TW200807152A - 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 high sensitivity, less lowered under the condition that the spectroscopic characteristics of the exposure light sources are different, can be used to form a protective layer, will not be colored when subjected to baking, and has good transmittance in the visible region. The thermosetting composition of the present invention comprises (A) an alkali soluble resin, (B) a compound having 2 or more ethylene unsaturated groups, and (C) a photopolymerization initiator. The thermosetting composition for a protective film has the transmittance of 90% or above per 1 μm film thickness at the wavelength of 400 nm. The component (C) has an absorption maximum wavelength at 310 to 370 nm.

Description

200807152 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a thermosetting composition using a light or heat protective film, and is more compact, for example, regarding a printed wiring board or a liquid crystal. , a plasma display, a large-scale integrated circuit, a thin transistor, a semi-sealed coating, a shirt color filter, an organic electroluminescence, etc., a solder resist film or a back film, and a shape of a coating of various electronic parts The remainder is a useful hardening composition. Further, the present invention relates to a curable composition useful for a color filter, a light sheet, a black matrix, a protective layer, a rib, and a spacer used in a liquid crystal panel such as a liquid crystal display, and is formed using the same. A cured product, and a liquid crystal display device having the same. [Prior Art] A thin film transistor (TFT, Thin used in a liquid crystal display device) is formed between a pair of array elements and a transparent conductive film forming a pixel electrode. The interlayer insulating film for protecting the TFT array element. Here, the interlayer insulating film is usually formed with a contact hole for connecting the germanium electrode of the TFT array and the wiring formed of the transparent conductive film. Therefore, the material of the interlayer insulating film is generally photosensitive. A thermosetting composition which is used in such an application, and more specifically, as a positive photosensitive composition, it is known to contain an alkali-soluble resin and 1,2-anthracene. A composition of a bismuth nitride (for example, refer to the patent document 丨). Further, as a negative thermosetting composition, a photopolymerizable composition is known (Example 31ZXP/Invention Manual (Supplement)/96-09/96119466 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The conventional positive photosensitive composition disclosed in 1, for example, there is a case where 1,2, bismuth nitride is colored by thermal decomposition during hard baking after exposure and development, and the visible light region In addition, in terms of sensitivity, the image formation requires a low sensitivity such as an exposure amount of 2 μm/cm 2 or more. In addition, photopolymerizable negative photosensitive property disclosed in Patent Document 2 The composition does not cause the coloring problem as described above, and there is an advantage that it is easy to obtain a higher sensitivity in terms of sensitivity. However, the photopolymerizable negative photosensitive composition has a sensitivity largely dependent on the light splitting of the exposure light source. In particular, in recent years, in the manufacture of liquid crystal display devices, an exposure apparatus using a high-illuminance light source has been used for the purpose of improving the yield, and it has been studied to cut off the wavelength of the deep UV region in order to prevent deterioration of the mirror surface. ^ If the protective film is a thermosetting composition as the conventional one, the sensitivity is largely dependent on the spectral characteristics of the exposure source, then the light is cut off in the deep uv region. There is a case where the sensitivity is extremely low. SUMMARY OF THE INVENTION An object of the present invention is to provide a thermosetting composition for a protective film which has less sensitivity and high sensitivity when the spectral characteristics of the exposure light source are different. Further, another object of the present invention is to provide a thermosetting composition for a protective film which is free from coloring during hard baking and has a good light transmittance in a visible light region. 312XP/Invention Manual (Supplement)/96-09/ Further, another object of the present invention is to provide a cured product comprising a thermosetting composition for a protective film, and a liquid crystal display device comprising the cured product as a protective film. The protective film of the present invention is thermally cured. A composition comprising (A) a soluble resin, (B) a compound having an ethylenically unsaturated group, and (c) a photopolymerization initiator, at a wavelength of 4 〇〇 nm The light transmittance is 90 g/q or more per 1 / m of the film thickness, and the above composition (the 〇 from 31 〇 nm to 370 nm has the maximum absorption wavelength. The cured product of the present invention is formed using the thermosetting composition for a protective film. The liquid crystal display device of the present invention includes the cured product as a protective film. [Embodiment] According to the present invention, a thermosetting composition for a protective film can be provided. When the spectral characteristics of the exposure light source are different, the sensitivity is less lowered, the sensitivity is high, and a protective layer can be formed. 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, the cured product formed of the thermosetting composition for a protective film has a high-quality film because it has no coloring during hard baking and a light-transmitting film having a good light transmittance in a visible light region. The liquid crystal display device of the present invention has a high-quality hardened material by using such a high-quality cured product. The embodiments of the present invention will be described in detail below. Further, the present invention is not limited to the following embodiments, and the present invention is not limited thereto. It is carried out in the range of the change. ° 312 ΧΡ / invention manual (supplement) / 96-09/96119466 8 200807152 [1] Thermosetting composition for protective film Thermosetting composition for protective film of the present embodiment (below In some cases, it is characterized by containing (A) to (C) each component, (A) an alkali-soluble resin, and (B) having two or more ethylidene groups. a saturated group compound, (C) a photopolymerization initiator, a light transmittance at a wavelength of 400 mn of 9 〇% or more per dry film thickness, and the above component (C) has an absorption maximum wavelength at 310 nm to 370 nm . In addition, it is preferable that the maximum peak of the spectral sensitivity is 325 nm to 4 〇〇 nm, and the ratio of the sensitivity at a wavelength of 300 nm to the sensitivity E365 at a wavelength of 365 nm is E365/E3. . It is 1 〇 below. Hereinafter, the "light transmittance at a wavelength of 400 nm", "absorption maximum wavelength", "maximum peak of spectral sensitivity", and rE365/Em will be described first. [Light transmittance at a wavelength of 400 nm] The thermosetting composition of the present embodiment is applied onto a glass substrate so that the dry film thickness is approximately i // m, and is 9 〇 on the hot plate. Bake for 90 seconds. In the present embodiment, the light transmittance is measured by a spectrophotometer UV3100PC manufactured by Shimadzu Corporation, and the light transmittance (measurement wavelength: 4 〇〇 nm) per unit thickness (1 Am) is measured. value. In the present embodiment, the light transmittance at a wavelength of 4,000 nm is 90% or more, preferably 92% or more, and more preferably 95% or more per 1 // m film thickness. Further, the upper limit is not particularly limited, but is usually 1% or less. If the light transmittance at a wavelength of 4 〇〇 nm is smaller than the above range, it is easy to absorb visible light, 312XP/invention specification (supplement)/96-09/96119466 9 200807152 color. [Absorption maximum wavelength] • Prepare a solution by dissolving the measurement object in tetrahydrofuran at a concentration of 10 mg/L. The absorption spectrum of the solution was measured using a spectrophotometer. The wavelength at which the absorption maximum point is observed is defined as the absorption maximum wavelength. In the present embodiment, the component (C) has an absorption maximum wavelength of 310 nm to 370 nm, preferably 315 nm to 370 nm, more preferably 315 nm to 3 60 nm. When the absorption maximum wavelength of the photopolymerization initiator is in a region shorter than the above range, the sensitivity is liable to be lowered when the light source that cuts off the light in the deep UV region (light having a wavelength of less than 350 nm) is exposed. Further, in the case where the absorption maximum wavelength of the photopolymerization initiator is in a region longer than the above range, the light transmittance of the thermosetting film is liable to lower (absorption of visible light to facilitate coloring). [Maximum peak of the spectral sensitivity] The "maximum peak of the spectral sensitivity" in the present embodiment can be described in detail by, for example, "Photopolymer Technology" (issued by Yamaoka Yasushi, published by Nikko Kogyo, Ltd., page 262). The method is carried out. #, A photosensitive image is formed on the surface of the reduced plate. • A sample material is formed, and a spectroscopic light measuring device is used to irradiate the split light from a light source such as a xenon lamp or a crane lamp. In this case, the light is irradiated (exposure) in such a manner that the horizontal exposure axis linearly changes and the exposure intensity is logarithmically changed in the vertical axis direction. Thereafter, development processing is performed to obtain an image corresponding to the sensitivity of each exposure wavelength. The exposure energy of the image can be formed according to the height of the image, and the exposure energy is depicted on the horizontal axis by the green wavelength, 抽: 324 ΧΡ / invention manual (supplement) / 96-09/96119466 1 〇 200807152 The reciprocal can obtain the spectral sensitivity curve. The maximum peak on the spectral sensitivity curve is referred to as "the largest peak of the spectral sensitivity". Further, in the above-described "photosensitive image forming material sample in which a photosensitive layer is formed on the surface of the substrate", the thermosetting composition of the present embodiment is applied onto a glass substrate to be heated. The plate was dried by 9 Q for 90 seconds. The maximum peak of the spectral sensitivity exhibited by the present thermostable composition is usually 325 nm to 400 nm, preferably 330 nm to 390 nm. If the dabbling peak of the light sensitivity is on the wavelength side longer than the above range, it may be exposed to light under yellow light and the workability may be poor. On the other hand, if the maximum peak of the spectral sensitivity is shorter than the wavelength side of the above range, the sensitivity of the exposure wavelength may be increased. [E365/E300] Similarly to the case of measuring the maximum peak of the spectral sensitivity, the wavelength is changed and exposed in the wavelength range of 3 〇〇 to 650 nm. The minimum exposure of the image that can be formed at a wavelength of 300 nm and the minimum exposure of the image at 365 nm (E365 (mJ/cm2)] are obtained, and the ratio is defined as e365/E3〇〇. E365/E3〇 of the thermosetting composition of the present embodiment. The value is usually! Hereinafter, it is preferably 0.3 to 1·〇, more preferably 〇·6 to 〇·9. If the value is too large than the e365/E3 ’, there is a case where the sensitivity is lowered. On the other hand, if the value is too small, the exposure wavelength dependence of the sensitivity may increase. In the present embodiment, in order to provide a difference in sensitivity when the spectral characteristics of the exposure light source are different, the sensitivity is high and the protective layer can be formed. 312XP/Invention Manual (Supplement)/96-09/96119466 11 200807152 The heat-curable composition is used to set the light transmittance of the thermosetting composition and the maximum absorption wavelength of the component (C) within a fixed range. Furthermore, this is an object of the embodiment (in the case where the spectral characteristics of the exposure light source are different, the sensitivity can be reduced), which is not a problem generally known to the industry. [Mixing component of thermosetting composition for protective film] Next, the 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 (Α) to (c) essential components, the following components may be blended. (D) Thermal crosslinking agent (E) Other components (F) Additives (G) Organic solvents Hereinafter, each component will be described. In the present embodiment, the "(meth)acrylic group" means "acrylic acid group and/or methacrylic acid 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 an acid and an anhydride thereof. The term "(poly)carboxylic acid" means both tannic acid and polycarboxylic acid. In addition, the "total solid content" means the total amount of components of the photopolymerizable composition from which the solvent is removed. (A) Alkali-soluble resin The alkali-soluble resin used in the present embodiment is not particularly limited as long as it is a resin soluble in 312XP/invention specification (supplement)/96-09/96119466 12 200807152 alkaline solvent. It is preferably a resin containing a carboxyl group or a hydroxyl group. Examples of such a soluble resin include unsaturated groups and carboxyl groups such as (meth)acrylic acid, (meth)acrylate, maleic acid, vinyl acetate, and maleimide. Epoxy resin; (meth)acrylic acid, (mercapto) acrylate, (meth)acrylonitrile, (mercapto propylene amide, maleic acid, styrene, vinyl acetate, vinylidene chloride, a vinyl-based resin containing a hydroxyl group or a carboxyl group and having a hydroxyl group or a carboxyl group; and a polydecylamine, a polyester, a polyether, a polyurethane, a polyvinyl butyral, a polyvinyl alcohol, a polyvinylpyrene Acridinone, acetaminophen, etc. These may be used alone or in combination of two or more. Among them, in view of alkali developability and image formability, it is preferred to contain an unsaturated group and a carboxyl group. The epoxy resin and the vinyl group containing a carboxyl group. Further, in view of the peeling property after exposure and development, it is preferred to use a vinyl group-containing resin which does not contain an unsaturated group and contains a mercapto group. Resin. & (A - 1) An epoxy resin having an unsaturated group and a carboxyl group as an epoxy resin containing an unsaturated group and a carboxyl group, and, for example, may be further exemplified by a carboxylic acid addition product containing an α, a 10,000-unsaturated group of an epoxy resin. Epoxy tree 312ΧΡ containing unsaturated groups and carboxyl groups of carboxylic acid and/or its anhydride/invention specification (supplement)/96-〇9/96119466 13 200807152 曰 。 即 。 。 。 。 。 。 。 。 。 环氧 环氧On the epoxy group of the resin, an ethylenically unsaturated bond is added via an ester bond (-coo-) formed by ring-opening addition of a carboxyl group of an oxime, a mono-unsaturated monocarboxylic acid, and at this time The resulting 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 containing an unsaturated group and a carboxyl group will be described, and the constituent components may be used singly or in combination. Mixing two or more types (A-1 to 1) The epoxy resin i used in the epoxy resin containing an unsaturated group and a carboxyl group is used as an epoxy resin used in an epoxy resin containing an unsaturated group and a carboxyl group, for example, Illustrate bisphenol A epoxy resin, bisphenol F epoxy resin: bisphenol S epoxy resin, phenol a phenolic epoxy resin, a cresol novolac epoxy resin, a trisphenol epoxy resin, a polymerized epoxy resin of a phenol and a dicyclopentane, etc. Among them, a phenol novolac epoxy resin is preferable in view of the strength of the cured film. Or a cresol novolac epoxy resin, a polymerized epoxy resin of phenol and dicyclopentadiene, a copolymer of glycidyl methacrylate and (meth)acrylic acid alkyl ester, etc. (A-1 - 2 α, a cold-unsaturated monocarboxylic acid as an α,/3-unsaturated monocarboxylic acid, and examples thereof include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, and econazole. Acid, citraconic acid, etc., and pentaerythritol tris(decyl) acrylate succinic anhydride adduct, pentaerythritol tris(decyl) acrylate tetrahydrophthalic anhydride anhydride, dipentaerythritol penta (meth)acrylic acid S Acryl anhydride anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adduct, (methyl) A reaction product of acrylic acid and monocaprolactone. Among them, in view of sensitivity, it is preferable that 3 UXP/invention specification (supplement)/96-09/96119466 14 200807152 is (mercapto)acrylic acid. (A-1 - 3) A polycarboxylic acid or an anhydride thereof as a polyhetic acid or an acid anhydride thereof, and examples thereof include crotonic acid, cis-butanoic acid, isaconic acid, phthalic acid, and tetrahydroortylene. Formic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydropyranoic acid, 4-ethyltetrahydrophthalic acid, hexahydroortho Benzoic acid, 3-methyl: hydrogen phthalic acid, 4-mercaptohexahydrophthalic acid, 3-ethylhexahydrobenzene: benzoic acid, 4-ethylhexahydrophthalic acid And such anhydrides and the like. Among them, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable in view of image reproducibility and development, and it is more preferably tetradecene phthalate. Formic anhydride. In the present embodiment, in view of improving the sensitivity and resolution of the thermosetting composition, and (4) the adhesion between the substrates, the epoxy resin containing an unsaturated group and a mercapto group is preferably an epoxy resin. Phenolic epoxy resin, biguanide, oxygen tree, hydroxy hydroxy (resin) or nonylphenol phenolic epoxy resin, a, unsaturated monocarboxylic acid is (mercapto) acrylic acid, polycarboxylic acid or its anhydride is four Hydrogen phthalic anhydride. Further, the unsaturated group and the epoxy resin are preferably those having an acid value of from ～200 mg to _/g, more preferably from 3 〇 to 18 () mg_KQH/0. Further, 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 'above or more', usually 4 Å or less, 乂仏 is 30,000 or less, and more preferably 2 Å or less. 312XP/Invention Manual (Supplement)/96-09/96119466 15 200807152 Further, the molecular weight in the present embodiment means polystyrene measured by gel permeation chromatography (GPC method) unless otherwise specified. The weight average molecular weight (Mw) converted. The details of this measurement method are as follows. [Machine] HLC-8020 manufactured by Tosoh Co., Ltd. [column] GMHXL-N 30 cmx2 manufactured by Tosoh Co., Ltd. [Mobile phase] 1 · 0 ml/min

