JP2013167786A - Curable resin composition for organic insulating film, cured material, tft active matrix substrate, and liquid-crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition for an organic insulating film which can form an organic insulating film having preferable sensitivity, resolving power and step-forming properties without causing residues even at fine contact holes.SOLUTION: A curable resin composition for an organic insulating film contains (A) a resin obtained by (co)polymerization of monomer components including compounds represented by the specified general formula (I) as essential components, (B) a photoinitiator, and (C) a compound having a radical-polymerizable double bond. (In the formula (I), Rand Reach independently represent a hydrogen atom or a C1-C25 hydrocarbon group with or without substituents.)

Description

  The present invention relates to a photopolymerizable curable resin composition for an organic insulating film useful for forming an insulating coating layer in a liquid crystal display device, in particular, to protect a TFT array element of a TFT active matrix substrate used in a liquid crystal display device. The present invention relates to a curable resin composition useful for forming an organic insulating film. The present invention also relates to a cured product formed using the curable resin composition for an organic insulating film, a TFT active matrix substrate having the cured product, and a liquid crystal display device.

  Conventionally, in a TFT active matrix substrate used for a liquid crystal display device, an interlayer insulating film for protecting the TFT array element is formed between the TFT array element and a transparent conductive film forming a pixel electrode. Here, a contact hole for connecting the drain electrode of the TFT array and the wiring formed by the transparent conductive film is formed in the interlayer insulating film. Therefore, a photosensitive curable resin composition is used as a material for the interlayer insulating film.

Among the curable resin compositions used for such applications, a curable resin composition comprising an alkali-soluble resin and a 1,2-quinonediazide compound is known as a positive photosensitive composition (patent) Reference 1).
However, in the thermosetting resin composition, the 1,2-quinonediazide compound is colored by thermal decomposition during hard baking after exposure and development, and the light transmittance in the visible light region may be reduced. Further, the conventional positive photosensitive composition has a problem that the sensitivity is low and the productivity is inferior to that of the photopolymerizable negative photosensitive composition.

Moreover, as a curable resin composition, the negative photosensitive thermosetting resin composition is also known (patent documents 2, 3).
In the photopolymerizable negative photosensitive composition, there are merits such that the above-mentioned coloring problem hardly occurs and the sensitivity can be easily increased.

JP 2004-4733 A JP 2002-131899 A Japanese Patent Application Laid-Open No. 6-256684

However, for example, the conventional negative photosensitive compositions described in Patent Documents 2 and 3 have a problem in that the resolution is deteriorated because swelling due to a developer tends to occur during development.
In order to solve the above problems, it is possible to lower the solubility and affinity of the photocured film in the developer. However, this method has a problem that a residue is generated on the substrate after development.
Further, in the TFT active matrix substrate of the liquid crystal display device, a step forming function between the central pixel portion and the peripheral portion is required for the interlayer insulating film. This step formation is performed by controlling the amount of light irradiation at the time of exposure using a halftone mask. However, in the case of a negative photosensitive composition, since swelling at the time of development is likely to occur, the halftone mask is used. The exposed thinned portion peeled off during development, and it was difficult to form a large step.

  Accordingly, the present invention provides a curable resin composition for an organic insulating film that can form an organic insulating film that has good sensitivity, resolving power, and step-formability, and that does not generate residue even in a fine contact hole. Is an issue.

  As a result of intensive studies, the present inventors have found that a curable resin composition for organic insulating films containing a specific resin can solve the above problems, and have completed the present invention.

  That is, the present invention provides (A) a resin obtained by (co) polymerizing a monomer component containing a compound represented by the following general formula (I) as an essential component, (B) a photopolymerization initiator, and (C) A curable resin composition for organic insulating films, which contains a compound having a radical polymerizable double bond, and a cured product formed using the curable resin composition for organic insulating films; , TFT active matrix substrate and liquid crystal display device having the cured product.

(In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

  By using the curable resin composition for an organic insulating film of the present invention, an organic insulating film having good sensitivity, resolving power, transparency, step forming property and no generation of residue even in a fine contact hole is obtained. Can do. Therefore, a high-quality TFT active matrix substrate and a liquid crystal display device can be realized using this curable resin composition for organic insulating films.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, this invention is not limited to the following embodiment, Various deformation | transformation can be implemented within the range of the summary.

In the present embodiment, “(meth) acryl” and “(meth) acrylate” mean “acryl and / or methacryl” and “acrylate and / or methacrylate”, respectively. The same applies to “(meth) acrylo”.
Further, “total solid content” means all components of the curable resin composition for an organic insulating film of the present invention other than the solvent component described later.
The “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
“(Co) polymerization” means “polymerization or copolymerization”.
“(Poly)...” Means one or both of the monomer compound “...” And a polymer obtained by polymerizing the monomer compound.

