Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

• the present invention relates to a thermosetting composition for a protective film by light or heat. More specifically, for example, printed circuit boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, solder resist films in organic-electricular luminescence, coverlay films, and various electronic devices.
• the present invention relates to a curable composition useful for forming an insulating coating layer of a part.
• the present invention also provides a curable composition useful for a color filter, a black matrix, an overcoat, a rib, and a spacer, which is used for a liquid crystal panel such as a liquid crystal display, and the like. And a liquid crystal display device having the cured product.
• an interlayer insulating film for protecting a TFT array element is formed between the TFT array element and a transparent conductive film forming a pixel electrode.
• a contact hole for connecting the drain electrode of the TFT array and the wiring formed of the transparent conductive film is usually formed in the interlayer insulating film. Therefore, a photosensitive thermosetting composition is generally used as a material for the interlayer insulating film.
• thermosetting yarn composition used in such applications, as a positive photosensitive composition, an alkali-soluble resin and a 1,2-quinonediazide compound are used.
• a composition is known (see, for example, Patent Document 1).
• a photopolymerizable composition is known as a negative thermosetting composition (see, for example, Patent Document 2).
• Patent Document 1 Japanese Patent Laid-Open No. 2004-4733
• Patent Document 2 JP 2002-131899 A
• 1,2-quinonediazide compound is hardened after exposure and development.
• Beta In some cases, it is colored by thermal decomposition, and the light transmittance in the visible light region is lowered.
• a cured film having a resistance to various etching solutions when processing the transparent conductive film on the upper layer after the contact hole is formed (cured with chemical resistance).
• Membrane Conventionally, it has been practiced to increase the crosslinking density by blending a large number of compounds containing vesicular unsaturated groups that improve chemical resistance. In other words, it was difficult to improve both chemical resistance and decrease tackiness.
• One object of the present invention is to provide a thermosetting composition for a protective film capable of forming a coating dry film (protective film) with reduced tackiness.
• Another object of the present invention is to provide a thermosetting composition for a protective film having a good light transmittance in the visible light region where coloring during hard beta is absent.
• the other object of this invention is to provide the thermosetting composition for protective films which can form the protective layer excellent in the chemical resistance after thermosetting.
• Still another object of the present invention is to provide a cured product formed from such a thermosetting composition for a protective film, and a liquid crystal display device comprising the cured product as a protective film.
• thermosetting composition for a protective film of the present invention contains (A) an alkali-soluble resin, (B) a compound having two or more ethylenically unsaturated groups, and (C) a photopolymerization initiator.
• the acid value of the component (A) is 80 mg—KOHZg or more, and the component (A) is formed into a film thickness.
• the breakpoint in the 0.4% by weight tetramethylammonium hydroxide aqueous solution (25 ° C) of the resin film formed in step 1 is characterized by 10 seconds or more.
• thermosetting composition for a protective film.
• the liquid crystal display device of the present invention includes this cured product as a protective film.
• thermosetting composition for a protective film capable of forming a coating dry film (protective film) with reduced tackiness.
• a thermosetting composition for a protective film having good light transmittance in the visible light region that is hard to be colored during hard beta.
• a protective layer having excellent chemical resistance after thermosetting can be provided.
• a thermosetting composition for a protective film that can be formed is provided.
• thermosetting composition for a protective film has a high quality because a protective film having a good light transmittance in the visible light region that is not colored during hard beta is used. It is.
• the liquid crystal display device of the present invention is of high quality because such a high quality cured product is used.
• thermosetting composition for protective film of the present embodiment (hereinafter sometimes simply referred to as “thermosetting composition”) includes the following components (A) to (C):
• Containing the acid value of component (A) 80mg- is at KOHZg or more and 0.4 weight 0/0 tetramethyl ⁇ film formed above component (A) with a thickness of 1 mu m
• a breakpoint in aqueous ammonium hydroxide solution (25 ° C) is characterized by 10 seconds or more.
• the dissolution rate in 20 wt% hydrochloric acid (40 ° C) of the thermosetting film obtained by beta treatment at 220 ° C for 1 hour after exposure at the optimum exposure dose hereinafter abbreviated as “hydrochloric acid dissolution rate”) ) Is preferably 0.1 mZ or less.
• the “acid value” in the present embodiment is a value measured in accordance with JIS-K0070 (standard oil and fat test method).
• the acid value of the component (A) is 80 mg-KOHZg or more, preferably 90 mg-KOHZg or more, more preferably lOOmg-KOH / g or more.
• the upper limit is usually 300 mg-KOHZg or less, preferably 200 mg-KOHZg or less.
• alkali-soluble resin on a 4 inch diameter silicon substrate so that the dry film thickness is about 1 ⁇ m, and beta on the hot plate at 90 ° C for 90 seconds. Then, it is immersed in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. The immersion time (seconds) when the surface of the silicon substrate begins to appear as the alkali-soluble resin dissolves or peels off is defined as a breakpoint.
• the value of the break point is 10 seconds or more, preferably 15 seconds or more, and more preferably 30 seconds or more.
• the upper limit is not particularly limited, but it is usually 1000 seconds or less.
• thermosetting composition when the acid value of the alkali-soluble resin increases, the thermosetting composition, and hence the exposed film obtained after exposure, tends to have higher solubility in an alkali developer. That is, film loss due to development increases, resolution may deteriorate, and image cross-sectional shape may deteriorate.
• a resist stripping solution such as N-methylpyrrolidone or immediately after hard beta may deteriorate.
• thermosetting composition having a good chemical resistance while having a certain acid value, and a good chemical resistance.
• node beta means a baking process performed after the exposure and development process. With the hard beta, the thermosetting composition of the present embodiment is sufficiently thermoset, and a thermoset film is obtained.
• examples of a method for realizing an alkali-soluble resin having a high acid value and a long break point include the following methods [a] to [c].
• the method [a] and [b] are preferred from the viewpoint of realizing good developability, and the method [b] is particularly preferred.
• thermosetting composition of the present embodiment is applied on a glass substrate so that the dry film thickness is about 4 m, and beta is applied on a hot plate at 90 ° C. for 90 seconds. Thereafter, exposure illuminance of 30MWZcm 2 by a high pressure mercury lamp. As exposure conditions, the exposure energy amount is set within the range of lOruJ / cm 2 to 320 mj / cm 2 and the exposure energy amount is set at intervals of 2 1/2 times. After exposure, immerse in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C for 70 seconds, rinse with pure water, and measure the thickness of the remaining cured film (exposure film).
• the film thickness of the obtained exposure film is plotted against the exposure amount.
• the minimum exposure value at which the difference in the film thickness of the exposed film between a given exposure value and the 2 1/2 times the exposure value is within 10% is defined as the optimum exposure value (mjZcm 2 ).
• thermosetting composition of the present embodiment is applied on a glass substrate so that the dry film thickness is about 4 m, and beta is applied on a hot plate at 90 ° C. for 90 seconds. Thereafter, exposure illuminance of 30MWZcm 2 by a high pressure mercury lamp. The exposure amount is the optimum exposure amount. After the exposure, it is further beta in an oven at 220 ° C. for 1 hour to obtain a thermosetting film. This thermosetting film is immersed in 20% by weight hydrochloric acid at 40 ° C, rinsed with pure water, and the thickness of the remaining thermosetting film is measured.
• thermochloric acid dissolution rate The difference between the film thickness of the thermosetting film and the film thickness of the thermosetting film remaining after rinsing with pure water divided by the immersion time (minutes) in 20% by weight hydrochloric acid is the hydrochloric acid dissolution rate. It is defined as
• the resistance to an etching solution when forming a wiring such as ITO may be lower.
• the hydrochloric acid dissolution rate is usually preferably 0 .: L mZ or less, more preferably 0.05 mZ or less. Further, the lower limit is not particularly limited, but is usually 0.001 ⁇ mZ or more.
• thermosetting composition that provides a thermosetting composition for a protective film capable of forming a protective film with reduced tackiness of the coated and dried film.
• the acid value and breakpoint of component (A) are each defined within a certain range. Note that the problem of the present embodiment (reduction of tackiness) was not a problem generally known to those skilled in the art.
• thermosetting composition of the present embodiment each component used in the thermosetting composition of the present embodiment will be described.
• thermosetting composition of the present embodiment In addition to the essential components (A) to (C) described above, the following components can be blended in the thermosetting composition of the present embodiment.
• (meth) acryl means “acrylic and / or "”.
• (meth) attalylate means “acrylic and / or "”.
• (meth) attalyloyl means “acrylic and / or "”.
• total solid content means the total amount of components of the photopolymerizable composition excluding the solvent.