[column temperature] 40 ° C

[Solvent] THF (tetrahydrofuran stabilized by 丁基·〇3 wt% of butylhydroxyindole) [Standard sample] Polystyrene (PSt) standard sample [Check line] 5 times [Detection] RI (Device [Incorporated] [Injection amount] 0.1% by weight 100#L (The sample is previously filtered by GL Chromatography Disc 13P manufactured by GL Science Co., Ltd.) The above-mentioned epoxy group containing an unsaturated group and a slow base in the present embodiment The resin can be synthesized by a conventionally known method. Specifically, the above-mentioned epoxy resin can be used in the organic solvent, and in the presence of a catalytic disk thermal polymerization inhibitor, a 4^-unsaturated single (four) is added to: carry out an addition reaction, thereby adding a plurality of The carboxylic acid or its anhydride continues to dance. Here, examples of the organic solvent include organic solvents such as methyl ethyl hydrazine, cyclohexyl hydrazine, diethylene glycol diethyl ether acetate, and propylene glycol monomethyl ether acetate. Further, 'the above-mentioned catalyst' may be a tertiary amine such as triethylamine, benzyldimethylamine or tribenzylamine, or a tetramethylammonium halide or a f-group triethylphosphonium 312XP. /Invention Manual (Supplement)/96-09/96119466 16 200807152 Known, tetraethylammonium vapor, tetrabutyl chloride, trimethyl sulfhydryl chloride = grade salt or triphenylphosphine The compound, or an anthracene such as triphenylsulfonium, is a benzoic acid. Further, examples of the thermal polymerization inhibitor include hydroquinone monophenolphthalein, methyl pivalidylphenol and the like. The compounding amount of the above-mentioned unsaturated monocarboxylic acid is usually set to 〇·7 to ΐ 3 222 ′ relative to the chemical equivalent of the epoxy group of the sap. In addition, in the addition reaction: 1 degree, the hanging can be set to 60~15 (rc, preferably 8〇~i2〇〇c and then the 'polycarboxylic acid or its anhydride blending amount' relative to the above addition The chemical equivalent of i = 经 成 通常 通常 通常 通常 通常 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 2 Illustrated in the following rigid grease 'will constitute a repeat 312XP / invention manual (supplement) / 96-09/96119466 17 200807152 [Chemical 1]

(XiH2CHCH2OOCCH«CH2 ooc

HOOO

ocH2cmH2ooccmcn2

312XP/Invention Manual (supplement)/96-09/96119466 18 200807152 [Chemical 2]

R

(A-2) Vinyl-based resin containing a carboxyl group The carboxyl group-containing vinyl resin of the present embodiment may, for example, be a copolymer of an unsaturated carboxylic acid and a vinyl compound. Examples of the unsaturated carboxylic acid include (meth)acrylic acid, crotonic acid, isobutylene I, maleic acid, maleic anhydride, isaconic acid, and citraconic acid. These may be used alone or in combination of two or more. Further, examples of the vinyl compound include styrene, α-mercaptostyrene, hydroxystyrene, decyl decyl acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Butyl acrylate, (decyl) propylene 312 ΧΡ / invention specification (supplement) / 96-09/96119466 19 200807152 acid pentane vinegar, (mercapto) hexyl acrylate, dodecyl (meth) acrylate, (mercapto) 2-ethylhexyl acrylate, (hydroxy) hydroxy decyl acrylate, (mercapto) - hydroxyethyl acrylate, (meth) propylene acrylate, (meth) acrylate _ §, (Mercapto) dicyclopentanyl acrylate, benzyl (meth) acrylate, N, N-didecylaminoethyl (meth) acrylate, n-(mercapto) propylene porphyrin, ( Acrylonitrile, acrylonitrile, (mercapto) acrylamide, N-hydroxyindole (fluorenyl) acrylamide, N,N-dimercapto(fluorenyl) acrylamide, N,n-dimethylamine A copolymer of a vinyl group (mercapto) 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, (fluorenyl) dicyclopentanyl acrylate is preferred in providing a wide latitude for development time or deterioration of the developing liquid. Examples of such a (fluorenyl) acrylic acid-containing dicyclopentan vinegar include compounds exemplified in JP-A-2002-89533, for example, a dicyclopentadiene skeleton, a dicyclopentyl skeleton, and a dicyclopentane. An alkenyl skeleton, a (fluorenyl) acrylate of a dicyclopentenyloxyalkyl skeleton, or the like. In the above copolymer (vinyl group-containing resin containing a carboxyl group), a (meth) acrylate-(meth)acrylic copolymer is preferable in view of image shape, sensitivity, and cured film strength, and more preferably A copolymer comprising 3 〇 8 8 mol% (meth) acrylate, 20 to 70 mol % (meth) acrylic acid. Particularly preferred is a copolymer comprising 50 to 75 mole % (mercapto) acrylate, 25 to 50 mole % (methyl) • acrylic acid. Further, the acid value of the carboxyl group-containing vinyl resin is usually from 3 to 250 mg-KOH/g, preferably from 50 to 200 mg-KOH/g, more preferably from 7 to 150 mg-KOH/g. 〇 312XP/Invention Manual (Supplement)/96-09/96119466 20 200807152 Further, the molecular weight of the carboxyl group-containing vinyl resin is usually 〇〇〇 〇〇〇 or more, preferably 1,500 or more, and more preferably More than 2 000, usually 1 GUG0 or less, preferably 5 〇, _ or less, more preferably 3 〇, _ or less, and particularly preferably 20,000 or less. When the carboxyl group-containing vinyl resin is used in the above range, since the peeling property after development is good, it is preferable that the alkali-soluble resin in the present embodiment is preferably not contained in the aromatic ring or contains no In place of this, in the case where the phenyl group having a substituent at the p (pair) position is substituted, the protective film is discolored (red) due to heat treatment, and cracking due to heat is suppressed. As such a soluble resin, for example, a copolymer of styrene or dicyclopentanyl (meth)acrylate; a double-type epoxy compound or epoxy resin; or an anthracene skeleton which may have a substituent may be mentioned. 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 polyfluorene carboxylic acid 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. Namely, the solubility-soluble resin containing an ethylenically 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-2) a vinyl group-containing resin. More specifically, an alkyl (meth)acrylate/(meth)acrylic acid copolymer, a styrene/alkyl (meth)acrylate/(mercapto)acrylic acid 312XP/invention specification (supplement) )/96-09/96119466 21 200807152 Polymer, hydroxyalkyl (meth) acrylate / alkyl (meth) acrylate / (mercapto) acrylate, styrene / hydroxyalkyl (meth) acrylate Ester • /(indenyl)alkyl acrylate/(meth)acrylic acid copolymer, (mercapto) propylene: acid alkyl ester/maleic acid copolymer, styrene/alkyl (meth) acrylate /maleic acid copolymer, hydroxyalkyl (meth) acrylate / (alkyl) alkyl acrylate / maleic acid copolymer, styrene / hydroxyalkyl (meth) acrylate / ( Alkyl methacrylate/maleic acid copolymer or the like. Further, as the alkali-soluble resin, it is preferable to satisfy the following relationship from the viewpoint of suppressing gas generation in the case of heating the thermosetting composition of the present embodiment and improving heat resistance. [Relationship] V2/V3^ 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 In the case of a distribution curve, the molecular weight corresponding to the molecular weight (Ml) of the maximum peak value is 10 1/2 times. V3: a molecular weight (M3) having a molecular weight (M1) corresponding to the maximum peak value (M1) The weight content of the alkali-soluble resin.) The so-called differential molecular weight distribution curve indicates the weight content of the alkali-soluble resin corresponding to the molecular weight of each molecular weight contained in the soluble resin. The molecular weight distribution curve is measured by the 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 L3 or higher, preferably h5 or higher, and 312XP/invention specification (complement) ()) /96-09/96119466 22 200807152 soil::, above, usually 1, 〇〇〇 below, preferably 5 ο 〇 below, eight, 00 or less. By using such a low molecular weight The less "knife house cloth alkali-soluble resin, image formation can be improved, increasing the strength of the protective film, indium tin oxide on the inhibition of the protective layer (ITO, indium tin ◦Xlde) cracking of the membrane defects. In addition, the alkali-soluble resin having the specific molecular weight distribution can be obtained by, for example, obtaining a '~' by dissolving a commonly obtained alkali-soluble resin in an organic solvent (such as isopropyl glycol monoacetic acid vinegar or the like). After being dissolved, it is mixed with a poor solvent of an alkali-soluble resin such as methanol to precipitate the resin, and the resin to be precipitated is, for example, 4 Torr under reduced pressure. 〇, 12 hours of conditions to make it dry. The content of the alkali-soluble resin in the thermosetting composition of the present invention is usually 5% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less based on the total solid content. Preferably, it is less than 7 ounces. 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. (B) Compound having an ethylenically unsaturated group The compound having an ethylenically unsaturated group used in the thermosetting composition of the present embodiment (hereinafter, abbreviated as "ethylenically unsaturated t δ substance") It is a compound which has one or more ethylenically unsaturated bonds in a molecule. Examples of the compound having one or more ethylenically unsaturated groups include (meth)acrylic acid, crotonic acid, methacrylic acid, maleic acid, and Ikon 312 ΧΡ/invention specification (supplement)/96-09. /96119466 23 200807152 Unsaturated carboxylic acids such as acid and citraconic acid, and alkyl esters thereof, (meth)acrylonitrile, (meth)acrylamide, phenelquinone, and the like. In addition, examples of the compound having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated tickic acid and polyhydroxy compound, and phosphates containing (fluorenyl) acryloxy group, (methyl) Ethylene methacrylate compound and (meth)acrylic acid urethane of polyisocyanate compound, and (meth)acrylic acid or (meth)propionic acid hydroxy ester compound and epoxy (meth) of polyepoxide Acrylic g is intended to be used. These may be used alone or in combination of two or more. (B-1) Ester 2 of an unsaturated carboxylic acid and a polyhydroxy compound is an ester of an unsaturated carboxylic acid and a polyhydroxy compound (hereinafter, it may be simply "Vinegar (meth)acrylic acid g)" Specifically, the following compounds can be exemplified. The reaction product of the unsaturated carboxylic acid and the sugar alcohol: examples of the sugar alcohol include ethylene glycol and polyethylene glycol (addition number 2 to (4), propylene glycol, polypropylene II (addition number 2 to 14), propylene glycol, Butylene glycol, hexanediol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, etc. The above-mentioned unsaturated sulphuric acid and sugar alcohol oxidized dilute adducts are the same as above. An adduct, for example, an oxyethylene adduct, or a propylene oxide adduct, etc. a reaction of an unsaturated (tetra)-amine: as an amine, for example, an ethanolamine, a triethanolamine Etc. For the ==:: with the poly-based compound, more specific ethylene glycol di(meth)acrylate ethylene glycol di(meth)acrylic acid 312XP / invention manual (supplement) / 96- 09/96119466 24 200807152 ^Propany (meth)acrylic acid _, trimethyl methacrylic acid di(methyl) acrylate, three singular sputum, r j- ^ ^ ^ ^ - 兀二 ( Methyl) acrylate, trimethylol propyl:: year: element σ, bis(indenyl) acrylate, glycerol bis(indenyl) propylene = glycerol tris(methyl) Acrylic vinegar, glycerol, propylene, propylene, trimethyl (meth) acrylate, pentaerythritol di(meth) propylene (tetra), pentaerythritol = bis(indenyl) acrylate, pentaerythritol tetra (methyl) Acrylate, = alcohol penta (meth) acrylate vinegar, dipentaerythritol hexa(indenyl) acrylate acid, and the same crotonic acid, isocrotonic acid, cis-butyric acid, Yikang The vinegar, the citric acid ester, etc. Further, as the vinegar of the above-mentioned unsaturated decanoic acid and the poly-based compound, the above-mentioned unsaturated dicarboxylic acid and the benzoic acid, the benzophenone, and the phthalic acid are mentioned. A reaction product of an aromatic (tetra)-based compound such as F, (d), or the like, or an ethylene oxide adduct thereof. Specifically, for example, bisphenol A (America Acrylic Acid, Double A A) Ethyl (meth)acrylic acid], bis-A bis [epoxypropyl squamous (meth) acrylate], etc. Further, as the ester of the unsaturated carboxylic acid and the polyhydroxy compound, the above may be a reactant of a heterocyclic polyhydroxy compound such as an unsaturated carboxylic acid and tris(2-hydroxyethyl)isocyanurate. For example, a di(meth) acrylate or a tri(meth) acrylate of triethylethyl)isocyanurate. In addition, as an ester of the above unsaturated carboxylic acid and a polyhydroxy compound, The reaction product of the above unsaturated carboxylic acid, polycarboxylic acid and polyhydroxy compound is exemplified by, for example, a condensate of (meth)acrylic acid, phthalic acid and ethylene: alcohol, (meth)propionic acid Condensation of (meth)acrylic acid, terephthalic acid and pentaerythritol, cis succinic acid and diethylene sulphate 312 χ 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 96 96 96 96 96 96 96 96 96 96 96 96 96 96 96 缩合 缩合 缩合 缩合 缩合 缩合 缩合A condensate of (mercapto)acrylic acid, adipic acid, butanediol and glycerol. (B-2) A phosphate containing a (meth)acryloxy group as a phosphate containing a (fluorenyl) acryloxy group, and if it is a phosphate compound containing a (meth) acryloxy group, It is particularly limited, and among them, those represented by the following general formulae (1a) to (Ic) are preferred. [3] h2c R10 Ο =4—C- o~^ch2^g 3-q