[Curable resin composition for organic insulating film]
The curable resin composition for organic insulating films of the present invention contains (A) a compound represented by the following general formula (I) (hereinafter sometimes referred to as “compound (I)”) as an essential component. Contains a resin obtained by (co) polymerizing a monomer component (hereinafter sometimes referred to as “specific resin”), (B) a photopolymerization initiator, and (C) a compound having a radical polymerizable double bond. .

(In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

[(A) Specific resin]
The (A) specific resin (hereinafter sometimes referred to as “component (A)”) in the present invention is obtained by (co) polymerizing a monomer component containing compound (I) as an essential component. There is no particular limitation, and for example, a resin obtained by copolymerizing compound (I) with another compound that may be copolymerized with compound (I) (hereinafter sometimes referred to as “compounding compound”) Is mentioned.

<Compound (I)>
The carbon number of the hydrocarbon group of R ¹ and R ² in the general formula (I) representing the compound (I) is usually 1 or more, usually 25 or less, preferably 10 or less, more preferably 6 or less. When the carbon number of the hydrocarbon group of R ¹ and R ² is within the above range, it is preferable because the resin hardly remains on the substrate as a residue during development.

The hydrocarbon group for R ¹ and R ² may be linear, branched or cyclic, and may be saturated or unsaturated. For example, a methyl group, an ethyl group, or an n-propyl group Preferred are chain alkyl groups such as iso-propyl group, n-butyl group, tert-butyl group and n-hexyl group, cycloalkyl groups such as cyclohexyl group, and aliphatic hydrocarbon groups such as adamantyl group and isobornyl group. It is done.

  Examples of the compound (I) include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n -Propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl)- 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (ste Ryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene)] bis- 2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like.

  Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.

  Compound (I) may be used alone or in combination of two or more.

The proportion of compound (I) in the total monomer component of the specific resin is usually 1 to 30 mol%, preferably 2 to 20 mol%, more preferably 3 to 15 mol%.
By using compound (I) at the above lower limit or more, as described later, there is an effect that deformation due to swelling during alkali development can be suppressed. However, if the proportion of compound (I) is excessively large, alkali developability is achieved. The resolution becomes lower.

<Compounding compound>
Although there is no restriction | limiting in particular as a compound copolymerized with compound (I), For example, the compound illustrated to the following (i)-(viii) is mentioned.

(I) Styrene derivatives such as styrene, α-methylstyrene and p-hydroxystyrene

(Ii) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) ) Alkyl (meth) acrylates such as acrylate

(Iii) Hydroxy group-substituted alkyl (meth) acrylates such as hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate and hydroxyethyl (meth) acrylate

(Iv) Cycloaliphatic alkyl (meth) acrylates such as isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, and 2-ethyladamantyl (meth) acrylate

(V) Aryl-substituted alkyl (meth) acrylates such as benzyl (meth) acrylate

(Vi) Amino-substituted alkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N- (meth) acryloylmorpholine

(Vii) Silyl-substituted alkyl (meth) acrylates such as trimethylsilylmethyl (meth) acrylate and 3- [tris (trimethylsilyloxy) silyl] propyl (meth) acrylate

(Viii) Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, or anhydrides thereof

  Among them, it is preferable to contain the unsaturated carboxylic acid (viii) or an anhydride thereof from the viewpoint of improving developability with respect to an alkaline developer.

  When the monomer component of the specific resin contains an unsaturated carboxylic acid or anhydride thereof, the acid value of the specific resin to be obtained is usually 100 mg-KOH / g or more, preferably 110 mg-KOH / g or more, and usually It is preferably used so as to be 250 mg-KOH / g or less, preferably 200 mg-KOH / g or less, more preferably 150 mg-KOH / g or less. If the acid value of the specific resin is less than the above lower limit, the alkali developability deteriorates, so the resolution may decrease, and if it exceeds the above upper limit, the solubility in an alkali developer becomes too high, so the remaining film ratio May decrease.

Furthermore, from the viewpoint of improving the remaining film ratio of the exposed area, it is preferable that the monomer component of the specific resin contains (i) a styrene derivative and / or (iv) an alicyclic alkyl (meth) acrylate.
When these (i) styrene derivatives and / or (iv) alicyclic alkyl (meth) acrylates are contained, the proportion of these components in the total monomer components is usually 5 to 70 mol%, preferably 10 -60 mol%, More preferably, it is 20-50 mol%. If the ratio of (i) styrene derivative and / or (iv) alicyclic alkyl (meth) acrylate is less than the above lower limit, it tends to swell at the time of alkali development, and the pattern may be easily deformed. If it exceeds, the film becomes brittle, and the adhesion to the substrate may deteriorate.