• the alkali-soluble resin used in the present embodiment is not particularly limited as long as it has an acid value and a breakpoint in the above-described ranges and is soluble in an alkaline solvent! / It is preferable that the cocoon is a coconut resin containing a carboxyl group or a hydroxyl group.
• an alkali-soluble rosin for example,
• Polyamide polyester, polyether, polyurethane, polybutyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, etc .;
• an epoxy resin containing an unsaturated group and a carboxyl group and a bull resin containing a carboxyl group are preferred.
• carboxyl group-containing bull resin a carboxyl group-containing bull resin that does not contain an unsaturated group is preferably used.
• Examples of the unsaturated resin and carboxyl group-containing epoxy resin include, for example, an O, ⁇ unsaturated group-containing carboxylic acid adduct of epoxy resin, a polyvalent carboxylic acid and / or An unsaturated group- and carboxyl group-containing epoxy resin added with an anhydride of That is, (Ethylene unsaturated via an ester bond (-coo-) formed by ring-opening addition of GO, ⁇ -unsaturated monocarboxylic acid rupoxyl group to epoxy group of epoxy resin) And (m) a carboxyl group of a polyvalent carboxylic acid or anhydride thereof is added to the hydroxyl group formed at that time.
• the components of fat are described below, but V, any of the following components may be used alone, or two or more may be used in combination.
• epoxy resins used in unsaturated and carboxyl group-containing epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, and creso.
• examples thereof include one-novolak epoxy resin, trisphenol epoxy resin, and polymerized epoxy resin of phenol and dicyclopentane.
• phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, glycidyl methacrylate and alkyl (meth) acrylate. Copolymers with stealth are preferred.
• a, j8-unsaturated monocarboxylic acids include, for example, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, and pentaerythritol tri (meth) phthalate anhydride Adducts, pentaerythritol tri (meth) atalylate tetrahydrohydrous phthalic acid adducts, dipentaerythritol penta (meth) ate acrylate anhydrous calories, dipentaerythritol penta (meth) acrylate anhydrous phthalic acid anhydride Products, dipentaerythritol penta (meth) atarylate tetrahydrophthalic anhydride adduct, reaction product of (meth) acrylic acid and ⁇ -strength prolatatone, and the like.
• (meth) acrylic acid is preferable from the viewpoint
• Polyvalent carboxylic acid or anhydride thereof examples include oxalic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyl tetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, and their Examples include anhydrous products.
• tetrahydrophthalic anhydride which is preferred to maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride, is more preferred.
• an epoxy resin containing unsaturated groups and carboxyl groups is phenol novolac epoxy resin, bisphenol epoxy resin, hydroxyfluorene epoxy (resin) or cresol novolac epoxy resin, and a, j8-unsaturated monocarboxylic acid is ( It is preferably a (meth) acrylic acid whose polyvalent carboxylic acid or anhydride is tetrahydrophthalic anhydride.
• epoxy resin containing unsaturated groups and carboxyl groups those having an acid value of 80 to 200 mg-KOHZg are preferred, and those having 85 to 180 mg-KOHZg are more preferred.
• the molecular weight of the unsaturated group and carboxyl group-containing epoxy resin is usually 1,000 or more, preferably 1,500 or more, usually 40,000 or less, preferably 30,000 or less, and Preferably it is 20,000 or less.
• the lower limit of the value of the formula (1) is more preferably 170 or more, and particularly preferably 180 or more.
• the upper limit of formula (1) is 400 or less, and 300 or less is particularly preferable.
• the breakpoint is shortened in the case of a rosin having a high acid value.
• the alkali solubility of the thermosetting composition is also increased, and the sensitivity and adhesion tend to decrease.
• the value of the formula (1) is large, it tends to contain a high molecular weight gelling component and tends to generate image residue.
• Examples of the method for obtaining a high molecular weight unsaturated group and carboxyl group-containing epoxy resin include a method using a high molecular weight epoxy resin as the epoxy resin.
• the molecular weight in the present embodiment means a weight average molecular weight (Mw) in terms of polystyrene measured using a gel permeation chromatography method (GPC method).
• the unsaturated group- and carboxyl group-containing epoxy resin in the present embodiment can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the coexistence of a catalyst and a thermal polymerization inhibitor, the ⁇ , ⁇ unsaturated monocarboxylic acid is added and subjected to an addition reaction, and a polyvalent carboxylic acid or anhydride thereof is further added. It is possible to use a method of adding a substance and continuing the reaction.
• examples of the organic solvent include organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycolenoretinoatenoacetate, and propylene glycolenolemonomethinoatenoate acetate.
• examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, or tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetraptylammonium.
• examples include quaternary ammonium salts such as -um chloride and trimethylbenzyl ammonium chloride, phosphorus compounds such as triphenylphosphine, and stibins such as triphenylstibine.
• thermal polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, and methylneuroquinone.
• the blending amount of the ⁇ , ⁇ unsaturated monocarboxylic acid is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to one chemical equivalent of the epoxy group of the epoxy resin.
• the amount can be
• the temperature during the addition reaction is usually 60 to 150 ° C, preferably 80 to 120 ° C.
• the blending amount of the polyvalent carboxylic acid or its anhydrate is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1 with respect to 1 chemical equivalent of the hydroxyl group generated in the addition reaction.
• the amount can be one chemical equivalent.
• Epoxy resin (A-1-1) as an aromatic group such as a phenylene group or a naphthylene group in the main chain; a condensed oil such as a norbornene group, a dicyclopentadiylene group or an adamantylene group
• a resin containing a cyclic group or the like it is preferable to use phenol novolac epoxy resin, cresol novolac epoxy resin, or polymerized epoxy resin of phenol and dicyclopentagen as (A-1-1).
• Examples of the carboxyl group-containing bulge resin according to the present embodiment include a copolymer of an unsaturated carboxylic acid and a vinyl compound.
• Examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and the like. These can be used alone or in combination of two or more.
• vinyl compound examples include styrene, at-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and pentyl.
• dicyclopental (meth) acrylate is preferred because it provides a wide latitude with respect to development time and developer deterioration.
• dicyclopental (meth) acrylate include compounds disclosed in, for example, JP-A-2001-89533, such as dicyclopentagen skeleton, dicyclopental skeleton, dicyclopental skeleton, and dipentapentenyloxy.
• examples thereof include (meth) acrylates having an alkyl skeleton.
• (meth) acrylate (meth) acrylic acid copolymers are preferred from the viewpoint of image shape, sensitivity, and cured film strength.
• (meth) Atari rate 30 to 80 mole 0/0, (meth) 20-70 mole 0/0 power et styrenesulfonate acrylate is more preferable.
• a copolymer comprising 50 to 75 mol% of (meth) acrylate and 25 to 50 mol% of (meth) acrylic acid is preferred! /.
• aryl (meth) acrylate such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopental (meth) acrylate, 2- Methyladamantyl (meth) atarylate, 2-ethyladamantyl (meth) aterylate
• alicyclic alkyl (meth) acrylates such as
• alicyclic alkyl (meta ) Atallate content is preferably 10 mol% or more, more preferably 15 mol% or more, more preferably 60 mol% or less, and even more preferably 50 mol% or less.
• the acid value of these carboxyl group-containing bur type rosins is usually 80 to 250 mg.
• -KOH / g preferably 80-200 mg-KOHZg, more preferably 90-150 mg-KOHZg.
• the molecular weight of these carboxyl group-containing vinyl-based resins is usually 1,000 or more, preferably 1,500 or more, more preferably 2,000 or more, and usually 100,000 or less. Less than 50, 000, more preferred, less than 30,000, less than 30,000, specially less than 20,000 or less. When using a carboxyl group-containing bur resin having the above-mentioned range, it is preferable because the peelability after development is good.
• the lower limit of the value of the formula (1) is more preferably 170 or more, and particularly preferably 180 or more.
• the upper limit of formula (1) is 400 or less, and 300 or less is particularly preferable.
• the breakpoint is shortened in the case of a resin having a high acid value, so that the alkali solubility as a thermosetting composition is also increased, and the sensitivity and adhesion tend to be lowered.
• the value of the formula (1) is large, it tends to contain a high molecular weight gelling component and tends to generate image residue.
• Examples of a method for obtaining a high molecular weight carboxyl group-containing bull resin include a method in which the amount of the polymerization initiator is reduced during the polymerization reaction of the vinyl compound.
• Carboxyl group-containing bur resin with styrene, a-methylstyrene as its copolymer component Styrenes such as len; carbon numbers such as butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate 4 or more chain alkyl (meth) atalylates; isobornyl (meth) acrylate, dicyclopental (meth) acrylate, 2-methyladamantyl (meth) acrylate, 2-ethyladaman Preferred are alicyclic alkyl (meth) acrylates
• the resin in the case of using a resin partially containing a crosslinked structure as the alkali-soluble resin in the present embodiment (the method of [c] above), the resin can be obtained by the following method. .