m da)

CH2-CUz-Q

^-^0C(^0)CH^H2CH2CN2C

(In the formulae (la), (lb) and (Ic), R represents a hydrogen atom or a methyl group, p and P' are integers of 1 to 25, and q is 1, 2, or 3.) Here, p and P' are respectively 1 to 1 〇, especially i to 4. Specific examples of such a compound include (indenyl) acetophenoxyethyl phosphate, bis[(meth)acryloxyethyl]phosphoric acid, and (methodyl) propylene. The decyloxyglycolic acid S is intended to be used alone or as a mixture. (B-3) (fluorenyl) acrylic acid carboxylic acid compound and polyisocyanate compound (mercapto) acrylamide phthalic acid ester as (mercapto) acrylic acid by a compound of 6, for example, (fluorenyl) Propylene 312χρ/Invention Manual (supplement)/96-09/96119466 26 200807152 Acid methyl ester, f ψ I Α π ^ & base) l methyl) acrylic acid ethyl ester, tetra- acrylate, etc. In the case of the polyisocyanate compound, for example, hexamethylene sulfonate, 1,8-diisocyanate, 4-isocyanate decyl octane says 4 sensitized polyisocyanate; % hexanyl diisocyanate, dimethylcyclohexane bisacetoic acid vinegar, 4, 4 fluorenyl bis(cyclohexyl isocyanate), An alicyclic polyisocyanate such as isophora-diisocyanate or bicycloheptane diisocyanate; aromatic polyisocyanate such as 4'4 monophenylmethane diisocyanate or tris(isocyanatephenyl) thiostearate; Heterocyclic polyisocyanate such as cyanurate; by Japanese Patent Laid-Open No. 2, No. 1,260,261 The allophanate-modified polyisocyanurate produced by the method disclosed in the publication; the polyiso-soy acid S-functional compound. The (meth)acrylic acid amine as the (meth)acrylic acid hydroxyester compound and the polyisocyanate compound a carbamate, preferably an (meth)acrylic acid amide derivative containing the above allophanate-modified polyisocyanurate. The allophanate-modified polyisocyanurate is contained. The ester (meth)propionate urethane has low viscosity, is excellent in solubility in a solvent, and is effective for improving adhesion to a substrate and film strength by photohardening and/or thermal hardening. good.