<Molecular weight>
The molecular weight of the specific resin is usually 3,000 or more, preferably 5,000 or more, and usually 100,000 or less, preferably 50,000 in terms of polystyrene-converted weight average molecular weight measured by GPC (gel permeation chromatography). 000 or less, more preferably 30,000 or less.
If the molecular weight of the specific resin is less than the above lower limit, the hardness of the film after curing is lowered, so the mechanical strength as an organic insulating film may be insufficient, and if it exceeds the upper limit, the high molecular weight that is difficult to dissolve during alkali development Since the components increase, residues may be easily produced.

<Synthesis method>
The specific resin can be synthesized, for example, according to the method described in JP-A No. 2004-300203 using the compound that is copolymerized with the compound (I).

<Reason for the effect of the present invention>
The reason why the effect of the present invention can be obtained when the specific resin is included in the curable resin composition for organic insulating films is estimated as follows.
In the specific resin according to the present invention, since the structure in the resin derived from the compound (I) is a six-membered ring structure as shown in the following general formula (II), molecular rigidity is imparted, and during alkali development Deformation due to swelling can be suppressed. Therefore, it is possible to form a high step without reducing the adhesion between the curable resin composition film for an organic insulating film and the substrate even in a low exposure region.

(In formula (II), R ¹ and R ² have the same meanings as in general formula (I).)

<Content>
The content of the specific resin (A) in the curable resin composition for organic insulating films of the present invention is usually 20% by weight or more, preferably 30% by weight or more, and usually 70% by weight or less, preferably in the total solid content. Is 60% by weight or less.
(A) If the content of the specific resin is excessively small, the reproducibility of the image cross-sectional shape may be deteriorated and the heat resistance may be decreased. If the content is excessively large, the sensitivity and the development dissolution rate may be decreased. There is.
In addition, only 1 type may be used for specific resin, and it may use together 2 or more types of what differs in the kind of compound (I) and the compound to copolymerize, the ratio in these monomer components, molecular weight, etc. Good.

[(B) Photopolymerization initiator]
The curable resin composition for organic insulating films of the present invention contains (B) a photopolymerization initiator (hereinafter sometimes referred to as “component (B)”).

  (B) As the photopolymerization initiator, any known compound may be used as long as it is a compound capable of generating a radical that polymerizes an ethylenically unsaturated group by ultraviolet exposure and does not impair the effects of the present invention. Things can also be used.

  Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.

(B-1) 2- (4-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine , 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, etc. Triazine derivatives

(B-2) 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methylphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenyl Imidazole derivatives such as imidazole dimer

(B-3) Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether

(B-4) Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone

(B-5) Benzanthrone derivatives

(B-6) Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone

(B-7) 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl -(P-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1 -Acetophenone derivatives such as trichloromethyl- (p-butylphenyl) ketone

(B-8) Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone

(B-9) Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate

(B-10) Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine

(B-11) Phenazine derivatives such as 9,10-dimethylbenzphenazine

(B-12) Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2, 4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluoro Phen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2, 6-di-fluoro E 1-yl, di - cyclopentadienyl -Ti- bis-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl

(B-13) 2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as

(B-14) Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide

(B-15) 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), oxime ester compounds such as initiators described in JP-A-2006-36750 and JP-A-2008-179611

  These photoinitiators may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The (B) photopolymerization initiator may further contain a hydrogen-donating compound for the purpose of improving the photopolymerization initiation ability.
Examples of the hydrogen donating compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline. , Β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, etc., mercapto group-containing compounds, N, N-dialkylaminobenzoate, N-phenyl Examples thereof include amino acids such as glycine and phenylalanine or derivatives thereof. These may be used alone or in combination of two or more.

  As photopolymerization initiators, (B-2) imidazole derivatives, (B-13) α-aminoalkylphenone compounds, (B-14) acylphosphine oxide compounds, and (B-15) oxime ester compounds are particularly visible. Part (B-13) α-aminoalkylphenone compounds and (B-15) oxime ester compounds are more preferred because of high sensitivity, most preferably (B-15) oxime. It is an ester compound.

The content of the (B) photopolymerization initiator in the curable resin composition for organic insulating films of the present invention is usually 0.1% by weight or more, preferably 0.5% by weight or more, based on the total solid content. It is 20 wt% or less, preferably 10 wt% or less.
(B) It is preferable for the content of the photopolymerization initiator to be in the above-mentioned range since the sensitivity is good and a residue is hardly generated.

[(C) Compound having radically polymerizable double bond]
The compound (C) having a radical polymerizable double bond (hereinafter sometimes referred to as “component (C)”) used in the curable resin composition for organic insulating film of the present embodiment is a polymerizable low molecule. The compound is not particularly limited as long as it is a compound, but is preferably a compound having one or more ethylenically unsaturated groups (hereinafter sometimes referred to as “ethylenically unsaturated compound”). Those containing a compound having 2 or more are preferred.

  Examples of the compound having one ethylenically unsaturated group include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof, (meth) Examples include acrylonitrile, (meth) acrylamide, and styrene.

