipro Chemical System) a benzophenone compound;

Sumi soap200, 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, TINUVIN900, TINUVIN928, TINUVIN1130 (Ciba Specialty Chemicals), EVERSORB70, EVERS0RB7, EVERS0RB72, EVERS0RB73, EVERS0RB74, EVERS0RB75, EVERS0RB76, EVERS0RB234, EVERS0RB77, EVERS0RB78, EVERSORB80, EVERS0RB81 (made by Taiwan Yongguang Chemical Industry Co., Ltd.), TomisoaplOO, Tomisoap600 (manufactured by API Corporation), SEESORB701, SEESORB702 , SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (Shipro Chemical System), etc. benzotriazole 312XP / invention specification (supplement) / 96-09/96119464 55 200809391 compound;

Sumisoap 400 (manufactured by Sumitomo Chemical Co., Ltd.), benzoate compound such as phenyl salicylate; hydroxyphenyl trimorphine compound such as TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477 DW, TINUVIN 479 (manufactured by Ciba Specialty Chemicals). Wherein ' is preferably a benzotristrin compound, a phenylphenyltrimorphine compound, and particularly preferably a benzoquinone tris-sine compound. When the ultraviolet absorber is added, the blending ratio is usually 〇〇1% by weight to 15% by weight, and preferably 5% by weight or more based on the total solid content of the thermosetting composition. 1% by weight or less. When the blending ratio of the right ultraviolet absorber is less than the above range, it is difficult to obtain an effect of improving the pattern shape and/or eliminating residue, and if it is too large, the sensitivity tends to decrease and/or the residual film ratio tends to decrease. (G) Organic solvent The above components are usually used in such a manner that the organic solvent is used in an amount of 5 to 60% by weight, preferably 1 to 5 parts by weight, based on the solid content. 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 exemplified by A, celecoxicil, butyl siroli, diethylene glycol monomethyl bond, (one: early vinegar vinegar, propylene glycol diacetate, propylene glycol single Methyl ether acetate ketone, abbreviated as "PGMAc"), methyl ethyl _, methyl isobutyl bromide - hexamethylene hexanoate, toluene, chloroform, dioxane, acetic acid, lactic acid 56 312 ΧΡ / __βί·)/%·_6119464 200809391 vinegar, ethyl lactate, propionic acid 3_曱4^^ ύ T-rolling methyl ester, propionic acid 3-ethoxyethyl alcohol early methyl ether, decyl alcohol, ethanol, propanol Butanol, tetrahydrofuran, mono-diol dimethyl bond, methoxy butyl acetate, S〇lvesso, carbitol and the like. ^ is the point of the above organic solvent, preferably (10) to (d). More preferably, c is in the range of 120 to 170 °C. In addition, the organic solvent may be used alone or in combination of two or more.乍: The combination of the organic solvents used in combination may be, for example, one or more organic solvents selected from the group consisting of diethylene glycol dimethyl ketone, methoxy butyl acrylate, and chlorhexidine. In the mixed solvent, the blending ratio of the organic solvent of 1# or more selected from diethylene glycol dimethyl ether, methoxybutyl acetate, S01vess, and carbitol is usually 10% by weight or more based on PGMAC, preferably 3〇% by weight or more, usually 80% by weight or less, preferably 7% by weight or less. Among the above mixed solvents, a mixed solvent of PGMAc and methoxybutyl acetate induces a moderate flow of the coating material. Therefore, it is preferable to flatten the unevenness of the substrate. [2] A method of forming a protective film, and a method of forming a protective film of the thermosetting composition of the present embodiment will be described. [2 - 1 ] Coating step First, on the substrate on which the TFT array is formed, the thermosetting composition of the above-described embodiment is a spinner, a ring-type wet film coater, a curtain coater, a die coater, and a roll. Coating machine, sprayer, etc. The coating film thickness of the thermosetting composition is usually 〇.5~5 #m. 57 312XP/invention specification (supplement)/96-09/96119464 200809391 [2-2] drying step from the above coating film Removal (dry, dry choice can use vacuum dry welding to become a dry coating film.) Fortunately, "the dry conditions of the soil is the temperature range of the minute. 15 〇 c, drying time 10 seconds ~ 60 [2 — 3 ] Exposure • Imaging step over ΐ罝 ΐ罝 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热Pixel. In addition, 'improve the sensitivity after exposure and before imaging: purpose, there are days, also for post-light baking. In this case, the heating plate, infrared oven, convection ng. t U, phase special can be used. Exposure and baking conditions are usually, the drying time is in the range of 1 〇 to 60 minutes. 2 Often for the image obtained by the _ obtain 2. &quot; wide thin line and then b. In addition to 'high-quality display, There is a tendency to require higher precision and field line reproducibility. On the other hand, as a rectangular shape in which the cross-sectional shape of the thin line image after development is clear, the contrast between the image and the image portion is clear, and the development time of the development time and the physical stimulus of the developing liquid is wide, so it is preferable. Helin y is used as a light source for the exposure of the dry coating film, and examples thereof include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and the like. Light source or argon ion laser, remember! Lu garnet laser (YAG lazer ' Yttrium A1