As the above (fluorenyl) acrylate urethane in the present embodiment, a commercially available one can be used. Specifically, for example, the brand name "U-4HA", "UA-306A", "UA-MC340H", "UA 312XP/Invention Manual (supplement)/96-09/96119466 27 200807152, manufactured by Shin-Nakamura Chemical Co., Ltd. MC340H" "U6LPA", a compound "AGROR4060" having an allophanate skeleton manufactured by Bayerin Japan Co., Ltd., and the like. In view of the sensitivity, the above-mentioned (meth)acrylic acid amide ruthenium amide is preferably contained in four or more molecules (preferably six or more, more preferably eight or more). a urethane bond [-NH-C0-0-], and a compound of four or more (preferably six or more, more preferably eight or more) (fluorenyl) propenyloxy groups. This compound can be obtained, for example, by reacting the following compound (i) with the following compound (i i). (i) A compound containing four or more amino phthalic acid ester 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 decyl diisocyanate; or two or more molecules including one molecule of ethylene glycol or the like The hydroxy compound is the "DURANATE 24A-100" manufactured by Asahi Kasei Kogyo Co., Ltd., the "DURANATE 22A-75PX", the "DURANATE 21S-75E", the "DURANATE 18H-70B" and the like, and the "DURANATE P — a compound obtained by reacting a compound containing three or more isocyanate groups in one molecule such as an additive type such as "DURANATE E-402-90T" or "DURANATE E-405-80T" (i) 2); Alternatively, the isocyanate (meth) acrylate or the like is polymerized or copolymerized to obtain a compound (i-3) of 312XP/invention specification (supplement)/96-09/96119466 28 200807152. A commercially available product can be used as the compound, and for example, "DURANATE ME20-1" manufactured by Asahi Kasei Kogyo Co., Ltd. can be used. Examples of the compound containing four or more (meth) propylene fluorenyl groups in the '(1) knives include pentaerythritol di(meth) acrylate, dipentaerythritol tri(meth) acrylate, and dipentaerythritol tetra (a) One molecule of acrylate, dipentaerythritol penta (meth) acrylate vinegar, dipentaerythritol hexa-propyl acrylate, and the like contains one or more hydroxyl groups and two or more, preferably three or more (subgroups) A compound that brews an oxy group. Here, the molecular weight of the compound (i) is preferably ～200,000, particularly preferably 100 (^50,000). Further, the molecular weight of the (meth)acrylic acid urethane is preferably 600 to 150, 〇 Further, such a (meth)acrylic acid urethane can be, for example, obtained by subjecting the compound of the above (1) and the compound of the above (ii) to an organic solvent such as toluene or ethyl acetate. 〇~15 (arc is produced by a method of rc reaction for about 5 minutes to 3 hours. In this case, it is preferred that the molar ratio of the former isocyanate group to the latter hydroxyl group is !/; [〇~〗 〇/1 Proportion, if necessary, use a catalyst such as n-butyltin dilaurate. (B 4) Epoxy (meth) acrylate as a (meth)acrylic acid or a hydroxyester (meth)acrylate compound and a polyepoxide Examples of the polyepoxy compound include (poly)ethylene glycol polyepoxypropyl ether, (poly)propylene glycol polyepoxypropyl ether, (poly)butylene glycol polyepoxypropyl ether, and (poly) Pentylene glycol polyepoxypropyl ether, (poly) neopentyl glycol polyepoxypropyl ether, (poly)hexanediol Oxypropyl propyl ether, (poly) 312XP / invention specification (supplement) / 96-09/96119466 29 200807152 dihydroxydecyl propane polyepoxypropyl ether, (poly) glycerol polycyclopropyl propyl ether, ( Poly) polyepoxy compound such as sorbitol polyepoxypropyl ether; phenolic phenolic polyepoxy compound, brominated phenolic phenolic polyepoxy compound, (〇-, m-, p-) indophenol phenolic polyepoxy Aromatic polyepoxides such as compounds, bisphenol A polyepoxides, bisphenol F polyepoxides; sorbitan anhydride polyepoxypropyl ether, triepoxypropyl isocyanurate, isocyanuric acid Heterocyclic polyepoxy compound such as epoxypropyl tris(2-hydroxyethyl) ester; polysilic oxide compound. Reaction as (meth)acrylic acid or hydroxyester (meth)acrylate compound with polyepoxide Examples of the epoxy (meth) acrylate include a reaction product of such a polyepoxy compound with (meth)acrylic acid or the above (meth)acrylic acid hydroxyester compound. (B-5) Other ethylenicity The saturated compound is another ethylenically unsaturated compound, and examples thereof include, for example, the above. (ethyl) acrylamide such as ethyl bis(methyl) acrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate a compound containing a thioether bond which is obtained by vulcanization of an ether bond of an ethylenically unsaturated compound containing an ether bond to a thioether bond by phosphorus pentasulfide or the like, thereby increasing the crosslinking rate. A polyfunctional (meth) acrylate compound having a particle size of 5 to 30 nm is disclosed using a decane coupling agent containing an isocyanate group or a mercapto group as disclosed in Japanese Patent No. 3,164,407, and the like. The sol is sol [for example, isopropyl alcohol-dispersed organic sol 312XP/invention specification (supplement)/96-09/96119466 30 200807152 ("IPA_ST" manufactured by 曰Chem Chemical Co., Ltd.), methyl ethyl hydrazine dispersed organic cerium sol ( "MEK-ST" manufactured by Nissan Chemical Co., Ltd., and methyl isobutyl- ketone-dispersed organic sol ("μιβκ_^τ W-bonded compound manufactured by Nissan Chemical Co., Ltd.). The compound is a compound which reacts with an ethylenically unsaturated compound via a Shi Xixuan coupling agent to bond the ethyl sulphate to the strength of the cured product. Further, as another ethylenically unsaturated compound, those known from the publication of Japanese Laid-Open Patent Publication No. 2005-165294 can also be known. They may be used alone or in combination of two or more. In the case of Benbe & Open/Sorry, a tetraethylenically unsaturated compound is preferably contained in the molecule and contains two ethylenically unsaturated groups in view of polymerizability and crosslinkability. Compound. Among them, ester (methyl) propionate, phosphate containing (meth) propylene oxime, or amino acid methacrylate (meth) acrylate, more preferably vinegar (methyl) Acrylic g is a class. In the category of (meth)acrylic acid S, 'excellently is a bis-A (meth)acrylic acid vinegar, biguanide A bis[oxyethyl (meth) acrylate], bisphenol a double An aromatic poly-based compound such as [epoxypropyl group=methyl)acrylic acid vinegar] or a reaction product with the ethylene oxide adduct thereof. In addition, 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), and therefore, as such an ethylenically unsaturated compound, for example, an aliphatic polyfunctional acrylate, and a (meth) acrylate compound of a poly-A or a hydrazine-containing polyol may be mentioned. Wait. 312XP/Invention Manual (Supplement)/96-09/96119466 31 200807152 The content of the ethylenically unsaturated compound in the thermosetting composition of the present embodiment is usually 10% by weight based on the total solid content. The above 'preferably 20% by weight or more, usually 70% by weight or less, preferably 6% by weight or less. When the amount of the compound having an ethylenically unsaturated group on the right is too small, the sensitivity is lowered and the development dissolution rate 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 of the weight is usually 1% 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. If the content of the compound containing two ethylenically unsaturated groups is too large, the chemical resistance may be lowered. On the other hand, if the content is too small, the peeling property may be lowered. In addition, when at least a part of a compound containing three or more ethylenically unsaturated groups is used as the component (β) in the present embodiment, the content of the compound containing three or more ethylenically unsaturated groups is relative to (Α) The component of the soluble resin is 100 parts by weight, usually 10 parts by weight or less, preferably 60 parts by weight or less, more preferably 55 parts by weight or less. The total weight of the compound containing 3 or more ethylenically unsaturated groups in the component (Β) relative to the total weight of the (Β) component is usually 8 parts by weight or less, preferably 60 parts by weight. It is more preferably 55 parts by weight or less. The ratio of the compound containing three or more ethylenically unsaturated groups to the total weight of the above component (Α) and the above component (Β) is usually 6% by weight or less, preferably 50% by weight or less, more preferably 4% by weight. Below 5% by weight, the lower limit 312 ΧΡ / invention specification (supplement) / 96 · 〇 9 / 9619 466 32 200807152 is usually 5% by weight or more. By using a compound containing three or more people's age groups, it is possible to use a soap to improve the hardness of the enamel, but the peeling property after exposure is lowered. Then, the valley is easy to v, and the ratio of ^(8) is less than 150 parts per liter, and is less than 120 parts by weight, and more preferably less than the weight of U0. It is usually 50 or more. Preferably, it is 7 parts by weight or more, more than 8 parts by weight, 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 one of A if it has an absorption maximum in the range of 310 to 370 nm. A compound which generates a radical which polymerizes an ethylenically unsaturated group by ultraviolet-ray to visible light is mentioned. Further, a photopolymerization initiator which does not have an absorption maximum in the range of 310 to 37 Gmn may be used in combination with a photopolymerization initiator having an absorption maximum in the range of 31 〇 to 37 () nm. Specific examples of the polymerization initiator which can be used in the present embodiment are listed below. (I) 2-(4-Methoxyphenyl)_4,6-bis(trichloromethyl)-tetrasyl, 2-U-methoxynaphthyl)-4,6-bis(trichloromethyl) All three, 2_(4_ethoxynaphthyl)-u-bis(trimethylmethyl) are all three 4,2_(4_ethoxyxoylnaphthyl)-4' 6-bis(trichloroanthracene) Base) three-tillage and other halogenated thiolated three-cultivated derivatives. (II) 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, _ chlorophyll and other brewing derivatives. 312XP/Invention Manual (supplement)/96-09/96119466 33 200807152 (ii Benzene benzopyrene} derivative. (iv) Benzophenone, Miclerone, 2-Methylbenzophenone, 3 Monobenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, benzophenone derivatives such as [bromobenzophenone, 2-carboxybenzophenone. (V) 2'2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyphenyridinium, 1-ylcyclohexylphenyl H-based 2-methylphenylpropanone, Bu Keji + methyl ethyl-(p-isopropylphenyl) ketone, dipyridyl-p-(p-phenyl) ketone, 2-methyl-(4,~(methylthio)benzole-2-imlin A acetophenone derivative such as 1,1'l-trichloromethyl-(p-butylphenyl) ketone. thi〇xanthone, 2_ethyl 嗟仙, 2 _ isopropyl thiazolone, 2-chloropyridone, 2,4-dimethyl fluorene, 2,4-diethyl ketone, 2, 4-diisopropyl thioxanthone and other thioxene Ketone derivatives. (6)) 9-phenyl ° acridine, 9-(p-methoxyphenyl) acridine, etc. oxime derivative (viii) 9' 1G--methylbenzophene Derivatives. Titanium (1 Γ bis 3 pentylene) dichlorinated (cyclopentadienyl) diphenyl (cycloindole and dilute) - bis (2' 3, 4, 5, 6-pentafluorophenyl-bu) titanium, diene wu) two (2 soil 4 wide, 3,5,6~tetraqibenzene+yl)titanium, bis(cyclopentadienyl-(fluorinated phenyl) titanium, bis(cyclopentadienyl)-2,6-i cone two t, double (cyclopentadienyl-2,4-di(fluorobenzene+yl). 土土王衣戊一烯)~二(2,3,4,5,6-pentafluorobenzene-;[-based) ( Cyclopentacyclopentanylbis(2,6-di-fluorophenyl-1-yl)titanium wide double 119466 312XP/invention specification (supplement)/96-09/96 34 200807152 002-methyl-1[4 -(Methylthio)phenyl]_2_imilinyl-bu-acetone, 2-benzyl-2-dimethylamino+ (4-aminophenylphenyl η-butyrene, 2-negyl'_2_ Di-aminoamidophenylphenyl)-ι-butanone, benzoic acid 4_: methylaminoethyl ester, 4-dimethylaminoisobenzoic acid heteronuclear, 4-diethylaminoethyl acetophenone , 4-dimethylaminopropiophenone, benzene-...ylamino, 2,5-bis(4-diethyl-based bis- ketone, 7-diethylamino-3-(4_2) Ethylaminobenzhydryl)coumarin, 4-(diethylamino)chalcone, etc. ^Aminoalkylphenone compound '., 〇ci) 2,j,6- A fluorenylphosphine oxide compound such as methylbenzhydryl-diphenylphosphine oxide or bis(2,4' 6-dimethylbenzylidene)-phenylphosphine oxide. (χιι)1,2- Octanedione, Bu [4_(phenylthio)phenyl]_2_(〇_benzoamyl), ethyl ketone, 1-[9-ethyl-6-(2-mercaptobenzylidene)_9H-indole Azole _3_ ki]-1-(0- 醯 醯月)) (X111) Japanese Patent Laid-Open No. 2000-80068, JP-A-2001-233842, JP-A-2001-235858, JP-A-2005-182004 Anthraquinone derivatives represented by the compounds disclosed in the specification of the Japanese Patent Application No. 2005-305074, and the Japanese Patent Application No. 2005-305074. Among them, 'good luck' is an acridonone derivative, an α-aminobenzophenone compound, and two derivatives, and more preferably an α-aminoalkylphenone compound or an anthracene derivative. The remote photopolymerization initiators are used singly or in combination of several. As a combination, for example, Japanese Patent Publication No. Sho 53_128〇2, Japanese Patent Laid-Open No. 312ΧΡ/Invention Manual (Supplement)/96-09/96119466 200807152, No. 1 - 279903, and JP-A No. 2-Reissue No. A combination of the initiators disclosed in Japanese Laid-Open Patent Publication No. Hei 4-16 or Japanese Patent Laid-Open No. Hei. The amount of the photopolymerization initiator contained in the thermosetting composition of the form is generally 〇.丨% by weight or more, preferably 0.5% by weight or more, usually 4%, based on the total solid content. It is below weight%, preferably by weight % j. When the amount of the photopolymerization initiator is too small, the sensitivity tends to decrease, and if it is overnight, the scum tends to cause a decrease in scum (developing solubility). The blending ratio of the component (6) to the component (8) is usually 2 parts by weight or less based on the component (B) by weight of the component (6), preferably less than or equal to the weight of the component, and usually 0.1 part by weight or more. It is preferably 0.5 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 heat resistance and chemical resistance of the film after heat curing. As the hot parent, if it is a cross-linking reaction by hard baking after image formation by exposure and development, a well-known person can be used. Specifically, the following may be mentioned, and these may be used alone or in combination of two or more. (D-1) A compound containing an epoxy group in the molecule as a compound containing an epoxy group in the molecule used in the present embodiment. For example, a monohydroxy compound or a polyhydroxy compound is reacted with epichlorohydrin. (poly)epoxypropyl ether compound, polyepoxypropyl ester compound obtained by reacting (poly)carboxylic acid compound with epichlorohydrin, and (poly)amine 2XP/invention specification (supplement)/96 - 〇 9/96119466 36 200807152 A compound obtained by converting a (poly)epoxypropyl aminated product obtained from a gas reaction with a low amount of 7 knives into a high molecular weight substance. . A polyepoxypropyl ether compound is used as a polyepoxypropyl ether compound, for example, a 4-oxopropyl ether type epoxy resin, a bis (4 alcohol bicyclic epoxy resin) , 5-2-1 base: two-ring double F-epoxy propyl ether type epoxy tree two pairs: A - latex propyl ether epoxy resin, four (four) epoxy resin, epoxy Ethylene burn Double dr: oxypropyl oxy-resin, _ A ! + t A - 裱 propyl propyl ether ring I storm type mulberry resin, dihydroxy oxy resin, bisphenol A / aldehyde phenolic epoxy ρ soil Lamb soil, % A secret type epoxy resin. ", home-type epoxy resin, in addition, polyepoxypropyl ether compound A contains as a polyepoxypropyl scale resin, can be cited both / / Feng II Epoxy resin, epoxy resin, epoxy resin, epoxy resin, epoxy resin, epoxy resin, epoxy resin, aging epoxy resin, etc. ♦ σ clothing oxygen resin, etc. Phenolic Resin The residue of the fish such as the (poly)epoxypropyl etherified character compound may also be introduced into the carboxyl group by the acid needle or the divalent acidified spear/residual reaction. (D - 1 - 2 Polyepoxypropyl esterification As a compound of a polyepoxypropyl group, a bicyclic oxime is exemplified, and a bismuth acetonate type epoxy resin, an phthalic acid type epoxy resin, etc. are mentioned. a propyl propyl ester 3) polyepoxypropylamine compound (D-1 312ΧΡ/Μ__ί_·_6119466 37 200807152

Amine type epoxy resin and the like. (D - 1 - 4) Others, for example, bis(4-aminophenyl) lipid, isomeric cyanuric acid triglycidyl