  Examples of compounds having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, and hydroxy (meth) acrylate compounds. And urethane (meth) acrylates of polyisocyanate compounds and epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds.

  These may be used alone or in combination of two or more.

  Specific examples of compounds having two or more ethylenically unsaturated bonds in the molecule are given below.

(C-1) Esters of Unsaturated Carboxylic Acid and Polyhydroxy Compound Esters of Unsaturated Carboxylic Acid and Polyhydroxy Compound (hereinafter may be abbreviated as “ester (meth) acrylates”). Examples of the saturated carboxylic acid include one or more of (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid and the like, and specific examples thereof include the following compounds. .

  Reaction product of unsaturated carboxylic acid and sugar alcohol: Examples of the sugar alcohol include ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, tetra Examples include methylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.

  Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol: Examples of sugar alcohol 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 of alcoholamines include diethanolamine and triethanolamine.

  More specifically, the following compounds can be exemplified as esters of an unsaturated carboxylic acid and a polyhydroxy compound.

  Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, and the like.

  In addition, as esters of unsaturated carboxylic acid and polyhydroxy compound, unsaturated carboxylic acid and aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts These reactants can be mentioned. Specific examples include bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], and the like.

  Furthermore, examples of the ester of an unsaturated carboxylic acid and a polyhydroxy compound include a reaction product of an unsaturated carboxylic acid and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate. Specific examples include di (meth) acrylate and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate.

  Furthermore, examples of the ester of an unsaturated carboxylic acid and a polyhydroxy compound include a reaction product of an unsaturated carboxylic acid, a polyvalent carboxylic acid, and a polyhydroxy compound. Specifically, for example, 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.

(C-2) (Meth) acryloyloxy group-containing phosphates (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing (meth) acryloyloxy groups. Those represented by (Ia) to (Ic) are preferred.

(In Formulas (Ia), (Ib) and (Ic), R ¹¹ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is an integer of 1 to 3)

  Here, p and p ′ are each preferably 1 to 10, particularly preferably 1 to 4.

  Specific examples of such compounds include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate, and these are used alone. Or may be used as a mixture.

(C-3) Urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound Examples of the hydroxy (meth) acrylate compound include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylol. Examples include hydroxy (meth) acrylate compounds such as ethanetri (meth) acrylate.

  Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate and 1,8-diisocyanate-4-isocyanate methyloctane; cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone. Alicyclic polyisocyanates such as diisocyanate and bicycloheptane triisocyanate; Aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate and tris (isocyanatophenyl) thiophosphate; Heterocyclic polyisocyanates such as isocyanurate; Allophanate-modified polyisocyanurate And polyisocyanate compounds such as;

  As urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound, urethane (meth) acrylates containing the allophanate-modified polyisocyanurate are particularly preferable. Urethane (meth) acrylates containing allophanate-modified polyisocyanurate have low viscosity, excellent solubility in solvents, and are effective in improving adhesion to the substrate and film strength by photocuring and / or thermal curing. This is preferable in terms of points.

  Commercially available urethane (meth) acrylates can be used. Specifically, for example, trade names “U-4HA” “UA-306A” “UA-MC340H” “UA-MC340H” “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd., and compounds having an allophanate skeleton manufactured by Bayer Japan “ AGROR 4060 "etc. are mentioned.

  In the present invention, the urethane (meth) acrylates include 4 or more (preferably 6 or more, more preferably 8 or more) urethane bonds [—NH—CO—O— in one molecule from the viewpoint of sensitivity. And a compound having 4 or more (preferably 6 or more, more preferably 8 or more) (meth) acryloyloxy groups. Such a compound can be obtained, for example, by reacting the following compound (C-i) with the following compound (C-ii).

(Ci) Compound having 4 or more urethane bonds in one molecule For example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, a compound having 4 or more hydroxyl groups in 1 molecule such as pentaerythritol and polyglycerol, Compound (Ci-1) obtained by reacting a diisocyanate compound such as isophorone diisocyanate or tolylene diisocyanate; or a compound having two or more hydroxyl groups in one molecule such as ethylene glycol, manufactured by Asahi Kasei Kogyo Co., Ltd. Biuret type such as “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 18H-70B”, “Duranate P-301-75E”, “Duranate E-402” -90T "," De Compound (Ci-2) obtained by reacting a compound having three or more isocyanate groups in one molecule, such as adduct type such as "Uranate E-405-80T"; or isocyanate ethyl (meth) And a compound (Ci-3) obtained by polymerizing or copolymerizing acrylate or the like.
A commercial item can be used as such a compound, for example, "Duranate ME20-100" by Asahi Kasei Kogyo Co., Ltd. is mentioned.