• Specific examples of the monofunctional or difunctional ethylenically unsaturated group-containing compound used for crosslinking of the unsaturated group and carboxyl group-containing epoxy resin include styrene, a-methylstyrene, and hydroxystyrene.
• polyfunctional ethylenically unsaturated group-containing compound used as a copolymerization component of the carboxyl group-containing vinyl resin include ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate.
• the polyfunctional ethylenically unsaturated group-containing compound for containing the cross-linked structure is preferably 5 mol% or less, preferably 3 mol% or less in the copolymer component. Even better.
• the resin obtained as a result of copolymerization becomes gely and becomes difficult to dissolve in the organic solvent described later, and development residues are likely to occur when a thermosetting composition is obtained. Tend to be.
• the alkali-soluble resin in the present embodiment is preferably one that does not contain an aromatic ring, or one that contains a phenyl group that is unsubstituted or has a substituent at the p (para) position. .
• discoloration red coloration
• generation of cracks due to heat tends to be suppressed.
• alkali-soluble rosin examples include, for example,
• Copolymer of styrene or dicyclopental (meth) acrylate is added with an ⁇ , ⁇ to unsaturated group-containing carboxylic acid.
• Adduct compounds obtained by:
• the alkali-soluble resin in the present embodiment is preferably a component that does not contain any ethylenically unsaturated group or epoxy group. That is, an alkali-soluble coconut resin containing an ethylenically unsaturated group or an epoxy group is preferred because the storage stability of the composition tends to decrease.
• alkali-soluble resin containing no ethylenically unsaturated group or epoxy group include ( ⁇ -2) carboxyl group-containing vinyl resin.
• Atalylate ⁇ -maleic acid copolymer hydroxyalkyl (meth) atalylate ⁇ -alkyl
• Examples thereof include (meth) acrylate / maleic acid copolymer, styrene / hydroxyalkyl (meth) acrylate / alkyl (meth) acrylate / maleic acid copolymer, and the like.
• the alkali-soluble coagulant satisfies the following relational expression from the viewpoint of suppressing generated gas when the thermosetting composition of the present embodiment is heated, or from the viewpoint of improving heat resistance. Is preferred to be.
• V2 Alkali-soluble sucrose having a molecular weight ( ⁇ 2) that is 10 1/2 times the molecular weight (Ml) corresponding to the maximum peak value when a differential molecular weight distribution curve is obtained by the GPC method using polystyrene as a standard substance
• V3 Weight content of alkali-soluble resin having a molecular weight (M3) of 10_1 / 2 times the molecular weight (Ml) corresponding to the maximum peak value.
• the differential molecular weight distribution curve means the weight content of the alkali-soluble rosin corresponding to the molecular weight for each molecular weight contained in the alkali-soluble rosin. Further, such a differential molecular weight distribution curve is measured by the GPC method using polystyrene as a standard substance, similarly to the molecular weight measurement method described above.
• the V2ZV3 value is usually 1.3 or more, preferably 1.5 or more, and more preferably 1.
• an alkali-soluble resin having a low molecular weight component and a molecular weight distribution improves the image-forming property, improves the strength of the protective film, and generates crack defects in the ITO film on the protective layer. Can be suppressed.
• the alkali-soluble coconut resin having the specific molecular weight distribution described above is prepared by, for example, dissolving an alkali-soluble coconut resin usually obtained in an organic solvent (such as isopropylene glycol monomethyl ether acetate) described later. After making into a solution, it is mixed with a poor solvent for alkali-soluble coagulant such as methanol to precipitate the coagulant, followed by filtration of the precipitated coagulant and, for example, air drying under reduced pressure at 40 ° C. for 12 hours. Can be obtained.
• an organic solvent such as isopropylene glycol monomethyl ether acetate
• the content of the alkali-soluble resin in the thermosetting composition of the present embodiment is usually 5% by weight or more, preferably 10% by weight or more based on the total solid content. In general, it is 80% by weight or less, preferably 70% by weight or less. If the amount of the alkali-soluble resin is excessively small, the reproducibility of the cross-sectional shape of the image may be deteriorated and the heat resistance may be decreased. If the amount is excessively large, the sensitivity may be decreased and the development dissolution rate may be decreased. .
• the compound having an ethylenically unsaturated group (hereinafter sometimes abbreviated as “ethylenically unsaturated compound”) used in the thermosetting composition of the present embodiment is an ethylenically unsaturated bond.
• the thermosetting composition of the present embodiment preferably contains a compound having two or more ethylenically unsaturated groups.
• Examples of the compound having one ethylenically unsaturated group include (meth) acrylic acid, croto Examples thereof include unsaturated carboxylic acids such as acid, isocrotonic acid, maleic acid, itaconic acid, and citraconic acid, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, and styrene.
• Examples of the compound having two or more ethylenically unsaturated bonds in the molecule include, for example, esters of unsaturated carboxylic acid and polyhydroxyl compound, (meth) ataryloxy group-containing phosphate , Urethane (meth) acrylates of hydroxy (meth) acrylate relay compounds and polyisocyanate compounds, and (epoxy) compounds of (meth) acrylic acid or hydroxy (meth) acrylate salts and polyepoxy compounds Epoxy (meth) acrylates with products. These can be used alone or in combination of two or more.
• esters of unsaturated carboxylic acids and polyhydroxy compounds include the following compounds.
• Reaction product of unsaturated carboxylic acid and sugar alcohol examples include ethylene glycol, polyethylene glycol (additional number 2-14), propylene glycol, polypropylene glycol (addition number 2-14) , Trimethylene glycol, tetramethylene glycol, hexamethylene glycol, trimethylol propane, glyceranol, pentaerythritol, dipentaerythritol and the like.
• Reaction product of unsaturated carboxylic acid and adduct of sugar alcohol with alkylene oxide examples include the same as described above.
• examples of the alkylene oxide adduct include an ethylene oxide adduct or a propylene oxide adduct.
• Reaction product of unsaturated carboxylic acid and alcoholamine examples include diethanolamine, triethanolamine and the like.
• esters of the unsaturated carboxylic acid and the polyhydroxy compound include the following compounds.
• esters of the unsaturated carboxylic acid and the polyhydroxy compound include the unsaturated carboxylic acid and an aromatic polyhydroxyl such as hydroquinone, resorcin, pyrogallol, bisphenol F, and bisphenol A. Or a reaction product thereof with an ethylene oxide adduct. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [tapoxyethylene (meth) acrylate), bisphenol A bis [glycidyl ether (meth) acrylate) and the like.
• examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include the unsaturated carboxylic acid and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate. And a reaction product with the product. Specifically, for example, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tri (meth) acrylate, and the like.
• examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include a reaction product of the unsaturated carboxylic acid, a polyvalent carboxylic acid, and a polyhydroxy compound.
• a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol a condensate of (meth) acrylic acid, maleic acid and diethylene glycol, (meth) acrylic acid, terephthalic acid and pentaerythritol
• a condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin a reaction product of the unsaturated carboxylic acid, a polyvalent carboxylic acid, and a polyhydroxy compound.
• 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.
• p and p ′ are each preferably 1 to 10, particularly 1 to 4.
• Specific examples of such a compound include, for example, (meth) atalylooxychetyl phosphate, bis [(meth) atalylooxychetyl] phosphate, (meth) ataryloxyethylene glycol phosphate, and the like. These may be used alone or as a mixture.
• hydroxy (meth) attareito toy compound examples include hydroxy (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylol ethanetri (meth) acrylate.
• a rate-i compound may be mentioned.
• polyisocyanate compound for example, poly(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
• Aliphatic polyisocyanates such as hexamethylene diisocyanate, 1,8 diisocyanate 4 isocyanate methinole octane;
• Cyclohexane diisocyanate dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexenoylisocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, etc.
• Polyisocyanate
• Heterocyclic polyisocyanates such as isocyanurates
• Alophanate-modified polyisocyanurate produced by the method described in JP-A-2001-260261;
• Urethane (meth) acrylates of hydroxy (meth) attalei toy compound and polyisocyanate compound are, among others, urethanes containing the above-mentioned allophanate-modified polyisocyanurate ( (Meth) atalylates are preferred.
• Urethane (meth) atalylates containing allophanate-modified polyisocyanurate have excellent solubility in solvents with low viscosity and improve adhesion to the substrate and film strength by photocuring and Z or thermal curing. It is preferable because of its effect.