Garnet Laser), excimer lasers, nitrogen lasers and other laser sources. In the case where only light of a specific wavelength is used, a filter can also be utilized. 312XP/Invention Manual (Supplement)/96-09/96119464 200809391 The solvent used in the development treatment is not particularly limited as long as it has a solvent capable of dissolving the unhardened coating film, as described above. In view of environmental pollution, harmfulness to the human body, fire hazard, etc., it is preferred to use an alkaline developing solution instead of an organic solvent. Examples of such an inspectable developing solution include an inorganic compound such as sodium carbonate, carbonic acid gas, iron sulphate, sodium oxychloride, i: potassium, or diethanolamine or triethylamine. An aqueous solution of an organic basic compound such as triethanol tetramethylammonium hydroxide. The t- and i-identifying imaging liquids may also contain a surfactant, a water-soluble agent, a humectant, a humectant, and a low molecular compound having a thiol group or a few acid groups, which are surfactants, imaging properties, and resolution. There are many improvements in scum and the like, so it is preferable to add them. Mistake 2: The surfactant used in the liquid is, for example, an anionic surfactant having naphthalene, oxonium or benzoic acid, and a non-ionic surfactant having a polycondensation. The four-burning base of the cationic cation king interface active agent. ^The method of image processing is not particularly limited, usually in the imaging temperature of ig~coffee, 啧~45C, by immersion imaging, dialing, ^ imaging, scanning imaging, ultrasonic imaging The method is carried out. N - 4 ] The heat treatment step is performed by the itr light and development steps to form an image of the thermosetting composition film to be baked, '', and the crucible is used for the purpose of suppressing the occurrence of degassing during hard baking. Full exposure. 312XP/Invention Manual (Replenishment)/96 Iron 119464 59 200809391 In the case of full exposure before the hard baking, the light source uses UV2, such as gas lamp, *sodium lamp, skein lamp, high pressure mercury 5 Mercury lamp, metal self-prime lamp, medium pressure mercury lamp, low pressure mercury lamp and light source or argon ion laser, YAG laser, excimer thunder. In addition, 'hard baking can use hot plate, as hard baking condition, usually 1 〇〇 ~ 90 minutes range. Infrared oven, convection oven, etc. 250 ° C, drying time is 3 sec. - [3] Liquid crystal display device (panel) Next, the manufacturing method of the liquid crystal display device (panel) of the present embodiment will be described. The liquid crystal display device of this embodiment is generally provided with a main matrix substrate. First, a cured material is formed on a substrate on which a TFT element array is formed, and an I τ film is formed thereon as a water-preserving film, and then an I τ λ wiring is formed by photolithography to form a TFT active matrix substrate. Further, the liquid crystal display device of the present embodiment can be formed by laminating the TFT active matrix substrate and the counter substrate to form a liquid crystal cell, injecting liquid crystal into the formed liquid crystal cell, and further connecting the counter 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. In the formation of the alignment film, gravure printing and/or flexographic printing are usually employed, and the thickness of the alignment film is formed to several tens of nm. After the hardening treatment of the alignment film by hot calcination, the surface treatment is carried out by irradiation with ultraviolet rays or a treatment of the alignment cloth, and the surface state of the liquid crystal can be adjusted to be inclined. Further, a protective film similar to the above may be formed on the film of the 312XP/invention specification (supplement)/96-09/96119464 60 200809391. The bonding gap between the TFT active matrix substrate and the counter substrate is different depending on the application of the liquid display, and is usually selected in the range of 2 or more and 8" or less. After bonding to the opposite substrate, the liquid crystal is injected. The portion other than the inlet is sealed with a sealing material such as an epoxy resin. As such a sealing material, it is usually cured by UV irradiation and/or heating to start and seal the periphery of the liquid crystal cell. After being cut into panel units, the inside of the vacuum chamber is decompressed, and the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal cell is injected into the liquid crystal cell to inject liquid crystal into the liquid crystal cell. It is lxl0-2 Pa or more, preferably lxl〇-3Pa or more, and is usually lxl (r7Pa or less, preferably lxi〇_6 Pa or less). Further, it is preferable to heat the liquid crystal cell under reduced pressure. The temperature is usually 3 (rc or more, preferably 5 Å or more, usually 100 ° C or less, preferably 90 ° C or less. As a heating condition under reduced pressure, usually 1 minute. Above, 6 minutes to The liquid crystal cell is immersed in the liquid crystal. The liquid crystal cell is injected into the liquid crystal cell to harden the UV hardening resin to seal the liquid crystal injection port. In this way, the liquid crystal display device (panel) can be completed. The liquid crystal known in the art, such as an aromatic system, an aliphatic system, or a polycyclic compound, may be used, and any of lyotropic liquid crystals and thermotropic liquid crystals may be used. Thermotropic liquid crystals are known to have nematic liquid crystals and layers. Any of the lining liquid crystal and the cholesteric liquid crystal may be used. [Examples] 312XP/Invention Manual (Supplement)/96-09/96119464 61 200809391 Next, the present embodiment will be more specifically described by way of examples and comparative examples. The present embodiment is not limited to the following examples, and the components of the thermosetting composition used in the following examples and comparative examples are as follows. (A) Solvent-reducing resin [Chemical 5]