(C-ii) Compound having 4 or more (meth) acryloyloxy groups in one molecule For example, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Examples thereof include compounds having one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyloxy groups in one molecule, such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexaacrylate.

Here, the molecular weight of the compound (Ci) is preferably a weight average molecular weight in terms of polystyrene measured by GPC, preferably 500 to 200,000, and 1,000 to 150,000. Particularly preferred.
Moreover, as molecular weight of the said urethane (meth) acrylates, it is a weight average molecular weight of polystyrene conversion measured by GPC, and it is preferable that it is 600-150,000.

  In addition, such urethane (meth) acrylates are, for example, the above compound (Ci) and the above compound (C-ii) in an organic solvent such as toluene or ethyl acetate at 10 to 150 ° C. Can be produced by a method of reacting for about 5 minutes to 3 hours. In this case, the molar ratio of the former isocyanate group to the latter hydroxyl group is preferably set to a ratio of 1/10 to 10/1, and a catalyst such as n-butyltin dilaurate is preferably used as necessary.

(C-4) Epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compound and (poly) epoxy compound As hydroxy (meth) acrylate compounds, for example, hydroxymethyl (meth) acrylate, hydroxy Examples include hydroxy (meth) acrylate compounds such as ethyl (meth) acrylate and tetramethylolethane tri (meth) acrylate.

  Examples of the (poly) epoxy compound include (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly Aliphatic polyepoxy compounds such as neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac poly Aromatic polyepoxy compounds such as poxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds; heterocyclic polyepoxies such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate (Poly) epoxy compounds such as compounds;

  As epoxy (meth) acrylates which are a reaction product of (meth) acrylic acid or hydroxy (meth) acrylate compound and (poly) epoxy compound, such (poly) epoxy compound and (meth) acrylic acid Or the reaction material with the said hydroxy (meth) acrylate compound, etc. are mentioned.

(C-5) Other ethylenically unsaturated compounds Other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, and allyl esters such as diallyl phthalate. And vinyl group-containing compounds such as divinyl phthalate, and thioether bond-containing compounds whose crosslinking rate is improved by sulfurizing ether bonds of ether-containing ethylenically unsaturated compounds with phosphorus pentasulfide to convert them into thioether bonds. It is done.

Further, for example, polyfunctional (meth) acrylate compounds described in JP-A-5-287215 and JP-A-9-100111 and silica sols having a particle diameter of 5 to 30 nm [for example, isopropanol-dispersed organosilica sol (Nissan Chemical Co., Ltd.) "IPA-ST"), methyl ethyl ketone-dispersed organosilica sol ("MEK-ST" manufactured by Nissan Chemical Co., Ltd.), methyl isobutyl ketone-dispersed organosilica sol ("MIBK-ST" manufactured by Nissan Chemical Co., Ltd.)), etc.] Examples thereof include compounds bonded using a group-containing silane coupling agent.
These compounds are compounds in which the strength and heat resistance as a cured product are improved by reacting and bonding silica sol to an ethylenically unsaturated compound via a silane coupling agent.

  As other ethylenically unsaturated compounds, known compounds described in JP-A No. 2005-165294 can also be used.

  These may be used alone or in combination of two or more.

  The ethylenically unsaturated compound in the present invention preferably includes a compound having two or more ethylenically unsaturated groups in the molecule from the viewpoint of better polymerization and crosslinkability. Among these, ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferable, and ester (meth) acrylates are more preferable. Among the ester (meth) acrylates, aromatic polyhydroxy compounds such as bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], or Particularly preferred are those reactants with ethylene oxide adducts.

  In the ethylenically unsaturated compound in the present invention, those which do not contain an aromatic ring, or those which contain an unsubstituted or phenyl group having a substituent at the p (para) position are discolored by heat treatment of the protective film. This is preferable because (red coloring) is suppressed. Examples of such ethylenically unsaturated compounds include aliphatic polyfunctional (meth) acrylates and polyhydric alcohol (meth) acrylate compounds having a bisphenol A or fluorene skeleton.

The content of the compound having a radically polymerizable double bond (C) in the curable resin composition for an organic insulating film of the present invention is usually 10% by weight or more, preferably 20% by weight or more in the total solid content, Usually, it is 70% by weight or less, preferably 60% by weight or less. Moreover, as the compounding ratio of the component (C) to the specific resin of the component (A), the compounding amount of the component (C) with respect to 100 parts by weight of the component (A) is usually 150 parts by weight or less, preferably 120 parts by weight or less. More preferably, it is 110 parts by weight or less, usually 50 parts by weight or more, preferably 70 parts by weight or more, and more preferably 80 parts by weight or more.
If the amount of the compound having a radically polymerizable double bond as the component (C) is excessively small, the sensitivity and the development dissolution rate are likely to be decreased. If the amount is excessively large, the reproducibility of the cross-sectional shape of the image is decreased. It is easy to invite film slipping.