• urethane (meth) acrylates in the present embodiment commercially available products can be used. Specifically, for example, trade names “U—4 ⁇ ”, ⁇ -3 06A ”,“ UA—MC340H ”,“ UA—MC340H ”,“ U6LPA ”manufactured by Shin-Nakamura Gakugaku Co., Ltd., a compound having an allophanate skeleton manufactured by Bayer Japan. A certain "AGROR4060” etc. are mentioned.
• the urethane (meth) acrylates in the present embodiment include 4 or more (preferably 6 or more, more preferably 8 or more) urethane bonds in one molecule [NH —CO—O—], and a compound having 4 or more (preferably 6 or more, more preferably 8 or more) (meth) ataryloxy groups.
• a powerful compound can be obtained, for example, by reacting the following compound (0) with the following GO compound.
• Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate are compounds having 4 or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerin.
• Asahi Kasei is a compound that has two or more hydroxyl groups in one molecule, such as ethylene glycol.
• Biuret type such as “Deyuranate 24A-100”, “Deyuranate 22A—75PX”, “Deyuranate 21S—75E”, “Deyuranate 18H—70B”, etc.
• adduct types such as“ deyuranate ⁇ —405-80 ”, etc., and compounds obtained by reacting compounds having 3 or more isocyanate groups in one molecule (i 2);
• a commercial item can be used as such a compound, for example, "Deyuranate ME20-100" by Asahi Kasei Kogyo Co., Ltd. is mentioned.
• pentaerythritol di (meth) acrylate dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol pent (meth) acrylate, dipentaerythritol hexa acrylate
• a compound having one or more hydroxyl groups and two or more, preferably three or more (meth) atalylooxy groups in one molecule a compound having one or more hydroxyl groups and two or more, preferably three or more (meth) atalylooxy groups in one molecule.
• the molecular weight of the compound (0) is preferably 500-200,000, particularly preferably 1,000-150,000.
• the urethane (meta) The molecular weight of attalylates is preferably 600 to 150,000.
• such urethane (meth) acrylates include, for example, the above (0 compound and GO compound in an organic solvent such as toluene and ethyl acetate at 10 to 150 ° C.
• the molar ratio of the former isocyanate group to the latter hydroxyl group is set to a ratio of 1Z10 to L0Z1, and if necessary, n-butyltin dilaurate, etc. It is preferable to use the catalyst.
• polyepoxy compound for example, (Poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl alcohol Aliphatic polyepoxy compounds such as sidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether; phenol novolak Polyepoxy compounds, Brominated phenol novolac polyepoxy compounds, (o—, m-, p—) Cresolol novolac polyepoxy compounds, Bisphenol A polyepoxy Consequences
• polyepoxy compounds such as heterocyclic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate;
• Epoxy (meth) acrylates which are the reaction product of (meth) acrylic acid or hydroxy (meth) atalytoi compounds and polyepoxy compounds, include polyepoxy compounds such as these, ) Acrylic acid or a reaction product with the above hydroxy (meth) ataretoy compound.
• ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allylic esters such as diaryl phthalate, and butyl group-containing compounds such as dibutyphthalate.
• Thioether bond-containing compounds that have improved the crosslinking rate by converting the ether bond of an ethylenically unsaturated compound containing an ether bond into a thioether bond by sulfation with pentasulfuryl phosphorus etc. Can be mentioned.
• a polyfunctional (meth) acrylate compound described in Japanese Patent No. 3164407 and JP-A-9 100111 and a silica sol having a particle diameter of 5 to 30 nm for example, isopropanol-dispersed organosilica sol (Nissan Chemical company "IPA-ST”), methyl ethyl ketone-dispersed organosilica sol (Nissan Chemical "MEK-ST”), methylisobutyl ketone-dispersed organosilica sol (Nissan Chemical "MIBK-ST”) etc.
• An isocyanate group or Examples thereof include compounds bonded using a mercapto group-containing silane coupling agent. These compounds are compounds whose strength and heat resistance as a cured product are improved by reacting and bonding silica sol with an ethylenically unsaturated compound via a silane coupling agent.
• the ethylenically unsaturated compound preferably includes a compound having two or more ethylenically unsaturated groups in the molecule from the viewpoints of polymerizability and crosslinkability. Good.
• ester (meth) acrylates, ester (meth) acrylates, (meth) attayloxy group-containing phosphates, or urethane (meth) acrylates are preferred.
• fragrances such as bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate] Particular preference is given to aromatic polyhydroxy compounds or their reactants with ethylene oxide adducts.
• the ethylenically unsaturated compound according to the present embodiment includes a compound that does not contain an aromatic ring, or a phenyl group that is unsubstituted or has a substituent at the p (para) position.
• an ethylenically unsaturated compound examples include aliphatic polyfunctional (meth) acrylates, and (meth) acrylate compounds of bisphenol A or polyhydric alcohols having a fluorene skeleton. .
• the content of the ethylenically unsaturated compound in the thermosetting composition of the present embodiment is usually 10% by weight or more, preferably 20% by weight or more, based on the total solid content. Usually, it is 70% by weight or less, preferably 60% by weight or less. If the amount of the compound having an ethylenically unsaturated group is excessively small, the sensitivity and the development dissolution rate are easily decreased, and if excessively large, the reproducibility of the image cross-sectional shape is decreased and the resist film is liable to be thin. .
• Component (B) in the present embodiment contains a compound having two ethylenically unsaturated groups
• the proportion of the compound having two ethylenically unsaturated groups in the total weight of the component (A) and the component (B) is usually 10% by weight or more, preferably 20% by weight or more, Usually, it is 70% by weight or less, preferably 60% by weight or less. If the content of the compound having two ethylenically unsaturated groups is excessively large, the chemical resistance may be lowered. On the other hand, if the content is too small, the peelability may be lowered.
• the component (B) in the present embodiment when a compound having 3 or more ethylenically unsaturated groups is used at least in part, the compound having 3 or more ethylenically unsaturated groups
• the content is usually 100 parts by weight or less, preferably 60 parts by weight or less, and 55 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin of component (A). Further preferred.
• the content of the compound having three or more ethylenically unsaturated groups in component (B) is usually 80 parts by weight or less and 60 parts by weight or less with respect to 100 parts by weight of the total weight of component (B). It is more preferable that it is 55 parts by weight or less.
• the proportion of the compound having 3 or more ethylenically unsaturated groups in the total weight of the component (A) and the component (B) is usually 60% by weight or less, preferably 50% by weight or less.
• the amount is preferably 40% by weight or less, and the lower limit is usually 5% by weight or more.
• the blending ratio of component (B) to component (A) is generally 150 parts by weight or less, preferably 120 parts by weight or less, and more preferably as the blending amount of component (B) with respect to 100 parts by weight of component (A) Is 110 parts by weight or less, usually 50 parts by weight or more, preferably 70 parts by weight or more, more preferably 80 parts by weight or more.
• thermosetting composition of the present embodiment any known photopolymerization initiator can be used, and a radical that superimposes an ethylenically unsaturated group with ultraviolet light and visible light.
• produce is mentioned.
• polymerization initiator examples include 2— (4-Methoxyphenol) 4, 6 bis (trichloromethyl) s triazine, 2— (4 — methoxynaphthyl) 4, 6-bis (trichloromethyl) s triazine, 2— (4 -Heteromethylated triazine derivatives such as 4,6 bis (trichloromethyl) s triazine, 2— (4 ethoxycarbo- naphthyl) 4,6-bis (trichloromethyl) s triazine.
• Benzoin and benzoin alkyl ethers such as benzoin methyl ether, benzoin phenol ether, benzoin isobutyl ether and benzoin isopropyl ether.
• Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethyl anthraquinone, 2-t-butylanthraquinone, and 1-mouth anthraquinone.
• Thioxanthone derivatives such as thixanthone, 2-ethylthioxanthone, 2-isopropylthixanthone, 2-chlorothixanthone, 2,4 dimethylthioxanthone, 2,4 jetylthioxanthone, and 2,4-diisopropylthixanthone.
• (ix) benzoic acid ester derivatives such as p-dimethylaminobenzoyl ethyl and p-demethylaminobenzoic acid ethyl.
• Atharidin derivatives such as 9-phenolacridine and 9- (p-methoxyphenol) atalysine.
• photopolymerization initiators may be used alone or in combination. Examples of the combination are described in, for example, JP-B 53-12802, JP-A-1-279903, JP-A-2-48664, JP-A-4-164902, or JP-A-6-75373. In addition, a combination of initiators may be mentioned.