Acid value: 110 mg-KOH/g

Mw: 17, 000

Acid price: 37 mg_K0H/g

Mw ·· 25, 000 312XP/Invention Manual (supplement)/96-09/96119464 62 200809391 P3:

Acid value: 130 mg-KOH/g Mw : 45,000

p:q:r=s 70:10:20 Acid value: 107 mg-KOH/g Mw ·· 4200 (B) Compound having two or more ethylenically unsaturated groups [Chemical 6] M1 : m+n - 2.6

Gongrongshe Chemical System Light Ester BP-2EM

DPHA 312XP / invention manual (supplement) / 96-09/96119464 63 09 化 化 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008

Gongrongshe Chemical Epoxy Ester 3000A M4:

〇Y% R604 M5 manufactured by Nippon Kayaku Co., Ltd.: Royal 9]β, χ h2c.-c-o-ch2-ch2o-〇-ch2^ =1. KAYARAD PM-21 M6 manufactured by Nippon Kayaku Co., Ltd.

OgasolEA— 0200 (C) Photopolymerization initiator (also known as Osaka Chemical Co., Ltd.) 312XP/Invention Manual (supplement)/96-09/96119464 64 200809391

π:

C-—Ν’ 〇Χν

Irpaacure369, manufactured by Ciba Specialty Chemicals

12: 〇 H3CS

Irpaacure 907, manufactured by Ciba Specialty Chemicals

Irjacure OXE-02 (D) Thermal Crosslinker manufactured by Ciba Specialty Chemicals Co., Ltd. [Chem. 8] 312XP/Invention Manual (supplement)/96-09/96119464 65 200809391

H3COH2C

CH2OCH3 CH2OCH3

HaGOWnCL ...

Nikalac MWIOOLM manufactured by Sanwa Chemical Co., Ltd.

Nippon Chemical Co., Ltd. NC-3000 (E) Other components SI · · Fluoride surfactant. F475 (F) additive made by Dainippon Ink Co., Ltd. R1: Polymerization accelerator. 2-Mercaptobenzimidazole Y2: UV absorber. Has the following formula. [Chemistry 9]