  When the component (C) in the present invention contains a compound having two ethylenically unsaturated groups, the compound having two ethylenically unsaturated groups is added to the total weight of the component (A) and the component (C). The occupying ratio is usually 10% by weight or more, preferably 20% by weight or more, and usually 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 excessively small, the peelability may be lowered.

Moreover, as a component (C) in this invention, when using the compound which has 3 or more of ethylenically unsaturated groups for at least one part, as content of the compound which has 3 or more of the said ethylenically unsaturated groups, (A ) With respect to 100 parts by weight of the specific resin of the component, it is usually 100 parts by weight or less, preferably 90 parts by weight or less, and more preferably 80 parts by weight or less.
Furthermore, the content of the compound having 3 or more ethylenically unsaturated groups in the component (C) is preferably 90 parts by weight or less, based on 100 parts by weight of the total weight of the component (C), and 80 parts by weight. More preferably, it is as follows.
Furthermore, the proportion of the compound having three or more ethylenically unsaturated groups in the total weight of the component (A) and the component (C) is usually 60% by weight or less, preferably 50% by weight or less, more Preferably, it is 40% by weight or less, and the lower limit is usually 5% by weight or more.
Within the above range, it is preferable in that the peelability after exposure is hardly lowered.

(D) Thermal crosslinking agent The curable resin composition for organic insulating films of the present invention is (D) a thermal crosslinking agent (hereinafter sometimes referred to as “component (D)”) for the purpose of increasing the hardness of the insulating film. It is preferable to further contain.

  Any known thermal crosslinking agent can be used as long as it undergoes a crosslinking reaction by baking after image formation by exposure and development. Specific examples include the following.

(D-1) Compound having epoxy group in molecule In the present invention, the compound having an epoxy group in the molecule is, for example, (poly) glycidyl obtained by reacting a monohydroxy compound or a polyhydroxy compound with epichlorohydrin. Low molecular weights such as ether compounds, (poly) glycidyl ester compounds obtained by reacting (poly) carboxylic acid compounds and epichlorohydrin, and (poly) glycidyl amine compounds obtained by reacting (poly) amine compounds and epichlorohydrin Compounds ranging from products to high molecular weight products.

(D-1-1) (Poly) glycidyl ether compound Examples of the (poly) glycidyl ether compound include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), bis (3 , 5-dimethyl-4-hydroxyphenyl) diglycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol A diglycidyl ether type epoxy, tetramethylbisphenol A diglycidyl ether type epoxy, ethylene oxide-added bisphenol A Diglycidyl ether type epoxy, dihydroxyoxyfluorene type epoxy, dihydroxyalkyleneoxyl fluorene type epoxy, bisphenol A / aldehyde novolak Type epoxy, phenol novolac type epoxy, and cresol novolac type epoxy.

  The (poly) glycidyl ether compound includes a polyglycidyl ether resin. Polyglycidyl ether resins include bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, phenol and dicyclopentadiene polymerized epoxy resin, phenol and naphthalene polymerized epoxy resin, etc. A type epoxy resin is mentioned.

  These (poly) glycidyl ether compounds may be those obtained by reacting a remaining hydroxyl group with an acid anhydride, a divalent acid compound, or the like to introduce a carboxyl group.

(D-1-2) (Poly) glycidyl ester compound Examples of the (poly) glycidyl ester compound include a diglycidyl ester type epoxy of hexahydrophthalic acid, a diglycidyl ester type epoxy of phthalic acid, and the like.

(D-1-3) (Poly) glycidylamine compound Examples of the (poly) glycidylamine compound include diglycidylamine-type epoxy of bis (4-aminophenyl) methane, triglycidylamine-type epoxy of isocyanuric acid, and the like. It is done.

(D-1-4) Other As other examples, for example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth ) Acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, etc. (Meth) acrylates having an epoxy group of (co) polymers obtained by reacting one kind alone or two or more kinds in combination. Or the copolymer which made the (meth) acrylate structural unit which has an epoxy group contain the other monomer for copolymerization normally 10-70 mol%, Preferably 15-60 mol% is mentioned.

  Examples of the monomer for copolymerization include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, ( Esters of (meth) acrylic acid such as phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate And vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, and vinylnaphthalene.

  The (meth) acrylate having an epoxy group is preferably glycidyl (meth) acrylate. Preferred examples of the monomer for copolymerization include (meth) acrylic acid, methyl (meth) acrylate, dicyclopentanyl (meth) acrylate, styrene, and α-methylstyrene.

  When the epoxy compound is a resin (hereinafter sometimes abbreviated as “epoxy resin”), the preferred molecular weight is that the curable resin composition for an organic insulating film of the present embodiment can be uniformly applied in a solution state. As long as it is, it is not particularly limited, and it 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 a polystyrene-reduced weight average molecular weight measured by GPC, usually in the range of 2,000 to 300,000, preferably 3,000 to 100,000, more preferably 4, 000 to 50,000.