The resulting polymer. A (meth) acrylate having an epoxy group such as acryl-6, 7-epoxyheptyl ester or ethyl hydrazine, or a (meth) acrylate having an epoxy group, usually The polymer of the other copolymerization monomer is from 1 to 7 mol%, preferably from 15 to 60 mol%. Examples of the monomer for copolymerization include (meth)acrylic acid, (mercapto) decyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and f-methyl)acrylic acid-2- Ethylhexyl ester, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyacetate (meth)acrylate, (meth)acrylic acid An ester of (meth)acrylic acid such as isobutyl ester, and a bis-fragrance compound such as styrene, α-mercaptostyrene, p-nonylstyrene or vinylnaphthalene. As the (fluorenyl) acrylate having an epoxy group, a (meth)acrylic acid propyl propyl ester is preferred. Further, preferred monomers for copolymerization include (cyclo)acrylic acid dicyclopentanyl ester, styrene, and α-mercaptostyrene. When the epoxy compound is a resin (sometimes abbreviated as "epoxy resin") 312XP/Invention Manual (Supplement)/96-09/96119466 38 200807152 K is a preferred molecular weight as long as it can be in a solution state: The protective film material (thermosetting composition) is not selected as appropriate, such as the thickness of the coating film, the coating conditions, and the purpose. As its molecular weight, it is usually in the range of _, _, preferably 3, _ ~ just, 2 = ~ ~ 50, 〇〇〇. 1 1 Tu Feng 4, 〇〇〇 Γ , , 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧For the purpose of the present invention, it is also possible to use an α-epoxy group (oxetanium; 4,3-1,3-oxocyclohexyl group. Further, as the epoxy compound of the present embodiment, it does not contain an aromatic group. The manufacturer or the unsuitable base material having an unsubstituted or substituted (p-) position is suitable for suppressing discoloration of the protective film by heat treatment (a red color is widely used as such an epoxy compound, and for example, (4) Α type Epoxy compound and ring & (4), an epoxy compound having a substituent-containing frame, a copolymer of epoxy diester, (meth)acrylic acid glycidyl ester, etc. The thermosetting composition of the present embodiment When the compound contains a compound having an epoxy group in the molecule as the (D) thermal crosslinking agent, the content of the compound having an epoxy group in the thermosetting composition = is usually the total solid content. 60% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less Usually, it is i% by weight or more. When the content of the compound containing an oxy group in the molecule is too large, the % stagnation property of the thermosetting composition solution is likely to decrease, and the peeling property after exposure and development is lowered. 2) Nitrogen-containing thermally crosslinkable compound 312XP / invention specification (supplement) / 96-09/96119466 39 200807152 屮佶ί Ϊ Only the nitrogen-containing thermally crosslinkable compound used in the form can be mentioned: In the case of melamine, benzoic melamine, or sulphur-based modified compounds. Α As an example of a compound that causes formalin to act on melamine or an alkane shellfish, Cytec (10) such as “Zh. "161" (registered trademark) 3GG, 3G Bu 303, 350, 736, 738, 771 325, 327, 703, 701, 266, 267, 285, 232, Xue Gong / 38; 1141, 272, 254, 202, 1156, 1158, Nkalac" (registered trademark) E_ 2151, MW-100LM, MX-750LM, etc., and as a compound for causing fumarin to act on phenyl melamine or its & base modification , which can be cited as "Cymel" (registered trademark) 11 23, 1125, 1128, etc. As an example of a compound which causes formalin to act on glycoluril or an alkyl modified substance, "Cymel" (registered trademark) 1170, 1171, 1174, U72, "Nikalac" (registered) (Trademark) Mx_27(), etc. Further, as an example of a compound which causes fumarin to act on urea or an alkyl modified substance thereof, "UFR" (registered trademark) 65, 300, "Nika lac" manufactured by Cytec Industries, Inc. (registered trademark) MX-290, etc. In the (D) thermal crosslinking agent in the present embodiment, a compound containing -N(CH2?R)2 group (wherein R represents an alkyl group or a hydrogen atom) is preferably contained in the molecule. Particularly preferred is a compound which causes formalin to act on urea or melamine or an alkyl modified product thereof. The thermosetting composition of the present embodiment contains a nitrogen-containing heat crosslinkable compound 312XP/invention specification (supplement)/96-09/96119466 40 200807152 as a thermosetting composition in the case of (8) thermal crosslinking agent The content of the thermally crosslinkable compound in the article is usually τ ^ or less with respect to the total solid content, preferably 30% by weight or less, more preferably 20% by weight to: : Too much amount of the right diazo thermally crosslinkable compound However, it is easy to cause a decrease in the filming rate and a decrease in resolution at the time of development. Among them, as the thermal crosslinking agent (8), a compound of -n(ch2〇r) 2 & (wherein, R represents 基 3 ^ κ or a ruthenium atom) is preferred. More specifically, it is a compound that causes formalin to act on urea or melamine or a burn-in modification thereof. (Ε) Other components (Ε ~ 1) Adhesive aid For the purpose of adhesion between the substrate and the substrate, the adhesive agent can be formulated in the hot hard niobium of the present embodiment. As the adhesion aid, for example, more specifically, for example, trimethoxydecyl benzoic acid is exemplified.

Methyl acrylate oxypropyl hydrazine I 1 I (four) - methyl milk money, vinyl triethyl ethoxylate shixiyuan, ethylene trimethoxy lanthanum, pull w kg τ decane, oxime propyl oxygen Propyl trimethoxy

Basestone, r-isocyanatopropyldiethylene 4, its work w D ^ A soil-G-decyl decane, cold-(3,4-epoxyhexyl)ethyldimethoxydecane, and the like. These materials may be used singly or in combination of two or more. In addition, the '(iv) coupling agent not only functions as an adhesion aid, but also imparts moderate heat fusion to the protective film during heat treatment (heat flow). Sex), the function of improving flatness. As a material coupling agent formulated for such a purpose, a decane coupling agent having a decyloxy group is exemplified by 312 ΧΡ/invention specification (supplement)/96-09/96119466 41 200807152. More specifically, for example, r-glycidoxypropylmethoxy-, 3-(3,4-epoxy nucleyl)ethyltrimethoxydecane, and the like are mentioned. In the case of using an adhesion aid, the total solid content relative to the thermosetting composition is usually 重量% by weight or more, usually 20% by weight or less, preferably ίο, in the formulation of the above-mentioned adhesion promoter. %the following. (E-2) Surfactant The thermosetting composition of the present embodiment may contain nonionic ions for the purpose of improving the coating property of the coating liquid of the composition and the developability of the thermosetting composition layer. A sexual, anionic or cationic amphoteric surfactant, or a surfactant such as a fluorine-based or polyfluorene-based surfactant. Examples of the nonionic surfactant include polyoxyethylene alkyl hydrazines: polyoxyethylene polyoxypropylene decylene, polyoxyethylene alkyl benzoquinones, polyoxyethylene alkyl esters, and polycondensation. Oxyethylene fatty acid esters, glycerol fatty acid vinegars, polyoxyethylene glycerol fatty acid g, pentaerythritol fatty acid®, poly-A vinyl pentaerythritol fatty acid g, sorbitol, fatty acid esters, polyoxygen Ethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like. As such a commercial item, a polyoxyethylene surfactant such as rEmulgen 1 () 20,000 "Emulgen A60" manufactured by Kao Corporation is used. Further, examples of the anionic surfactant include alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkyl ethersulfonates, and alkyl groups. Sulfates, alkyl sulfates, higher alcohol sulfates, aliphatic alcohol sulfates, polyoxyethylene alkyls = sulfur 312XP / invention instructions (supplements) / 96-09/96119466 42 200807152 acid Salt, polyoxyethylene, typography, p I # ate 7 π alkenyl ether sulfates, alkyl phosphate salts, water-oxyethylene decyl ether phosphate 蹿 | | Phytate, special polymer interface interaction sword _ ^ ^ ^, oysters. Among these, a special high score "1" is preferred, and a special polycarboxylic acid type polymer surfactant is more preferred. As such an anionic and surfactant-injecting agent, a commercially available product can be used, for example. Alkyl sulphate I can use salt ^ μ τ, "Emal 10" manufactured by Niu Xinghua Wang Co., Ltd., etc., and the naphthalene sulfonate can be combined with Manufactured pelex NB-I, 笪, & l First-class special molecular-based surfactants can be exemplified by Kao Co., Ltd.

Homogenol L·—18”, “Homogenol L—100”, etc. Further, 'the above-mentioned cationic surfactant may, for example, be a quaternary salt: a carbazole: a derivative, a genus, an amine salt, or the like, and an amphoteric interface η can be a sweet potato-based compound or imidazole. Barium salts, imidazolines, amino acids, and the like. Among these, it is preferably a quaternary (four) class, more preferably a stearyl quinone sulfonium salt. As a commercial product, for example, the "Quartamin 24P" manufactured by the Quaternary Ammonium Salt Co., Ltd., "Quetamin 24" manufactured by the Quaternary Ammonium Salt Co., Ltd., etc. "Quartamin 86W" and so on. On the other hand, as the fluorine-based surfactant, a compound having m or a fluorine-expanding group at least at any of the terminal, main chain and side bonds is preferred. > Specifically, for example, ι,ι,2,2-tetrafluorooctyl (^, pheno-tetra-propyl propyl), 1,1,2,2-tetrafluorooctyl hexyl ether, octane Ethylene glycol II 312XP / invention specification (supplement) / 96-09/96119466 43 200807152 pentyl) ether, octylpropylene di(p-, 2, 2-tetrafluorobutyl) ether, propylene glycol-one (1, 1, 2, 2, 3, 3-hexafluoropentyl)ether, sodium perfluorododecylsulfonate, Μ'2, 2, 8,8, 9, 9, 10,10-decafluorododecane, n 2, 2, 3, 3-hexafluorodecane, etc. As such commercial products, "βΜ-1 000", "ΒΜ-1100" manufactured by BM Chemie, "Megaface F142D" by Dainippon Ink Chemical Industry Co., Ltd., "Megaface F172", "Megaface" F173", Megaface F183", "Megaface F470", "Megaface F475", "FC43〇" manufactured by Sumitomo 3M Co., Ltd., "DFX-18" manufactured by NE〇s Co., Ltd., etc. In addition, as a polyoxo-type surfactant, for example, "T〇ray si j soil c〇ne D (:3pA", "same as SH7PA", "same DC11PA" manufactured by Si 1 i cone Co., Ltd.) , "Same SH21PA", "Same SH28pa", "Same SH29PA", "Same SH30PA", "Same SH8400", Toshiba

"tsf_444〇" and "tsf" manufactured by Silicone Co., Ltd.

4300", "TSF-4445", "TSF-444(4)(5)(6)(7)6", "TSF 4460", "TSF-4452", "KP341" manufactured by Silicone Co., Ltd., BYK Commercial products such as "ΒΥΚ323" and "βγΚ3 manufactured by Chemie Co., Ltd. ^ Among these surfactants, fluorine-based surfactant and polyfluorene-based interfacial activity are preferred from the viewpoint of uniformity of 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 molecular-based surfactant, and a fluorine-based interface. Active agent/special polymer system boundary = 312 ΧΡ / invention specification (supplement) / 96-09/96119466 44 200807152 A combination of active agents, etc. Among them, a polyfluorene-based surfactant/fluoroquinone surfactant is preferred. In the combination of the polyoxo-based surfactant/fluorine-based surfactant, for example, "TSF446〇" manufactured by GE Toshiba Silicone Co., Ltd. / "DFX - 8" manufactured by NEOS, and βγκ Chemie Manufactured "Βγ" κ — 300” or “BYK_ 330 j /Seimi Chemical Company "s -3 9 3", "κ p 3 4 〇" manufactured by Shin-Etsu Chemical Co., Ltd. / "F-478" or "F-475" from Dainippon Ink Co., Ltd., "SH7PA" manufactured by Toray Silicone "DS_4〇1" manufactured by DAIKIN, "L-77" manufactured by Unicar Corporation of Japan, and "FC4430" manufactured by Sumitomo 3M. 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, and more preferably i to 5, based on the total solid content. weight%. (E-3) Hardener In order to shorten the time in the curing condition or to 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-based compound, a polyvalent carboxylic acid (anhydride), a polymer containing a polyvalent carboxyl group (anhydride), and a thermal acid. Agents, amine compounds, polyamine compounds, and block carboxylic acids. In particular, in the case where the above epoxy group-containing compound is used as the thermal crosslinking agent, a thermosetting agent is preferably used. (E-3 - 1) benzoic acid-based compound as a sulphuric acid-based compound, which may be derived from benzoic acid, benzoic acid, benzene ring 312XP / invention specification (supplement) / 96-09/96119466 45 200807152 to The substituent at the 6 position has a substituent such as a hydroxyl group, a halogen group, an alkyl group, a decyl group, an anthracene, an alkoxy group, an aryl group or an allyl group. Among them, it is preferred that a radical having a high curing ability for an epoxy resin is used as a substituent, and it is particularly preferred to have two or more radicals. Examples of such a benzoic acid compound include 3,4,5-trihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, and fluorene-dihydroxybenzoylbenzene. Formic acid, etc. 't 3~2) polycarboxylic acid (anhydride)