• the content of the photopolymerization initiator in the thermosetting composition of the present embodiment is usually 0.1% by weight or more, preferably 0.5% by weight or more, based on the total solid content. It is usually 40% by weight or less, preferably 30% by weight or less. If the amount of the photopolymerization initiator is excessively small, the sensitivity tends to decrease, and if excessively large, the background stain (development solubility) tends to decrease.
• the compounding ratio of component (C) to component) is usually 20 parts by weight or less, preferably 10 parts by weight or less, and usually 0.1 or less, based on 100 parts by weight of component) Part by weight or more, preferably 0.5 part by weight or more.
• thermosetting composition of the present embodiment may contain a thermal crosslinking agent for the purpose of improving the heat resistance and chemical resistance of the film after thermosetting.
• thermal crosslinking agent known thermal crosslinking agents can be used as long as they undergo a crosslinking reaction by beta after image formation by exposure and development. Specific examples include the following. These may be used alone or in combination of two or more.
• Examples of the compound having an epoxy group in the molecule used in the present embodiment include (poly) glycidyl ether obtained by reacting a monohydroxy compound or a polyhydroxy compound with epichlorohydrin.
• Low molecules such as (poly) glycidylamine compounds obtained Examples include compounds ranging from a mass to a high molecular weight.
• polyglycidyl ether compounds include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenol), and diglycidyl ether type of bis (3,5-dimethyl-4-hydroxyphenol).
• the polyglycidyl ether compound includes polyglycidyl ether resin.
• Polyglycidyl ether resins include bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentagen, phenol Phenolic resin type epoxy resin such as polymerized epoxy resin of styrene and naphthalene.
• These (poly) glycidyl ether compounds may be those obtained by reacting an acid anhydride or a divalent acid compound with the remaining hydroxyl group to introduce a carboxyl group.
• polyglycidyl ester compound examples include diglycidyl ester type epoxy of hexahydrophthalic acid, diglycidyl ester type epoxy of phthalic acid, and the like.
• polyglycidylamine compound examples include diglycidinoreamine type epoxy of bis (4-aminophenol) methane, triglycidinoleamine type epoxy of isocyanurenoic acid, and the like.
• glycidyl (meth) acrylate a ethyl acrylate Glycidyl, a-n-propyl acrylate, glycidyl an-butyl acrylate, (meth) acrylic acid 3, 4, 4-epoxybutyl, (meth) acrylic acid 4, 5, 5-epoxy pentyl, (meth) acrylic acid 6, 7-Epoxyheptyl, ⁇ -ethylacrylic acid 6, 7
• a polymer in which a (meth) acrylate structural unit having an epoxy group contains usually 10 to 70 mol%, preferably 15 to 60 mol% of another copolymerization monomer.
• Examples of the monomer for copolymerization include (meth) acrylic acid, (meth) methyl acrylate, (meth) ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth (Meth) acrylates such as acrylic acid fulleryl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid dicyclopental, (meth) acrylic acid dicyclopenta-roxetil, (meth) acrylic acid isopropanol Mention may be made of esters of acrylic acid and bur aromatic compounds such as styrene, trimethyl styrene, ⁇ -methyl styrene and urnaphthalene.
• the (meth) acrylate having an epoxy group glycidyl (meth) acrylate is preferable.
• Preferred examples of the monomer for copolymerization include (meth) acrylic acid dicyclopental, styrene, and ⁇ -methylstyrene.
• the preferred molecular weight is that the protective film material (thermosetting composition) of the present embodiment is in a solution state.
• the coating is not particularly limited as long as it can be uniformly applied, and is appropriately selected according to the thickness of the coating film to be formed, coating conditions, purpose, and the like.
• the molecular weight is preferably in the range of 2,000-300,000, and the force S is suitable, preferably 3,000 to 100,000, and more preferably 4,000 to 50,000.
• the epoxy group used in the epoxy compound or epoxy resin used in the present embodiment is usually a 1,2-epoxy group, but it improves stability over time or imparts flexibility.
• 1, 3 epoxy group (oxetane), 4, 3 epoxy cyclohexyl group can also be used.
• epoxy compound according to the present embodiment those that do not contain an aromatic ring, Alternatively, it is preferable to contain a non-substituted or furan group having a substituent at the P (para) position, since discoloration (red coloration) due to heat treatment of the protective film can be suppressed.
• epoxy compounds include bisphenol A type epoxy compounds and epoxy resins, epoxy compounds having a fluorene skeleton, and epoxy resins having substituents, Examples thereof include a glycidyl (meth) acrylate copolymer.
• thermosetting composition of the present embodiment contains (D) a compound having an epoxy group in the molecule as a thermal crosslinking agent
• the epoxy group in the molecule occupies in the thermosetting composition.
• the content of the compound having it is usually 60% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less, and usually 1% by weight or more based on the total solid content.
• the content of the compound having an epoxy group in the molecule is excessively large, the storage stability of the thermosetting composition solution is lowered and the peelability after exposure and development is easily lowered.
• nitrogen-containing thermally crosslinkable compound used in this embodiment examples include melamine, benzoguanamine, glycoluril, a compound obtained by allowing formalin to act on urea, or an alkyl-modified compound thereof. be able to.
• Cymel (registered trademark) 300, 301, 303, 350, 736, 738, manufactured by Cytec Industries, Inc. 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 23 5, 238, 1141, 272, 254, 202, 1156, 1158, Sanwa Chemical's “-Karak” (registered trademark) ) E-2151, MW-100LM, MX-750LM, etc.
• Examples of compounds obtained by allowing formalin to act on benzoguanamine or alkyl-modified products thereof include “Cymel” (registered trademark) 1123, 1125, 1128, and the like.
• Examples of compounds in which formalin is allowed to act on glycoluril or alkyl-modified products thereof include “Cymel” (registered trademark) 1170, 1171, 1174, 1172, “two-strength rack” (registered trademark) MX-270, Etc.
• examples of compounds obtained by reacting urea with formalin or alkyl-modified products thereof include “UFR” (registered trademark) 65, 300, “Futatsurak” (registered trademark) manufactured by Cytec Industries, Inc. MX-290, etc.
• UFR registered trademark
• Futatsurak registered trademark manufactured by Cytec Industries, Inc. MX-290, etc.
• thermosetting composition of the present embodiment contains (D) a nitrogen-containing heat-crosslinkable compound as a heat-crosslinking agent
• the content of the nitrogen-containing heat-crosslinkable compound in the thermosetting composition For example, the total solid content is usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less. If the amount of the nitrogen-containing thermally crosslinkable compound is excessively large, the residual film ratio during development and the resolution are liable to be reduced.
• thermal crosslinking agent (D) As a particularly preferred compound as the thermal crosslinking agent (D), — N (CH OR)
• a compound having 2 2 groups (wherein R represents an alkyl group or a hydrogen atom).
• R represents an alkyl group or a hydrogen atom.
• a compound obtained by allowing formalin to act on urea or melamine or an alkyl-modified product thereof is particularly preferable.
• an adhesion assistant can be blended for the purpose of improving the adhesion to the substrate.
• the adhesion assistant include a silane coupling agent.
• trimethoxysilylbenzoic acid ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, ⁇ -gusilidoxypropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane J8 — (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
• silane coupling agents can be used alone or in combination of two or more.
• the silane coupling agent also has a function of imparting appropriate thermal melting (thermal fluidity) to the protective film and improving flatness not only in the heat treatment function but also as an adhesion aid.
• Examples of the silane coupling agent compounded for such a purpose include a silane coupling agent having an epoxy group. More specifically, for example, ⁇ -dalidoxypropyl methoxysilane, j8 — (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Can be mentioned.
• the amount of the adhesion aid is usually 0.1 wt% or more, usually 20 wt% or less, preferably based on the total solid content of the thermosetting composition. Is less than 10% by weight.
• thermosetting composition of the present embodiment has a non-ionic property, a char-on property, and the like for the purpose of improving the coating property of the composition as a coating liquid and the developability of the thermosetting composition layer. It may contain a cationic or amphoteric surfactant, or a fluorine or silicone surfactant.
• nonionic surfactant examples include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyoxyethylene alkyl esters, polyoxyethylenes. Shechille
• Fatty acid esters Fatty acid esters, glycerin fatty acid esters, polyoxyethylene glyceryl fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters , Sorbite fatty acid esters, polyoxyethylene sorbite fatty acid esters and the like.
• Examples of these commercially available products include polyoxyethylene surfactants such as “Emulgen 104P” and “Emulgen A60” manufactured by Kao Corporation.
• Examples of the above-mentioned surfactants include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfates. Esters, higher alcohol sulfates, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, Examples include polyoxyethylene alkylphenyl ether phosphates and special high molecular surfactants. Of these, special polymer surfactants are preferred. Shigu special polycarboxylic acid type polymeric surfactants are more preferred.