(G) Organic solvent PGMAc: propylene glycol monoterpene ether acetate The evaluation methods of the prepared thermosetting composition, the exposed film thereof, and the thermosetting film are as follows. 312XP/Invention Manual (Supplement)/96-09/96119464 66 200809391 [Ethylene Unsaturated Group Equivalent] For the thermosetting composition, the chemical structural formula of the component (B) and the component (A) contain ethylenic unsaturation. In the case of the base, it is calculated from the chemical structural formula of the polymer predicted from the monomer addition ratio. [Dynamic Dissolution Speed] In the order of formation of the above-mentioned exposed film, the difference (# m) between the film thickness after application and drying and the film thickness after development is measured, and the value is divided by the development time (minutes). As the imaging dissolution rate (//m/min). [NMP dissolution rate] The thermosetting film obtained by the order of formation of the above-mentioned thermosetting film was immersed in N_ decylpyrrolidone at 6 (TC for 20 minutes, and then rinsed with pure water. The difference in film thickness before and after immersion) (/am) The value of the soaking time (2 minutes) was used as the NMP dissolution rate (//m/min) after hard baking. [Optimum exposure amount] The measurement was carried out according to the method disclosed in the above embodiment (mJ/). Cm2) [Resolving property] The image of the thermosetting film which is formed by the order of the above-mentioned thermosetting film is observed by an optical microscope, and the minimum line width (mouth) of the image is analyzed as [pattern shape]. The line pattern of the 20 &quot;line width of the thermosetting film obtained in the order of formation of the above-mentioned thermosetting film was observed by an electron microscope. The pattern shape was evaluated on the basis of the following criteria. In this case, A · good squareness, no error side 312XP / invention Instruction manual (supplement)/96-09/96119464 67 200809391 β : Good rectangularity, but a little skirt c : poor rectangularity, or no resolution [residue] observed by optical microscope in the order of formation of the above-mentioned thermosetting film A gap of 30 //m line width of the known thermosetting film In the case, the residue of the blank portion was evaluated on the basis of the following criteria: A: no residue B. Only the residue was found in the peripheral portion of the photoresist C. The residue was also found in the central portion of the blank portion. [Releasability] The order of formation of the above-mentioned thermosetting film was The obtained thermosetting film was immersed in N-methylpyrrolidone at 6 ° C for 1 minute in a N-methylpyrrolidone, and evaluated on the following basis: Ο : No thermosetting film remained on the substrate. X : On the substrate Residual thermosetting film. [Chemical resistance] The thermosetting film obtained in the order of formation of the above-mentioned thermosetting film was evaluated in 4 (TC) at 20% by weight in 4% by weight of hydrochloric acid, and evaluated by the following criteria. The optical ray mirror was observed on the surface, and the hole or surface enemies (concavity and convexity) were observed by the wire. 'The hole or surface enemies were observed. 浊7 turbidity 0 X : Surface observation fold (concavity and convexity) by optical microscope. Or, by visual observation To white [transmittance] In addition to full exposure without using a photomask, a cured film is obtained according to the above-described thermosetting 312xp/invention specification (supplement)/96-09/96119464 68 200809391 formation of a film. Production office The light transmittance of the cured film was measured by UV3100PC, and the minimum transmittance (%) in the range of 600 nm to 400 nm of the wavelength of ηπ Bu Wuyi was observed. [Examples 1 to 7 Comparative Examples 1 to 3] A thermosetting composition was prepared by the preparation shown in Table 1. The obtained thermosetting composition was applied to a glass plate "AN100" glass substrate for a shirt color filter manufactured by Asahi Glass Co., Ltd. Then, it was dried at 90 ° C for 90 seconds on a hot plate 1 to obtain a coated crucible having a dry film thickness of 4 / m. After that, a mask having a fine line pattern having a line width of 10 was passed through the coating film side, and exposure was performed using a 3 kW high pressure mercury lamp. As an exposure condition, the image illuminance measured by an illuminance meter having a wavelength of 365 nm was 3 〇 mW/cm 2 , which was set as the exposure amount of the above optimum exposure amount. Next, a 0.4% by weight aqueous solution of tetramethylammonium hydroxide was used as a developing solution, and the substrate was immersed in a developing solution at 25 ° C for 7 sec to perform development, and further rinsed with pure water. Exposure film. The thermosetting film was obtained by heating the exposed film of p obtained at 220 ° C for 1 hour in a convection oven. Various evaluations were made on the above thermosetting composition, exposed film, and thermosetting film. The results are also shown in Table 1. 3 GXP/Invention Manual (supplement)/96-09/96119464 69 200809391—. 2呑 ss 8 inch