  The epoxy group used in the epoxy compound or epoxy resin in the present invention is usually a 1,2 epoxy group, but for the purpose of improving the stability over time or imparting flexibility, the 1,3 epoxy group (oxetane) is used. ), 4,3-epoxycyclohexyl groups can also be used.

  In addition, the epoxy compound in the present invention does not contain an aromatic ring or contains a phenyl group that is unsubstituted or has a substituent at the p (para) position. Coloration) is suppressed, which is preferable. Examples of such epoxy compounds include bisphenol A type epoxy compounds and epoxy resins, epoxy compounds and epoxy resins having an optionally substituted fluorene skeleton, and copolymers of glycidyl (meth) acrylate. Can do.

  When the curable resin composition for organic insulating films of the present invention contains a compound having an epoxy group in the molecule, the content thereof is usually 60% by weight or less, preferably 50% by weight based on the total solid content. % Or less, more preferably 30% by weight or less, and usually 1% by weight or more. When 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 / development is easily lowered.

(D-2) Nitrogen-containing thermally crosslinkable compound Examples of the nitrogen-containing thermally crosslinkable compound in the present invention include melamine, benzoguanamine, glycoluril, a compound obtained by allowing formalin to act on urea, or an alkyl-modified compound thereof. it can.

Specifically, as an example of a compound in which formalin is allowed to act on melamine or an alkyl-modified product thereof, “Cymel” (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771 manufactured by Cytec Industries, Ltd. 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, “Nikarak” (registered trademark) E-2151, Sanwa Chemical Co., MW -100LM, MX-750LM, and the like.
Examples of the compound obtained by allowing formalin to act on benzoguanamine or an alkyl-modified product thereof include “Cymel” (registered trademarks) 1123, 1125, 1128, and the like.

  Examples of compounds obtained by allowing formalin to act on glycoluril or alkyl-modified products thereof include “Cymel” (registered trademark) 1170, 1171, 1174, 1172, “Nicarak” (registered trademark) MX-270, and the like. Can do.

  Further, examples of a compound in which formalin is allowed to act on urea or an alkyl-modified product thereof include “UFR” (registered trademark) 65 and 300, “Nicarak” (registered trademark) MX-290 manufactured by Cytec Industries, and the like. be able to.

As the nitrogen-containing thermally crosslinkable compound, a compound having —N (CH ₂ OR) ₂ group (wherein R represents an alkyl group or a hydrogen atom) in the molecule is preferable, and urea or melamine is preferable. A compound in which formalin is allowed to act or an alkyl-modified product thereof is particularly preferable.

  When the curable resin composition for organic insulating films of the present invention contains a nitrogen-containing thermally crosslinkable compound, the content thereof is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content. More preferably, it is 20% by weight or less. If the amount of the nitrogen-containing thermally crosslinkable compound is excessively large, the remaining film ratio during development and the resolution are liable to be reduced.

  One of the above thermal crosslinking agents may be used alone, or two or more thereof may be mixed and used.

(D) As a particularly preferred compound as a thermal crosslinking agent, a compound having —N (CH ₂ OR) ₂ group (wherein R represents an alkyl group or a hydrogen atom) in the molecule can be mentioned. A compound in which formalin is allowed to act on melamine or an alkyl-modified product thereof is particularly preferable.

  The content of the thermal crosslinking agent (D) in the curable resin composition for organic insulating films of the present invention is usually 1% by weight or more, preferably 2% by weight or more, and usually 40% by weight or less in the total solid content. Preferably it is 30 weight% or less. If the amount of the thermal crosslinking agent is excessively small, the hardness of the film after thermosetting tends to decrease, and if it is excessively large, the resolution tends to decrease.

(E) Other components The curable resin composition for an organic insulating film of the present invention impairs the object of the present invention in addition to the above-mentioned components (A), (B), (C) and (D). Other components such as the following may be contained within the range.

(E-1) Adhesion aid The curable resin composition for organic insulating films of the present invention may contain (E-1) an adhesion aid for the purpose of improving the adhesion to the substrate.
(E-1) Examples of the adhesion assistant include silane coupling agents. More specifically, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxy Examples include silane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

  Further, the silane coupling agent has not only a function as an adhesion assistant but also a function of imparting appropriate thermal melting (thermal fluidity) to the protective film in heat treatment to improve flatness. As a silane coupling agent mix | blended for such a purpose, the silane coupling agent which has an epoxy group is mentioned, for example. More specifically, for example, γ-gridoxypropylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

  (E-1) In the case of using an adhesion assistant, the amount of the adhesion assistant is usually 0.1% by weight or more with respect to the total solid content of the curable resin composition for organic insulating films, and usually 20 % By weight or less, preferably 10% by weight or less.