(E) The polybasic acid (anhydride) may, for example, be: - biscycloheptylene dicarboxylic anhydride, hexahydrophthalic anhydride, tetrahydro phthalic acid or the like: ί: dialkyltetrahydroortylene Methacrylic anhydride, methylcyclohexene dicarboxylic acid, needle temple, 式% polycarboxylic acid (anhydride); phthalic anhydride, trimellitic anhydride, pyromellitic acid monocarboxylic anhydride, benzophenone IV Carboxylate 醅 醅 醅 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸 羧酸Etc.: etc. 'preferably trimellitic acid (anhydride), phthalic anhydride. 3-3) a polymer containing a polycarboxylic acid (anhydride) as a polymerization containing a polycarboxylic acid (anhydride) [轩 笪 笪 _ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Part of the half-ester modified polymer and the like. A phthalic anhydride is a compound containing one or more ethylenically unsaturated bonds in a molecule, and 312 ΧΡ /__» (supplement) /96·_6119466 46 200807152 (meth)acrylic acid, and its alkyl ester, ( Acrylonitrile, (methacrylamide, styrene, an olefin having a substituent such as a (poly)alkyloxy group or a burnt group. As a polymer containing a polyvalent carboxylic acid (anhydride), From the viewpoint of the strength of the light-transmitting film, a copolymer of maleic anhydride and an olefin having a substituent such as a (poly)alkyloxy group or a burn group is preferred. CE-3-4) Thermal acid generator 趟Examples of the thermal acid generator include various iron-based compounds such as an aromatic diazonium salt, a diaryl taper, an early base-based salt, a triallyl (tetra), and a triallylsulfonium salt. , dentate compounds, and the like. The hoof as a specific example 'Aromatic diazonium salt can be exemplified by chlorobenzene hexa(10) acid:: methylaminophenyl hexafluorolysine diazonium salt, naphthyl hexa(tri) acid diazonium 1, monomethylaminonaphthyl group Diazonium tetrafluoroborate and the like.錤4,4-di-tert-butyl-diphenyl# L as an aryl sulfonium salt, examples thereof include diphenyltetramethane hydride, dioxane, fluorinated fluorene, and phenylhexafluorodisc acid. Bismuth, diphenyltrisorphate, fluoromethanesulfonate, 4,4,-di-tert-butyl-diphenylhexabutyl-diphenyltetrafluoroborate, 4, 4, fluorine Barium phosphate and the like. Further, as the monophenylphosphonium salt, jujube . ^ . ^ ^ ^ j exemplifies a benzyl-p-hydroxyphenylmethyl-p-phenylene dimethyl hexahydrate, a ruthenium oxime An acid such as a monophenyl (tetra) type such as a compound represented by the following formula (2), which is an acid group, or a p-group-p-phenylenemethyl hexahydrate. I early base (four) type, or card base [Chemical 4] 312XP / invention manual (supplement) / 96-09/9^^^ 200807152 CH: h-Z SbFe (Π) where Z represents phenyl. Further, 'as a tri-propyl propyl salt, triphenyl tetrahydrofuran acid: 'p-phenyl hexafluorophosphate, triphenyl hexafluoroantimonate bismuth, three (p-chlorobenzene sulphate) Acid bismuth, tris(p-chlorophenyl)phosphonium hexafluorophosphate, tris(p-phenylphenyl) hexahydrate, acid, 4-tert-butyltriphenyl hexa-phosphate, etc. Triamyl propyl tetra-acid selenium, tri-saturate ^ /, fluorine & 1 lithi, di-propyl hexahydro acid code, bis (chlorophenyl) phenyl four rat sphagic acid West, two [翕 Μ Μ ^ ^ ^ C milk base) base hexafluorophosphate selenium, bis (gas phenyl) this | hexafluoroantimonate selenium and so on. Examples of (10) vinegar include, for example, f-benzoic acid (4), stone-based soil, 10, ethyl lactate-n-acid vinegar, 2-based basal-based toluene vinegar, and broad-based toluene-sour vinegar 2,4_2, 2, 2, 2, 2, 2, 2, 4 The mono-compound can be exemplified by 2-chloro-2-phenylphenone and 2,2,4,ketone "2,4'6-tris(trichloromethyl) all three wells, 2-( p-Methoxy fine)-4,6-bis(trichloromethyl)-tri-morphine, 2-phenyl-4,6-bis (three C-three: well, 2-(p-methoxyphenyl) )-4,6_bis(trichloromethyl) 1 :, 2 —( 4 —methoxy-oxime-naphthyl)乂6-bis(trichloromethyl) are all three-plowed, double-2-(4) -Chlorophenyl)~—One pound ^)-2 2 2 - « r , 丨, 卜二虱 ethane, bis-1-(4-chlorophenyl parent 2, etc. 2. 2-diethanol, double _ 2_("oxyphenyl..., the strength of the trichlorosulfuric film, the thermal acid generator, considering the light transmittance, 312XP / invention manual (supplement) / 96-09/96119466 200807152 points, Preferably, it is a monophenyl salt-salt type or a succinyl-phenyl salt-salt type. (E-3 - 5) Amine compound as an amine compound, for example, ethylamine, 3-aminopropane, 1,4 -diaminobutane, hexamethylenediamine, 2'5-dimethylhexamethylenediamine, piperidine, pyrrolidine, triethylenediamine, trimethylhexylamine, monomethylcyclohexylamine, tetramethyl胍, triethanolamine, N, N, _ dimethyl Iptylphenidate, dicyandiamide, or a derivative thereof; DBU (1,8-diazabicyclo(5,4, fluorene) undecene), an aliphatic amine such as DBU tetraphenylborate (first grade, two Grade, tertiary); m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiethylmethane, benzyldiamine, dimethylamino- P-cresol, 2 - 曱月女一曱曱), 2,4,6-tris(didecylamino fluorenyl), pyridine, acridine, DBU (1,8-diaza Aromatic amines such as bicyclo(5,4,0)undecene-1), 2,4,6-tris(didecylaminoindenyl)phenol, tris-ethylhexyl acid salt (first grade, two Grade, tertiary); 2-mercaptopurine, 2-ethyl-4-methyl sputum, 2-ethyl-4-methyl oxime, 2-111 alkyl ΰ ΰ, 2- Hexazepine base, 2_phenyl miso, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-mercaptoimidazole, 1-cyanoethyl-2-ethyl 4-mercaptoimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium Isocyanurate, 2-phenylimidazolium, isocyanide Sour vinegar, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-distributive, 2,4-diamino-6-[2-ethylimidazolyl -(1)]-Ethyl-all-seven, 2,4-diamino-6-[2-indolenosyl imidazolyl-(1)]-ethyl one-dimension, 2-stupyl one 4, 5-312ΧΡ/Invention Manual (supplement)/96-09/%119466 49 200807152 Monohydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxydecyl imidazole, 1-arylethyl An imidazole compound such as -2-phenyl-4,5-di(cyanoethoxymethyl)imidazole; monoethylenediamine, imine bispropylamine, bis(hexamethylene)triamine, and the like. Among the 4th and the like, dicyandiamide and DBU-based tetraphenylborate are preferred from the viewpoint of the strength of the cured film. CE-6) Polyamine compound As the polyamine compound, for example, triethyltetramine, tetraethylidene May, pentaethylhexamine, dimethylaminopropylamine, diethylaminopropylpropane Phytophthora, N-Aminoethylpiperine, menthanediamine, isofluorodiamine, bis(4-amine-3-methylcyclohexyl)methane, diaminodicyclohexylamine, N,N An aliphatic polyamine such as monodecyl hexylamine, an aromatic polyamine such as m-xylylenediamine, xylylenediamine, xylylenediamine derivative or the present monomethylamine dimer. Among these, N,N-dimethylcyclohexylamine is preferred. (E-3-7) Block carboxylic acid, as a block carboxylic acid, for example, the above-mentioned (poly) carboxylic acid and a carboxylic acid containing the same are disclosed in Japanese Laid-Open Patent Publication No. Hei-4-218561. The block carboxylic acid of the ether and the like disclosed in Japanese Laid-Open Patent Publication No. 2003-66223, JP-A No. 4, pp. Among the above-mentioned curing agents, the polymer containing a polyvalent carboxylic acid (anhydride), a rust salt compound, a block carboxylic acid compound, and a benzoic acid compound have good curing activity, and high hardness and adhesion to a support can be obtained. Aspect: Jia 2 More specifically, it can be mentioned that: 3 UXP / invention manual (supplement) / 96-09/96119466 50 200807152 j butene-g-anhydride and self-containing alkyl group having a carbon number of 丨~2〇, a polycarboxylic acid copolymer of a vinyl compound having at least one selected from the group consisting of a carbon number of 1 to Η = ♦ a propylene oxypropylene group or a carbon number propylene propylene propylene compound; a sulphuric acid-containing compound containing trimellitic acid or an adduct of maleic acid and ethyl vinyl ether; 2, 5--benzoic acid, 3, 4, tri-benzoic acid, etc. Benzoin compound; mercapto-p-p-phenylmethylhexafluoro acid, p-phenylenediyl hexafluoro-acid, p-acetoxyphenyl dimethyl hexafluoride (four), section a monophenyl sulfonium salt such as a compound represented by the above formula (1), or a phenylphenyl salt type, etc. Monophenyl salt and the like. These hardeners may be used singly or in combination of two or more. The hardening agent n poly-domain acid copolymer and the benzoic acid compound are superior to the support (10), and the single salt is superior in hardness improvement. In particular, a benzoic acid 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 0.05% by weight or more based on the total solid content, preferably i. i% by weight or more, usually 20% by weight or less, preferably 1% by weight or less. If the amount of the hardener is too small, the adhesion to the support tends to be small, and if the amount is too large, the increase in the heat weight is likely to occur. 312XP/Invention Manual (Supplement)/96-09/96119466 51 200807152 (F) Additive The thermosetting composition of the present embodiment, in addition to the above-mentioned components, may also be formulated with various additives, for example, a substituent having a substituent. Base 2::: human to phenol, p-methoxyphenol, 2, 6_ di-t-butyl-p-cresol I... preventive agent. The solid content of the compound to be formulated is usually U% by weight or less, preferably 2% by weight or less. Further, it is also possible to contain a plasticizer such as dioctyl phthalate, di(dodecyl) phthalate or tricresyl phosphate in a ratio of 40% by weight or less, preferably 2% by weight or less. . 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-phenylglycine or a bipolar ion compound thereof, a mercaptobenzothiazole, a 2-mercaptobenzimidazole, and a 2-fluorenyl group. Benzooxazole, 3 bis, 1, 2, 4 fluorene, 2-sulfanyl-4(3H)- 啥嗤 lin, cold-wei naphthalene, ethylene glycol dithiopropionate, tris a compound containing a mercapto group such as methyl propane trithiopropionate or pentaerythritol tetrathiopropionate, hexanediol, trimethoprimic dithiogluconate, pentaerythritol tetrathiopropionate, etc. Functional thiol compound, N,N-dialkylamino benzoate, n-phenylglycine or a derivative thereof such as ammonium or sodium salt, phenylalanine, or its = or sodium salt An amino acid having an aromatic ring such as a salt or an ester-derived derivative or a derivative thereof. In the case where a polymerization accelerator is added to the thermosetting composition of the present embodiment, the content ratio thereof is preferably 2% by weight or less, more preferably 1 to 10% by weight based on the total solid content. Further, in the thermosetting composition of the present embodiment, an ultraviolet absorber may be added as needed. The ultraviolet absorber is added for the purpose of controlling the thermosetting composition of the present embodiment formed on the substrate by absorbing the specific wavelength of the light source used for the exposure by the ultraviolet absorber. The rate of photohardening at the time of film exposure. By adding an ultraviolet absorber, it is possible to obtain an effect of improving the pattern shape after exposure and development, or eliminating the residue remaining in the non-exposed portion after development. As the ultraviolet absorber, for example, a compound having an absorption maximum between 250 nm and 400 nm can be used. More specifically, for example,

Sumisoapl30 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORBIO, EVERS0RB11, EVERS0RB12 (made by Taiwan Yongguang Chemical Industry Co., Ltd.), T(10)isoap800 (manufactured by API Corporation), SEESORBIOO, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEES0RB151 (Shipro Chemical System), etc. Benzophenone compound;

Sumisoap200, Sumisoap250, Sumisoap300, Sumisoap340, Sumisoap350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by Seongbuk Chemical Industry Co., Ltd.), TINUVIN PS, TINUVIN99 - 2, TINUVIN109, TINUVIN384 - 2, TINUVIN900, TI.VIN928, TINUVIN1130 (manufactured by Ciba Specialty Chemicals), EVERSORB70, EVERS0RB7, EVERS0RB72, EVERS0RB73, EVERS0RB74, EVERS0RB75, EVERS0RB76, EVERS0RB234, EVERS0RB77, EVERS0RB78, EVERSORB80, EVERS0RB81 (made by Taiwan Yongguang Chemical Industry Co., Ltd.), TomisoaplOO, 312XP/Invention Manual (supplement)/ 96-09/96119466 53 200807152

Benzotrixamide (made by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, · SEESORB707, SEESORB709 (Shipro Chemical), etc.