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[m7yl-_J 2 i#紫叶铋采(3) fss isiG) ssi $00 0i si#^ i ¥ inch 9 inch 6II96/60-96/(#I紫)_K^S micro/dxCNle 200809391 From Table 1 As a result, it is understood that the thermosetting film formed of the thermosetting composition of the present embodiment is a thermosetting film which is excellent in chemical properties, light transmittance, pattern shape, and residual characteristics, and has removability. In particular, in the fourth embodiment of the polymerization accelerator and the ultraviolet absorber, a thermosetting film in which both the pattern shape and the residue characteristics coexist can be obtained. The thermosetting film formed of the thermosetting composition of Comparative Examples 1 and 2 is a thermosetting film having a developing solution dissolution rate of a predetermined value or less but having poor peeling properties. When the ethylenically unsaturated group equivalent is more than 5 mmol/g, the peelability is lowered. In addition, since the thermosetting film formed of the thermosetting composition of Comparative Example 3 has an ethylenically unsaturated group equivalent of a predetermined value or less, the peeling property is good, but the developing dissolution rate exceeds a predetermined value, and the chemical property is poor. Further, the resin P3 used as the component (A) has a relatively large molecular weight and tends to have poor resolution. (Industrial Applicability) According to the present invention, for example, it is possible to form no coloration during hard baking, good y light transmittance in a visible light region, and excellent peelability after exposure and development, and chemical resistance after heat curing. A thermosetting composition for an excellent protective film. In addition, a high quality liquid crystal display device can be provided thereby. Therefore, it is industrially highly available in the field of a thermosetting composition for a protective film and a liquid crystal display device. Further, according to the present invention, a solder resist such as a printed wiring board, a liquid crystal display element, a plasma display, a large-scale integrated circuit, a thin transistor, a semiconductor package, a color light-emitting sheet, an organic electroluminescence or the like is provided. Membrane or cover film, and the formation of an insulating coating layer of various electronic parts. Useful heat hard 312XP / invention specification (supplement) / 96-〇9/96119464 71 200809391 Chemical composition. Further, a thermosetting composition suitable for use as a color filter, a black matrix, a rib, and a spacer used in a liquid crystal panel such as a liquid crystal display is provided. Therefore, the industrial availability in this field is extremely high. • In addition, this application is based on the Japanese patent application filed on May 31, 2006 (Patent 2006-1 52046), and the patent application filed on July 28, 2006 (patent 2006-206544) and 2007. The Japanese patent application (patent 2007-134316) filed on May 21, 2011, is used by reference to the whole. 312XP/Invention Manual (supplement)/96-09/96119464 72

Claims (1)

200809391 X. Patent application scope: 1 · A thermosetting composition for a ruthenium film, which comprises the following components (A) to (C): (A) a soluble resin, 1 (B) a compound having two or more ethylenically unsaturated groups and (C) a photopolymerization initiator; the content of the ethylenically unsaturated group relative to the total weight of the component (the phantom component (B) is 1 耄 mol/g or more and The exposure film of 5 mmol/g or less, which is exposed and hardened at the optimum exposure amount, has a dissolution rate of 2.3 //m/min in a 4% by weight aqueous solution of tetramethylammonium hydroxide (25 ° C). 2. The thermosetting composition for a protective film according to the first aspect of the invention, wherein the component (B) is a component containing a compound having two ethylenically unsaturated groups, and the ethylene has two ethylene groups. The ratio of the compound of the unsaturated group to the total weight of the above-mentioned (A) and the above-mentioned component (β) is 1% by weight or more. ^3. The thermosetting composition for a protective film according to the scope of the application of the patent application' Wherein 'the above component (A) is not having an ethylenically unsaturated group and an epoxy group 4. The thermosetting composition for a protective film according to the first aspect of the patent application, wherein the thermosetting film obtained by baking at 220 ° C for 1 hour after exposure to an optimum exposure amount is used in N- The dissolution rate of the decyl pyrrolidone (60 ° C) is 〇·1 /zm/min or less. 5. The thermosetting composition for a protective film according to the first aspect of the invention, further comprising the following components ( D): 312XP / invention manual (supplement) / 96-09/96119464 73 200809391 (D) thermal crosslinking agent 6. a hardened material characterized by the use of the thermal curing of the protective film of claim 1 Formed by a composition. 7. A liquid crystal display device characterized by having a cured product of claim 6 as a protective film. 312XP/Invention Manual (supplement)/96-09/96119464 74 200809391 VII. Designation Representative diagram: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: No. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: No 312XP/Invention Manual ( Supplement)/96-09/96119464 5