• a surfactant such as “Emar 10” manufactured by Kao Co., Ltd. for alkyl sulfates and “Perex” manufactured by Kao Co., Ltd. for alkylnaphthalene sulfonates.
• Examples of special polymer surfactants such as “NB-L” include “Homogenol L-18” and “Homogenol L-100” manufactured by Kao Corporation.
• the cationic surfactants include quaternary ammonium salts, imidazoline derivatives, ammine salts and the like, and the amphoteric surfactants include betaine compounds, imidazolium salts, Examples include imidazolines and amino acids. Of these, stearyltrimethylammonium salts are preferred, with quaternary ammonium salts being preferred. Examples of commercially available products include “Acetamine 24” manufactured by Kao Corporation for alkylamine salts, and “Cotamine 24P” and “Coatamine 86W” manufactured by Kao Corporation for quaternary ammonia salts.
• a compound having a fluoroalkyl group or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable.
• silicone surfactants include "Toe Silicone Co., Ltd.” Resilicon DC3PA, SH7PA, DC11PA, SH21PA, SH28 PA, SH29PA, SH29PA, SH30PA, SH8400, TOSHIBA Silicone Corporation TSF-4440 ”,“ TSF— 4300 ”,“ TSF— 4445 ”,“ TSF— 444 (4) (5) (6) (7) 6 ”,“ TSF— 4460 ”,“ TSF— 4452 ”, manufactured by Silicone Co., Ltd.
• Commercial products such as “KP 341” and “BYK323” and “BYK330” manufactured by BYK-Chem.
• fluorine-based surfactants and silicone-based surfactants are preferred from the viewpoint of uniformity of the coating film thickness.
• Silicone surfactant Z Fluorosurfactant Silicone surfactant Z Special polymer surfactant, Fluorosurfactant Z Special polymer And combinations of surfactants. Of these, silicone surfactants Z-fluorine surfactants are preferred.
• thermosetting composition of the present embodiment contains a surfactant
• the content of the surfactant in the thermosetting composition is 10% by weight or less based on the total solid content. It is more preferably 1 to 5% by weight.
• thermosetting composition of the present embodiment further contains a curing agent for shortening the time under curing conditions and changing the set temperature, and it is possible to appropriately select different curing conditions depending on the manufacturing process of each element. it can.
• Such a curing agent is not particularly limited as long as it does not impair the required function.
• it contains a benzoic acid compound, a polyvalent carboxylic acid (anhydride), and a polyvalent carboxylic acid (anhydride).
• the epoxy group-containing compound as a thermal crosslinking agent In the case of containing, it is preferable to use a thermosetting agent.
• benzoic acid compounds include benzoic acid and benzoic acid such as a hydroxyl group, a halogen group, an alkyl group, an acyl group, an acyloxy group, an alkoxyl group, an aryl group, and an aryl group at positions 2 to 6 on the benzene ring.
• benzoic acid compounds include benzoic acid and benzoic acid such as a hydroxyl group, a halogen group, an alkyl group, an acyl group, an acyloxy group, an alkoxyl group, an aryl group, and an aryl group at positions 2 to 6 on the benzene ring.
• the thing which has a substituent can be mentioned. Among them, those having a hydroxyl group having high curing ability for epoxy as a substituent are preferred, and those having two or more hydroxyl groups are particularly preferred.
• benzoic acid compounds examples include 3, 4, 5-trihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2, 4, 6-trihydroxybenzoic acid and the like.
• Cycloaliphatic polycarboxylic acids such as methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride;
• Aromatic polycarboxylic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tricarboxylic anhydride, benzophenone tetracarboxylic anhydride; succinic acid, trimellitic acid, maleic acid, Cycloaliphatic acid anhydrides such as cyclopentanetetracarboxylic acid;
• trimellitic acid (anhydride) and phthalic anhydride are preferable.
• Polymers containing polyvalent carboxylic acids include (anhydrous) maleic acid (anhydrous
• Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include (meth) acrylic acid and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, Examples include styrene, alkylene having a positioning group such as (poly) alkyleneoxy group or alkyl, and the like.
• polymers containing polyvalent carboxylic acid (anhydride), maleic anhydride and (poly) alkyleneoxy, alkyl, or other locating groups are particularly preferred from the viewpoints of light transmission and cured film strength.
• thermal acid generator examples include aromatic diazo-um salt, diaryl-dhodenium salt, monophenylsulfo-um salt, triarylsulfo-um salt, and triarylselenium salt.
• thermal acid generator examples include various salt compounds, sulfonate esters, and halogen compounds.
• aromatic diazonium salts include black-and-mouth benzene diazo-um hexafluorophosphate, dimethylaminobenzene diazo-um hexafluoro antimonate, and naphthyl diazo-um. Hexafluorophosphite, dimethylaminonaphthyl diazo-tetrafluororeborate and the like.
• dioleodonium salt diphenyl-tetrahydroborate, diphenyl-dinitrohexoxanoleole antimonate, diphenyl-dinitrohexafluorophosphate, Diphenyl-trifluorite, 4, 4 'zi- te teyl ti-di-trifluorate, 4, 4'-di-tert-butyl-dimetho-trifluor-borate, 4, 4 Examples include 't-butyl-diphenyl-hexahexafluorophosphate.
• monophenylsulfo salts include benzyl mono-p-hydroxyphenol methylsulfo-hexafluorophosphate, p-hydroxyphenyldimethylsulfo-hexafluoroantimonate, p Monophenyls such as acetophenol, dimethylsulfohexafluoroantimonate, benzyl monohydroxylmethylsulfohexafluoroantimonate, compounds represented by the following general formula (II) -Rusulfo-sulfur salt type or benzyl-sulfur-foam salt type.
• the triarylsulfum salts include triphenylsulforium tetrafluoroborate, triphenol-noresnorofolhexafanololeophosphate, and triphenol-norresulfoumumoxafluo.
• Loantimonate tri (p black mouth file) sulfo-tetrafluoroborate, tri (p black mouth file) sulfo hexafluorophosphate, tri (p black mouth file) ) Sulfon-hexafluoroantimonate, 4-t-butyltriphenylsulfo-hexafluorophosphate, and the like.
• the triaryl selenium salts include triaryl selenium tetrafluoroborate, triaryl selenium hexafluorophosphate, triaryl selenium hexafluoroan titanate, di (black-and-white) fe-noreselenium tetraphenol. Examples thereof include roborate, di (black and yellow) -phenenoreselenium hexafunoleolophosphate, and di (black and yellow) phenol selenium hexafluoroantimonate.
• sulfonate esters examples include benzoin tosylate, p-trobenzyl 1,9,10 ethanthanthracene 2-sulfonate, 2-trobenzyl ditosylate, 2,6 dinitrobenzyl disilate, 2,4-dinitrobenzyl disilate, and the like. Is mentioned.
• Halogen compounds include 2-chromato-2-phenacetophenone, 2, 2 ', 4'-trichloroacetophenone, 2, 4, 6 tris (trichloromethyl) s triazine, 2- (p-methoxy) Stylyl) 1,4,6 bis (trichloromethyl) s triazine, 2 phenol 1,4,6 bis (trichloromethyl) s triazine, 2— (p-methoxyphenyl) -1,4,6 bis (trichloromethyl) s Triazine, 2— (4′-Methoxy-1′-naphthyl) 4,6 Bis (trichloromethyl) s Triazine, Bis-2- (4-Chlorophenyl) 1,1,1,1-Trichloroethane Bis-1,2- (4-chlorophenol) 1,2,2,2 trichloroethanol, bis-2- (4-methoxyphenol) -1,1,1-trichloroethane, and the like.
• thermal acid generators from the viewpoint of light transmittance and cured film strength, a monophenylsulfur salt type or a benzylphenolsulfum salt type is preferred. (E— 3— 5) Amine compounds
• DBU (1,8 diazabiscyclo (5,4,0) undecene 1), aliphatic amines such as DBU tetraphenolate salts (first, second, third);
• dicyanamide and DBU-based tetraphenyl phosphate are preferred from the viewpoint of cured film strength.
• polyamine compounds examples include triethyltetramine, tetraethylenepentamine, pentaethylenehexamine, dimethylaminopropylamine, and jetylaminopropylamine.
• Aliphatic polyamines such as N-aminoethylpiperazine, mensendiamine, isofluoramine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylamine, N, N-dimethylcyclohexylamine, m — Aromatic polyamines such as xylenediamine, xylylenediamine, xylylenediamine derivatives, and xylylenediamine trimer. Of these, N, N-dimethylcyclohexylamine is preferred.