Sumisoap 400 (manufactured by Sumitomo Chemical Co., Ltd.), phenyl phthalate compound such as phenyl salicylate; hydroxyphenyl sulfonate compound such as TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477 DW, TINUVIN 479 (manufactured by Ciba Specialty Chemicals). Among them, a benzotriazole compound, a phenyltriazine compound, and a benzotriazole compound are preferred. When the ultraviolet absorber is added, the total solid content of the thermosetting composition is usually 〇1% by weight to 15% by weight, preferably 0.05% by weight or more, based on the blending ratio. Below weight%. When the blending ratio of the 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-mentioned respective components are usually used in a solution or blended so as to use an organic solvent to have a solid content concentration of 5 to 60% by weight, preferably 10 to 50% by weight. The organic solvent is not particularly limited as long as it can dissolve and disperse the above components and has good workability. Specific examples include, for example, thioglycosin, ethyl acesulfame, butyl quercetin, diethylene glycol monoterpene ether, 312 ΧΡ/invention specification (supplement)/96-09/96119466 54 200807152 Propyl alcohol early acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate below 'sometimes abbreviated as "PGMAc"), methyl ethyl ketone, methyl isobutyl di-, cyclohexyl, Toluene, chloroform, dichloromethane, ethyl acetate, methyl lactate, ethyl lactate, propionic acid 3_methoxyformic acid vinegar, propylene glycol monomethyl scale, methanol, ethanol, propanol, butanol, tetrachloromethane , Ethyl dimethyl ether, methoxy butyl acetate, S〇lvesso, carbitol and the like. As the above-mentioned organic solvent, it is preferably (10)~, more preferably 120~l7 (the range of rc. Back# ί, 1 胄 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 》 The combination of the organic solvents to be used in combination may be, for example, one or more organic solvents selected from the group consisting of diethylene glycol dimer, acetic acid butyl acrylate, S〇lvesso, and carbitol. t In the above mixed solvent, the ratio of the organic solvent selected from the group consisting of diethylene glycol dimethyl ether, methoxybutyl:::olveSSO, and carbitol is usually 10% by weight or more based on PGMAc. Preferably, it is 3% by weight or more, usually 80% by weight or less, preferably 70% by weight or less. In the above mixed solvent, coating in the coating drying step is induced by PGMAc and methoxy acetoacetate. It is preferable to flatten the unevenness of the film, and to make the base [the method of adjusting the physical properties of the thermosetting composition] to the thermosetting composition of the present invention so that the wavelength is 4 〇〇 (10). The rate of advance reaches a film thickness of 9 Å per i (four), and the photopolymerization initiator is in the training ~370 The means for having an absorption maximum in nm includes the following methods: 1) The component (A) is used as a resin having high transparency to visible light. 312XP/Invention Manual (Supplement)/96-09/96119466 55 200807152 Specific examples of such an alkali-soluble resin include an alkali-soluble resin which does not contain a phenolic hydroxyl group, and more specifically, a carboxyl group-containing resin Ethylene: a resin. : 2) Using a high-sensitivity photopolymerization initiator as the component (C) to reduce the content of the photopolymerization initiator. Further, as the photopolymerization initiator, specifically, the α-aminoalkylphenone compound and the anthracene derivative are preferred because they have a high sensitivity even when the content is small. 3) Reducing the content of the photopolymerization initiator by using a polymerization accelerator which does not absorb visible light. When a lactic acid of an amino acid such as Ν-phenylglycine or a bipolar ionic compound thereof is used as a polymerization accelerator, there is a case where the content of the photopolymerization initiator is low, and high sensitivity is used. The tendency is better. In addition, in the case where the amount of the photopolymerization initiator is reduced according to the above 2) and 3), the compounding amount is preferably, for example, 1 part by weight based on the total of the (Α) component and the component, so that (c) The photopolymerization initiator of the component is 〇. 3 to 7 parts by weight. [2] Method of forming protective film Next, a method of forming a protective film of the thermosetting composition of the present embodiment will be described. ~ [ 2 - 1 ] 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 applicator, a curtain coater, A coating device such as a die coater, a roll coater, or a sprayer is applied. 312XP/Invention Manual (Supplement)/96-09/96119466 56 200807152 200807152 β ΠΙ The coating thickness of the thermosetting composition is usually 〇·5~ [2 - 2 ] drying step

It is removed from the above-mentioned coating film (the age, the original U can be dried using a vacuum dry bomb, = Γ Γ Γ Γ = = = , , , , , , , , , , , , , , , , , 』 』 』 』 』 』 』 』 』 』 』 』 』 10 seconds ~ [2 - 3 ] Exposure • Imaging step Next 'Dry coating film on the thermosetting composition layer = image exposure. After exposure, use the image to remove unexposed: Γ :: 2: into pixels. In addition, after exposure, before the development, the sense of improvement is second, (4) also after the exposure and baking. In this case, the baking can be used 1, the outside line oven, convection oven, etc. The exposure and baking conditions are usually 40~ 150 c, drying time (four) seconds ~ 6 〇 minutes range. Usually for the image obtained after development requires 2G_ wide thin line; 'raw. In addition, in order to achieve high-quality display, there is a need for higher precision The tendency of reproducibility of fine lines. In terms of stably reproducing high-precision thin lines, as a cross-sectional shape of a fine line image after development, a rectangular type in which the contrast between the non-image and the image portion is clear, the development time and development The liquid imaging time, physical stimulation, etc. have a wide range of imaging, so ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Such as light source or argon ion · 射, 石铭石权石射 (YAG lazer, mrium

Garnet Laser), excimer lasers, nitrogen lasers and other laser sources. In 312XP/Invention Manual (Supplement)/96-09/96119466 200807152 Only light of a specific wavelength is used as a development process:: 'A filter can also be used. One of the materials of the ability to dissolve the coating film has the ability to make the unhardened part, and the test is not limited to the case of '1 蜊', as the above can be used to get the color, touch the face, Jia is not an organic solvent;; the risk is equal to Ah 4 and the use of an experimental imaging solution. Examples of the sodium or the image forming liquid include an aqueous solution containing sodium carbonate, hydrogen carbonate, an organic compound, or an organic compound such as diethanolamine, triethylamine or triethylamine. : 'Alkaline imaging solution may also contain a surfactant, water-soluble two-tagent, a wetting agent, a low-molecular compound having a warp group or a fiber, and a surfactant, imaging property, resolution, Since scum or the like has many improvement effects, it is preferably added.廿 As a surfactant used in the shoulder fluid, for example, an anionic surfactant having a naphtha-only sodium group and a sodium benzenesulfonate group, and a nonionic surfactant having a polyalkylene emulsion group may be mentioned. The agent is a cationic surfactant having a tetraalkylammonium group, etc. The method for developing the image is not particularly limited, and is usually at a temperature of 1 〇 5 5 Å and A it is 15 to 4 5 C. Immersion imaging, hybrid imaging, jet imaging, sweep imaging, ultrasonic imaging, etc. [2~4] Heat treatment step #The thermosetting composition of the image formed by the exposure and development steps The film is formed by a heat treatment (hard baking) step to form a cured product (thermosetting film). Further, after development, it is sometimes used for hard 312XP/ for the purpose of suppressing the occurrence of degassing during hard baking. Invention manual (supplement)/96-09/96119466 58 200807152 Roasting is not subject to full exposure. ^In the case of full exposure before hard roasting, the light source makes = see light, for example, can be used to illuminate, s-lamp, job High t = ultra high mercury lamp, metal (four) lamp, medium pressure mercury lamp = lamp source or argon ion laser YAG (four), laser light source such as excimer laser, etc. The mouse field can also use a hot plate as a hard-baked condition, usually in the range of 1 〇〇 to 90 minutes. Infrared oven, convection oven, etc. 250 ° C The 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 the present embodiment is usually provided with a tft main matrix substrate. First, the cured product is formed as a protective film on the substrate on which the TFT element array is formed, and after the IT0 is formed thereon, the photoresist is formed by photolithography, thereby forming a TFT active matrix substrate. The liquid crystal display device of the present embodiment can be formed by bonding the TFT active matrix substrate and the counter substrate to form a liquid crystal cell, and injecting liquid crystal into the liquid crystal cell, and connecting the counter electrode. For the substrate, a color filter substrate having an alignment film is generally used. As the alignment film, a resin film such as polyimide or a polyimide film is preferable. Gravure printing method and/or flexographic printing method are often used, 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 performed by irradiation of ultraviolet rays or treatment of the alignment cloth. 312XP/Invention Manual (Supplement)/96-09/96119466 59 200807152 Processed to adjust the surface state of the liquid crystal. Further, a protective film similar to the above may be formed on the alignment film. The bonding between the matrix substrate and the counter substrate differs depending on the application of the liquid helium display device, and is usually selected in the range of 2 "claws or more, 8" below. After bonding with the counter substrate, the liquid crystal is not included in the population. The seal is sealed by a sealing material such as an epoxy resin. As such a sealing material, those which can be cured by liver irradiation and/or heating are usually used, and the periphery of the liquid crystal cell is sealed. After the peripherally sealed liquid crystal cell is cut into panel units, the pressure is reduced in the vacuum chamber, and the liquid crystal injection port is bubbled into the liquid crystal to inject liquid crystal into the liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is usually lxl 〇 -2 Pa or more, preferably 1 x 10 3 Pa or more, and usually 1 χ 1 〇 -7 Pa or less, preferably in the range of ha e Pa or less. Further, it is preferable to warm the liquid crystal cell at the time of pressure reduction. The heating temperature is usually 30 ° C or higher, preferably 50 ° C or higher, usually 10 0 C or lower, preferably 90 ° C or lower. The temperature holding condition at the time of pressure reduction is usually in the range of 1 minute or more and 6 minutes or less. Thereafter, the liquid crystal cell is immersed in the liquid crystal. The liquid crystal cell injected into the liquid crystal hardens the UV hardening resin to seal the liquid crystal injection port. In this way, the liquid crystal display device (panel) can be completed. Further, the type of the liquid crystal is not particularly limited, and conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds can be used. Any of lyotropic liquid crystals and thermotropic liquid crystals may be used. The thermotropic liquid crystal is known to have a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, or the like. 312XP/Invention Manual (Supplement)/96-09/96119466 60 200807152 [Embodiment] Next, the present embodiment will be described more specifically by way of examples and comparative examples, and the present embodiment is not limited thereto as long as it does not deviate from the gist of the present embodiment. The following examples '. Further, the constituent components of the thermosetting composition used in the following examples and comparative examples are as follows. (A) test soluble resin [Chemical 5]

Acid value: 110 mg-KOH/g

Mw: 17, 000

Acid price·· 107 mg-KOH/g

Mw : 4200 (B) Compound having ethylenically unsaturated group 312XP / invention specification (supplement) /96-09/96119466 61 200807152 [Chem. 6]

Ml: Co., Ltd. Chemical Light Junction BP-2EM h2c=g Female o{ch2,ch2,o

0-CH2-CH2^〇-G· CH3 H2 m+n = 2.6

M2: DPHA manufactured by Nippon Kayaku Co., Ltd.

M3: Co., Ltd. Chemical Epoxy Ester EP3000A /==\ ψ^^/==\

H2C=CH-C-〇-CH29H-CH2-〇-H^ ^〇^CHr^(^2〇^<^CH O OH ^-7 CHs^-7 OH 0 (c) Photopolymerization initiator [ 7] II : Irgacure369 by Ciba Specialty Chemicals Inc. Maximum absorption · · 319 nm

12: Irgacure379, manufactured by Ciba Specialty Chemicals, Inc. Maximum absorption: 319 nm 312XP/invention manual (supplement)/96-09/96119466 62 200807152

14: Absorption maximum: 351 nm

15 : Ciba Specialty Chemicals Public absorption maximum .3 0 5 hid system Irgacure907 〇

[Chem. 8] Irgacure 819 16 : Ciba Specialty Chemicals Public absorption maximum · · 373 nm

312XP/Invention Manual (supplement)/96-09/96119466 63 200807152 17 : Ciba Specialty Chemicals, Inc. DarocureTPO Absorption Maximum·· 382 nm

18: Irjacure OXE-02, manufactured by Ciba Specialty Chemicals, Inc. Maximum absorption: 336 nm

(D) Thermal crosslinking agent [Chemical 9]

XI: Nikalac MW100LM manufactured by Sanwa Chemical Co., Ltd.

6h2och3 CH2OCH3 H3CX3HaCVNAN^kN.CH2OGH3 (E) Other components SI: Fluorine-based surfactant. F475 (F) additive manufactured by Dainippon Ink Co., Ltd. Y1: Polymerization accelerator. Has the following formula. [Chem. 10] 312XP / invention manual (supplement) / 96-09/96119466 64 200807152

Γ2 : UV absorber. Has the following formula. [化11]

TINUVIN384-2 γ3: Polymerization accelerator manufactured by Ciba Specialty Chemicals. Benzyl n-phenylglycine (G) organic solvent PGMAc: propylene glycol monomethyl ether acetate In addition, the photopolymerization initiator used, the prepared thermosetting composition, the exposed film thereof, and the thermosetting film The evaluation method is as follows. [Absorption Maximum of Polymerization Initiator] The photopolymerization initiator was dissolved in tetramine at a concentration of 1 〇 mg/L, and its absorption spectrum was measured with a spectrophotometer UV3100PC manufactured by Shimadzu Corporation. [Light transmittance] The thermosetting composition having the composition shown in Table 1 was applied onto a glass plate for a color filter manufactured by Asahi Glass Co., Ltd., and dried on a hot plate at 90 ° C. After 90 seconds, a coating film having a dry film thickness of 1/m was obtained. The coating film was measured for a light transmittance at a wavelength of 4 〇 〇 nm using a spectrophotometer UV3100PC manufactured by Shimadzu Corporation. [Maximum peak of spectral sensitivity] 312Xp/Invention manual (supplement)/96-09/96119466 65 200807152

The thermosetting composition having the composition shown in Table 1 was applied to a glass substrate (glass plate "AN100" for color filters manufactured by Asahi Glass Co., Ltd.) and dried on a hot plate at 90 ° C for 90 seconds. A coating film having a dry film thickness of 4 was obtained. Using a diffraction spectroscopic irradiation device ("RM-23" manufactured by NARUMI Co., Ltd.), a xenon lamp ("UI-501C" manufactured by USHI0 Electric Co., Ltd.) was used as a light source'. The sample was irradiated at 3 〇〇 to 600 nm. Light in the wavelength domain. In this case, exposure is performed by setting the linearity of the exposure wavelength linearly in the horizontal axis direction and the strong logarithmic change in the vertical axis direction, and irradiating for 15 minutes. Subsequently, after soaking for 60 seconds in a 0.4 wt% aqueous solution of tetradecyl ammonium hydroxide at 25 ° C, an image corresponding to the sensitivity of each exposure wavelength was obtained by rinsing with pure water. The exposure energy of the image can be calculated from the image height, and the spectral sensitivity curve is obtained by drawing the wavelength of the edge on the horizontal axis and the reciprocal of the exposure energy on the vertical axis. The maximum peak on the spectral sensitivity curve is taken as the maximum peak (nm) of the spectral sensitivity. [E365/E300 ] Similarly to the measurement of the maximum peak of the spectral sensitivity, the wavelength is changed in the wavelength range of 3 〇〇 to 65 () nm to expose and develop. The minimum exposure amount [E3〇〇(mJ/cm2)] at which the image can be formed at a wavelength of 3〇〇〇111 and the minimum exposure amount [E365 (mJ/cm2)] at which the image can be formed at a wavelength of 365 nm are obtained, respectively. In the case of the E365/E300 〇 [optimum exposure amount], the thermosetting composition having the composition shown in Table 1 was applied to the production of Asahi Glass Co., Ltd. in a film thickness of approximately 4 // m. The color filter was baked on a glass plate "AN100" glass substrate and baked on a hot plate = 312XP / invention manual (supplement) / 96-09/96119466 66 200807152 90 C for 90 seconds. Thereafter, the exposure was carried out by a high pressure mercury lamp at an illumination of 3 〇 mW/cm 2 . As an exposure condition, the amount of exposure energy is 1 〇...allows "to a range of 320 mJ/cm, and the exposure energy amount is set every 2"2 times into the exposure. Exposure, after exposure, at the muscle 〇.4 | The solution was immersed in a tetramethylammonium hydroxide aqueous solution 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 against the exposure amount. Light = the minimum exposure amount within 1% of the film thickness difference of the exposure film at the exposure amount of 2 times is the optimum exposure amount (mJ/cm2). In addition, the cutoff wavelength is short when the exposure is set on the mask. In the case of a filter of 35 〇 light (DUV cut filter) and the case where it is not provided, the optimum exposure amount (mj/cm 2 ) is obtained. [Resolving property] a The above heat is observed by an optical microscope. The image of the thermosetting film obtained by the formation order of the cured film, the minimum line tUm of the resolution is taken as the precipitation property 0 [pattern shape] The thermal hardening obtained by the formation order of the above-mentioned thermosetting film is observed by a scanning electron microscope. 2020 line width line pattern shape, by which, with the following basis 9 A · Good rectangular shape, no skirt B: Good rectangularity, but a little skirt C · · Poor rectangularity, or no resolution [residue] M2XP / invention manual (supplement) / 96_〇9/96119466 67 200807152 The blank pattern of the 30 #m line width of the thermosetting film obtained in the order of formation of the above-mentioned thermosetting film was observed by an optical microscope, and the residue of the blank portion was evaluated by the following criteria: A : No residue B : Residue found only in the peripheral portion of the photoresist C: Residue was also found in the central portion of the blank portion [Releasability] The thermosetting film obtained in the order of formation of the above-mentioned thermosetting film was combined with the glass substrate at N-曱. The pyridone was immersed in 6 (rc for 1 minute, and was evaluated on the following basis. Ο: no thermosetting film remained on the substrate. X: A thermosetting film remained on the substrate. [Chemical resistance] The thermosetting film obtained by the formation of the cured film was immersed in 20% by weight of hydrochloric acid at 4 (TC for 20 minutes, and evaluated on the following basis. 即使 Even if the surface was observed by an optical microscope, no pores or surface folds were observed. (bump) X: by light The surface of the microscope was observed, and the pores or surface wrinkles (concavities and convexities) were observed. Alternatively, white turbidity was observed by visual observation. [Examples 1 to 7 and Comparative Examples 1 to 3] Thermosetting compositions were prepared by the formulation shown in Table 1. The thermosetting composition obtained was applied to a glass plate "AN100" glass substrate for color filters manufactured by Asahi Glass Co., Ltd., and dried on a hot plate at 90 C for 90 seconds to obtain a dried film thickness of 4 coating. 312XP/Invention Manual (Supplement)/96·〇9/96119466 68 200807152 Z The film side passes through a thin line with a line width of 1〇(4)~5〇(4), 之, 、, hood, using 3 kW high voltage Mercury lamps are exposed. As an exposure condition, the image illuminance measured by an illuminometer having a wavelength of 365 nm was 3 〇 mW/cm, and the exposure amount of the above-described optimum exposure amount was set. Next, a 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 seconds to perform development, and then rinsed with pure water. The exposed film was obtained. 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ooeirnH $ titf一# φ ¥ ros w 99 inch 6u96/60-96/ffsi)_s^SRa^/cixne 200807152 It can be seen from the results of Table 1 that the thermosetting composition of the present embodiment has light rate and sensitivity (optimal exposure) A component having excellent resolution. Further, EWE3Dfl_ is close to i, and the composition of the thermosetting composition of the present invention (4) has a low dependence on wavelength. Further, it is obtained that the hardened film is excellent in pattern shape, crumb property, peelability, and chemical resistance = thermosetting film. In particular, a polymerization accelerator and a UV absorber were used in combination: In Example 4, a tantalum hardened film having excellent pattern shape and residue characteristics was obtained. The thermosetting composition of Comparative Example 1, the absorption maximum of the component ((:) is on the wavelength side of the wavelength range below the fixed range, especially in the case of using the _cutting photo sheet t's sensitivity and resolution. The thermosetting composition of Comparative Example 1 has a composition in which the curing property is highly dependent on the wavelength. In the thermosetting composition of Comparative Examples 2 and 3, the absorption maximum of the component (c) is longer than the fixed range. On the wavelength side of the domain, the coloring was caused and the light transmittance was lowered. Further, the thermosetting compositions of Comparative Examples 2 and 3 were compositions having poor sensitivity and resolution, and having high dependence on the wavelength of the curing property. The obtained thermosetting film is a thermosetting film which is inferior in peeling property and chemical resistance. (Industrial Applicability) According to the present invention, for example, it is possible to form a hard baking without coloring, and a light transmittance in a visible light region is good. Further, the light-distributing light distribution of the light source is also small, and the thermosetting composition for the protective film is excellent in chemical resistance after heat curing. In addition, high-quality liquid crystal display can be provided. Therefore, the industrial applicability is extremely high in the field of the thermosetting composition for a protective film and the liquid crystal display device 312XP/invention specification (supplement)/96-09/96119466 71 200807152. w _ According to the present invention, there is provided a solder resist cover film for, for example, a printed wiring board, a liquid-dissipating member, an electric t-display, a large-scale integrated circuit, a thin transistor, a bulk conductor, a color filter, an organic electroluminescence, or the like. 'and a useful heating composition for forming an insulating coating layer of various electronic parts. Further, it is suitable for use as a color filter, a light sheet, a black matrix, a rib, and a spacer used in a liquid crystal panel such as a liquid crystal display. The thermosetting composition is therefore highly industrially available in the field. Further, the present application is based on a Japanese patent application filed on May 31, 2006 (Patent 2006-152059), 2006 The patent application (patent 2006-206563) filed on July 28, and the Japanese patent application (patent 2007-134318) filed on May 21, 2007, by reference 312XP / present specification (complement member) / 96-09 / 9611946672

Claims (1)

200807152 X. Patent application scope: 1. A thermosetting composition for a protective film, which comprises the following (A) to (〇 each component: (A) an alkali-soluble resin, (B) having an ethylenically unsaturated group The compound (C) photopolymerization initiator has a light transmittance at a wavelength of 400 nm of 9 〇% or more per film thickness, and the above component (C) has a maximum absorption wavelength at 310 nm to 370 nm. The thermosetting composition for a protective film according to the invention of claim 2, wherein the component (B) is a component containing a compound having two ethylenically unsaturated groups, and the two ethylenically unsaturated The ratio of the compound of the above-mentioned component (A) to the total weight of the above-mentioned component (B) is 1% by weight or more. 3. The thermosetting composition for a protective film according to the scope of the patent application, wherein the component (A) is a component having no ethylenically unsaturated group and an epoxy group. 4. A thermosetting composition for a protective film of a worker in the patent application scope, wherein the maximum peak of the spectral sensitivity is 325 nm to 4 〇. () nm, and the sensitivity Em at the wavelength 300 rnn The sensitivity E365 ratio at 365 nm is less than 1·〇 for E365/E3GG. 5. As for the protective thermosetting composition of item i of the patent system, which further contains the following ingredients (D) 6. A kind of hardened material, which is characterized by the use of the thermosetting composition of the protective film for the use of the thermosetting composition of the 312XP/invention specification (supplement)/96-09/96119466 73 200807152. A liquid crystal display device characterized by having a cured product of the sixth application of the patent application scope as a protective film. 312XP/invention specification (supplement)/96-09/96119466 74 200807152 VII. Designation representative map ( a) 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)/ 96-09/96119466 5