• block carboxylic acid for example, the above (polyvalent) carboxylic acids and polymer carboxylic acids containing them are disclosed in JP-A-4-218561, JP-A-2003-66223, JP-A-2004-339332, Examples thereof include block carboxylic acids to which butyl ether is added by the method described in JP-A-2004-339333.
• polymers containing polyvalent carboxylic acids (anhydrides), onium salt compounds, block carboxylic acid compounds, and benzoic acid compounds have high curing reaction activity and high hardness.
• U which is preferred in terms of adhesion to the support.
• Block carboxylic acid compound consisting of adduct of trimellitic acid or maleic acid and ethyl vinyl ether
• Benzoic compounds such as 2, 5-dihydroxybenzoic acid and 3, 4, 5-trihydroxybenzoic acid; Benzyl mono-p-hydroxyphenyl methyl sulfo-hexafluorophosphate, p-hydroxyphenyl dimethyl sulfo-hexafluoroantimonate, p-acetoxyphenyl dimethyl sulfone Xafluoroantimonate, benzyl
• curing agents may be used alone or as a mixture of two or more.
• polyvalent carboxylic acid copolymers and benzoic acid compounds are excellent in improving the adhesion to the support, and monosulfo salt is excellent in improving the hardness.
• Benzoic acid compounds are particularly preferred because they are excellent in thermosetting properties and have high light transmission and are less affected by color change due to heat.
• the content of the curing agent in the thermosetting composition is usually 0.05% by weight or more with respect to the total solid content. Preferably it is 0.1% by weight or more, usually 20% by weight or less, preferably 10% by weight or less.
• the amount of the curing agent is too small, the adhesion to the support and the hardness tend to be reduced.
• the amount is too large, the thermal weight loss tends to increase.
• thermosetting composition of the present embodiment may have various additives such as o-hydroxybenzophenone, hydroquinone, p-methoxyphenol, 2, Thermal polymerization inhibitors such as 6-di-tert-butyl-p-taresol can be blended.
• the compounding ratio of these compounds is usually 10% by weight or less, preferably 2% by weight or less, based on the total solid content.
• a plasticizer such as dioctyl phthalate, didodecyl phthalate, and tricresyl phosphate may also be contained in a proportion of 40% by weight or less, preferably 20% by weight or less.
• a polymerization accelerator may be added to the thermosetting composition of the present embodiment as necessary.
• the polymerization accelerator include esters of amino acids such as N-phenyldaricin or dipolar ionic compounds thereof, 2-mercaptobenzothiazole, 2- Mercaptobenzoimidazole, 2 Mercaptobenzoxazole, 3 Mercapto 1, 2, 4 Triazolene, 2 Mercapto 4 (3H) Quinazoline, 13 Mercaptonaphthalene, Ethylene glycol dithiopropionate, Trimethylolpropane tristhiopropionate, Mercapto group-containing compounds such as pentaerythritol tetrakisthiopropionate, polyfunctional thiol compounds such as hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate, N, Derivatives such as N-dialkylaminobenzo
• the content ratio is preferably 20% by weight or less based on the total solid content. It is more preferably 1 to: LO weight%.
• an ultraviolet absorber may be added to the thermosetting composition of the present embodiment, if necessary.
• the ultraviolet absorber absorbs a specific wavelength of a light source used for exposure by the ultraviolet absorber, and is photocured when the film of the thermosetting composition of the present embodiment formed on the substrate is exposed. It is added for the purpose of controlling the speed. By adding an ultraviolet absorber, it is possible to improve the pattern shape after exposure / development and to eliminate residues remaining in the non-exposed areas after development.
• the ultraviolet absorber for example, a compound having an absorption maximum between 250 nm force and 400 nm can be used. More specifically, for example,
• Sumisoap 130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORBl l, EVERSORB 12 (manufactured by Taiwan Ekko Chemical Industry), Tomisohap 800 (manufactured by API Corporation), SEE SORB100, SEESORB101S, SEESORB102, SEESORB1 03, SEESORB105, SEESORB106, SEESORB106, SEESORB106, SEESORB106, SEESORB106 Benzophenone compounds such as SEESORB151 (Cipro Kasei);
• Benzoate compounds such as Sumithorpe 400 (manufactured by Sumitomo Chemical) and salicylic acid; hydroxyphenol triazine compounds such as TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477DW, TINU VIN479 (manufactured by Chinoku 'Specialty Chemicals)
• benzotriazole compounds and hydroxyphenol triazine compounds are preferred.
• Benzotriazole compounds are particularly preferred.
• the blending ratio is usually 0.01% by weight or more and 15% by weight or less, preferably 0.05% by weight, based on the total solid content of the thermosetting composition. More than 10% by weight. If the blending ratio of the UV absorber is less than this range, effects such as improving the shape of the pattern and eliminating Z or residues tend to be difficult to obtain.If it is too large, the sensitivity decreases and the Z or residual film ratio decreases. Tend to happen.
• Each of the above-mentioned components is usually used by preparing an organic solvent so that the solid content concentration is 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-described components and has good handleability.
• Ethyl acetate methyl lactate, ethyl lactate, 3-methoxymethylpropionate, 3-ethoxyl propionate, propylene glycolenomonomethinole ether, methanol, ethanol, propanol, butanol, tetrahydride furan
• Examples include diethylene glycol dimethyl ether, methoxybutyl acetate, sorbest, carbitol and the like.
• the boiling point of the organic solvent is preferably in the range of 100 to 200 ° C, more preferably 120.
• organic solvent can be used alone, but two or more types may be used in combination.
• examples of the combination of organic solvents used in combination include a mixture of PGMAc and one or more organic solvents selected from diethylene glycol dimethyl ether, methoxybutyl acetate, sorbest, carbitol and the like.
• the mixing ratio of one or more organic solvents selected from diethylene glycol dimethyl ether, methoxybutyl acetate, sorbest, carbitol, etc. is usually 10% by weight or more based on PGMAc. It is preferably 30% by weight or more, usually 80% by weight or less, preferably 70% by weight or less.
• a mixed solvent of PGMAc and methoxybutyl acetate induces appropriate fluidity of the coating film in the coating drying step, and thus is suitable for flattening the unevenness of the substrate. is there.
• thermosetting composition of the present embodiment Next, a method for forming a protective film using the thermosetting composition of the present embodiment will be described.
• thermosetting composition of the present embodiment described above is applied onto a substrate on which a TFT array has been formed using an application device such as a spinner, a wire coater, a flow coater, a die coater, a rono coater, or a spray. To do.
• the coating thickness of the thermosetting composition is usually 0.5 to 5 / ⁇ ⁇ .
• Drying process Volatile components are removed (dried) from the coating film to form a dry coating film.
• drying vacuum drying, hot plate, IR oven, competition oven or the like can be used.
• Preferred drying conditions are a temperature of 40 to 150 ° C. and a drying time of 10 seconds to 60 minutes.
• a photomask is placed on the dried coating film of the thermosetting composition layer, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel.
• post-exposure baking is performed after exposure and before development to improve sensitivity.
• a beta, an IR oven, a competition oven, or the like can be used for beta.
• Post-exposure beta conditions usually range from 40 to 150 ° C and drying times from 10 seconds to 60 minutes.
• an image obtained after development is required to have a fine line reproducibility of 20 m width.
• fine line reproducibility there is a tendency to demand finer fine line reproducibility than the realization of high-quality displays.
• a rectangular shape with a clear contrast between the non-image and the image area is used as the cross-sectional shape of the fine line image after development. A wide development margin is preferable.
• Examples of the light source used in the exposure process of the dried coating film include lamps such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal lamp, a ride lamp, a medium pressure mercury lamp, and a low pressure mercury lamp.
• Examples of the light source include laser light sources such as an argon ion laser, a YAG laser, an excimer laser, and a nitrogen laser. When using only light of a specific wavelength, an optical filter can be used.
• the solvent used in the development process is not particularly limited as long as it is a solvent capable of dissolving the coating film of the uncured portion, but as described above, as described above, environmental pollution, harm to human body, fire risk For these reasons, it is preferable to use an alkaline developer that does not use organic solvents.
• Examples of such an alkaline developer include inorganic alkaline compounds such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, and the like. Or organic alkali compounds such as diethanolamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The aqueous solution contained is mentioned.
• the alkali developer may contain a surfactant, a water-soluble organic solvent, a wetting agent, a low-molecular compound having a hydroxyl group or a carboxylic acid group, and the like, if necessary.
• a surfactant it is preferable to add a surfactant because many surfactants have an improving effect on developability, resolution, and background stains.
• Examples of the surfactant used in the developer include a cation surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, and a nonionic surfactant having a polyalkyleneoxy group. And a cationic surfactant having a tetraalkylammonium group.
• the development processing method is not particularly limited, but it is usually immersion development, paddle development, spray development, brush development, ultrasonic development at a development temperature of 10 to 50 ° C, preferably 15 to 45 ° C. Etc. are performed.
• thermosetting composition film that has been image-formed by the exposure and development process then becomes a cured product (thermosetting film) through a heat treatment (hard beta) process.
• hard beta heat treatment
• the entire exposure is performed after development for the purpose of suppressing the outgassing during the hard beta before the hard beta.
• ultraviolet light or visible light is used as the light source.
• lamp light sources such as mercury lamps and low-pressure mercury lamps include argon ion lasers, YAG lasers, excimer lasers, and nitrogen lasers.
• hot plates, IR ovens, competition ovens, etc. can be used for the hard beta.
• the hard beta conditions are usually in the range of 100 to 250 ° C and the drying time of 30 seconds to 90 minutes.
• the liquid crystal display device according to the present embodiment usually includes a TFT active matrix substrate.
• the TFT active matrix substrate is formed by forming the above-mentioned cured product as a protective film on the substrate on which the TFT element array is formed, forming an ITO film thereon, and then applying a photolithography method to the ITO. Created by creating wiring.
• the TFT active matrix substrate is bonded to a counter substrate to form a liquid crystal cell, and a liquid crystal is injected into the formed liquid crystal cell.
• a color filter substrate having an alignment film is suitably used as the counter substrate.
• the alignment film a resin film such as polyimide is suitable.
• the Daravia printing method and the Z or flexographic printing method are usually employed, and the thickness of the alignment film is set to several lOnm.
• the surface is treated by treatment with a rubbing cloth after being irradiated with ultraviolet rays to form a surface state in which the tilt of the liquid crystal can be adjusted.
• a protective film similar to the above may be further formed on the alignment film.
• the bonding gap between the TFT active matrix substrate and the counter substrate is selected in the range of usually 2 m or more and 8 m or less depending on the application of the liquid crystal display device. After bonding to the counter substrate, the part other than the liquid crystal inlet is sealed with a sealant such as epoxy resin.
• a sealing material a material curable by UV irradiation and Z or heating is usually used, and the periphery of the liquid crystal cell is sealed. After the liquid crystal cell whose periphery is sealed is cut into panels, the pressure in the vacuum chamber is reduced, the liquid crystal inlet is immersed in the liquid crystal, and the inside of the chamber is leaked, so that the liquid crystal is contained in the liquid crystal cell. Can be injected.
• the vacuum degree in the liquid crystal cell typically 1 X 10 _2 Pa or more, preferably 1 X 10 _3 Pa or more, usually 1 X 10 _7 Pa or less, preferably in the range of 1 X 10 _6 Pa is there.
• the heating temperature is usually 30 ° C or higher, preferably 50 ° C or higher, and is usually 100 ° C or lower, preferably 90 ° C or lower.
• the heating and holding conditions during decompression are usually in the range of 10 minutes to 60 minutes. Thereafter, the liquid crystal cell is immersed in the liquid crystal.
• the liquid crystal cell filled with liquid crystal is UV-cured resin Is cured to seal the liquid crystal inlet.
• the liquid crystal display device (panel) can be completed.
• thermo-mouth pick liquid crystal may have any known force such as nematic liquid crystal, smectic liquid crystal, and cholesteric liquid crystal.
• thermosetting compositions used in the following Examples and Comparative Examples are as follows.
• ⁇ 2 UV absorber. It has the following structural formula.
• TINUVIN384— 2 manufactured by Ciba Specialty Chemicals
• thermosetting film [0205]
• the alkali-soluble resin used, the prepared thermosetting composition, the exposure film thereof, and the evaluation method of the thermosetting film are as follows.
• Alkali-soluble resin was applied onto a silicon substrate with a diameter of 4 inches so that the dry film thickness would be about 1 ⁇ m, and beta was applied at 90 ° C for 90 seconds on a hot plate. Thereafter, 25 0.4 wt 0/0 tetramethylammonium of ° C - were immersed in Umuhidorokishido solution. The immersion time (seconds) when the surface of the silicon substrate began to appear due to dissolution or peeling of the alkali-soluble resin was taken as a breakpoint.
• thermosetting film obtained by the procedure for forming the thermosetting film was immersed in 20 wt% hydrochloric acid at 40 ° C. for 20 minutes, and then rinsed with pure water.
• the value obtained by dividing the difference in film thickness m) before and after immersion by the immersion time (20 minutes) was taken as the 20 wt% hydrochloric acid dissolution rate after hard beta ( ⁇ mZ minutes).
• the film was coated on a glass substrate “AN100” for color filters manufactured by Asahi Glass Co., Ltd. and dried on a hot plate at 90 ° C. for 90 seconds to obtain a coating film having a dry film thickness of 4 m.
• the adhesion of the film surface was evaluated according to the following criteria.
• ⁇ Marks are not strong even when pressed with a sticky finger.
• X Sticky and marks when pressed with a finger.
• thermosetting film obtained by the procedure for forming the thermosetting film is observed with an optical microscope and resolved.
• the minimum line width ( ⁇ m) was defined as the resolution.
• the pattern shape was evaluated according to the following criteria.
• thermosetting film obtained by the procedure for forming the thermosetting film was observed with an optical microscope, and the residue in the space portion was evaluated according to the following criteria.
• thermosetting film obtained by the procedure for forming the thermosetting film was dipped in N-methyl bi-lididone at 60 ° C. for 10 minutes together with a glass substrate, and evaluated according to the following criteria.
• thermosetting film remained on the substrate!
• thermosetting film remained on the substrate.
• thermosetting film obtained by the thermosetting film forming procedure was immersed in 20% by weight hydrochloric acid at 40 ° C. for 20 minutes and evaluated according to the following criteria.
• ⁇ Surface roughness (irregularities) was not observed even when the surface was observed with an optical microscope.
• a cured film was obtained by the above-described procedure for forming a thermosetting film except that the entire surface was exposed without using a mask.
• the light transmittance of the cured film was measured with a spectrophotometer UV3100PC manufactured by Shimadzu Corporation to determine the minimum transmittance (%) in the wavelength range of 600 nm to 400 nm.
• Thermosetting compositions were prepared with the formulations shown in Table 1.
• thermosetting composition is made from Asahi Glass Co., Ltd. glass plate “AN100” for color filters.
• the film was coated on a glass substrate and dried on a hot plate at 90 ° C for 90 seconds to obtain a coating film having a dry film thickness of 4 m. Thereafter, exposure was performed from the coating film side using a 3 kW high-pressure mercury lamp through a mask having a fine line pattern with a line width of 10 ⁇ to 50 / ⁇ m.
• the image plane illuminance measured with an illuminometer with a wavelength of 365 nm was 30 mWZcm 2 , and the exposure amount corresponding to the optimum exposure amount described above was used.
• thermosetting composition Various evaluations were performed on the thermosetting composition, the exposure film, and the thermosetting film. The results are also shown in Table 1.
• thermosetting film formed from the thermosetting composition of the present embodiment has excellent peelability, chemical resistance, light transmittance, pattern shape, and residue characteristics. It was a thermosetting film that not only was excellent, but also achieved low tack. In particular, in Example 5 in which an ultraviolet absorber was used in combination, a thermosetting film having both a pattern shape and residual characteristics was obtained.
• thermosetting film formed from the thermosetting composition of Comparative Example 1 is inferior in tackiness because the acid value of component (A) is not more than a specified value, and peelability is also chemical resistance. It is a thermosetting film that is inferior to o
• thermosetting film formed from the thermosetting composition of Comparative Example 2 is a thermosetting film having poor chemical resistance and poor resolution because the breakpoint is not more than a specified value. It was.
• the light transmittance in the visible light region without coloring during hard beta is good, and the tackiness of the coating film is reduced, so that defects can be reduced.
• a thermosetting composition for a protective film that is excellent in chemical resistance after thermosetting. This also provides a high-quality liquid crystal display device. Therefore, the industrial applicability in the fields of the thermosetting composition for a protective film and the liquid crystal display device is extremely high.
• thermosetting composition useful for forming an insulating coating layer of various electronic parts.
• a thermosetting composition suitable for a color filter, a black matrix, a rib and a spacer used for a liquid crystal panel such as a liquid crystal display is provided. Therefore, industrial applicability is extremely high even in this field.
• Patent 2006-1 52051 Japanese patent applications filed on July 28, 2006
• Patents 2006-206555 Japanese patent applications filed on July 28, 2006
• Patent 2007-134317 Based on a Japanese patent application filed on May 21, 2007 (Patent 2007-134317), which is incorporated by reference in its entirety.

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