(E-2) Thermal polymerization inhibitor The curable resin composition for organic insulating films of the present invention may contain (E-2) a thermal polymerization inhibitor.
As the thermal polymerization inhibitor, for example, o-hydroxybenzophenone, hydroquinone, p-methoxyphenol, methylhydroquinone, 2,6-di-t-butyl-p-cresol, etc., which may have a substituent, may be used. Can do. These may be used alone or in combination of two or more.

  (E-2) When a thermal polymerization inhibitor is used, the amount of the thermal polymerization inhibitor is usually 10% by weight or less, preferably 2% in the total solid content of the curable resin composition for organic insulating films. % Or less.

(E-3) Ultraviolet absorber Furthermore, the curable resin composition for organic insulating films of this invention can also add (E-3) ultraviolet absorber as needed.
(E-3) The ultraviolet absorber is a curable resin for an organic insulating film of the present invention formed on a substrate by absorbing a specific wavelength of a light source used for exposure by the (E-3) ultraviolet absorber. It is added for the purpose of controlling the photocuring rate when the film of the composition is exposed. 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.

  (E-3) As the ultraviolet absorber, for example, a compound having an absorption maximum between a wavelength of 50 nm and 400 nm can be used. More specifically, for example, Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Yongkou Chemical Industry Co., Ltd.), Tomissorb 800 (manufactured by API Corporation), SEESORB100, SESORB101S, SEESORB102S, SEESORB102, SEESORB102 Benzophenone compounds such as SESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Cypro Kasei Co., Ltd.); Johoku Chemical Industry Co., Ltd.), TINUVIN PS, TINUVIN99-2 TINUVIN109, TINUVIN384-2, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (made in Taiwan Yongguang Chemical Industry Co., Ltd.), Tomisobu 100, Tomisosorb 600 (manufactured by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Sipro Kasei) Any benzotriazole compound; benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical Co., Ltd.) and phenyl salicylate; Among these, benzotriazole compounds and hydroxyphenyltriazine compounds are preferable, and benzotriazole compounds are particularly preferable. These ultraviolet absorbers may be used alone or in combination of two or more.

  When these (E-3) ultraviolet absorbers are added, the blending ratio is usually 0.01% by weight or more and 15% by weight or less, preferably based on the total solid content of the curable resin composition for organic insulating films. Is 0.05 wt% or more and 10 wt% or less. If the blending ratio of the UV absorber is less than this range, effects such as improvement of the pattern shape and / or removal of the residue tend to be difficult to obtain, and if it is large, the sensitivity and / or the remaining film ratio are decreased. Tend.

(E-4) Surfactant The curable resin composition for organic insulating films of the present invention is nonionic for the purpose of improving the coatability and developability of the film of the curable resin composition for organic insulating films, It may contain anionic, cationic, amphoteric surfactants or (E-4) surfactants such as fluorine and silicone.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxy And ethylene sorbite fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as “Emulgen 104P” and “Emulgen A60” manufactured by Kao Corporation.

  Examples of the anionic surfactant include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, and higher alcohol sulfate esters. , Aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymers And surface active agents. Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

  Commercially available products can be used as such anionic surfactants. Examples of alkyl sulfates include Kao's trade name “Emar 10”, and alkylnaphthalene sulfonates include Kao's trade name “Perex”. Examples of special polymer surfactants such as “NB-L” include “Homogenol L-18” and “Homogenol L-100” manufactured by Kao Corporation.

  Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and amine salts. Examples of the amphoteric surfactant include betaine-type compounds, imidazolium salts, imidazolines, and amino acids. It is done. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Examples of commercially available products include “Acetamine 24” manufactured by Kao Corporation for alkylamine salts, and “Cotamine 24P” and “Cotamine 86W” manufactured by Kao Corporation for quaternary ammonium salts.

Further, as the above-mentioned fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain is suitable.
Specifically, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2, 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8, Examples include 9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, and the like.

  As these commercial products, trade names “BM-1000” and “BM-1100” manufactured by BM Chemie, trade names “Megafuck F142D”, “Megafuck F172”, “Megafuck F173” manufactured by Dainippon Ink & Chemicals, Inc. ”,“ Megafuck F183 ”,“ Megafuck F470 ”,“ Megafuck F475 ”, Sumitomo 3M product name“ FC430 ”, Neos product name“ DFX-18 ”, and the like.

Examples of the silicone surfactant include trade names “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “SH30PA”, “SH8400” manufactured by Toray Silicone Co., Ltd. Product names “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4446”, “TSF-4460”, “TSF-4442” manufactured by Momentive Performance Materials, Shin-Etsu Silicone Commercial products such as the product name “KP341” and the product names “BYK323” and “BYK330” manufactured by Big Chemie may be mentioned. These surfactants may be used alone or in combination of two or more.
Of these, silicone surfactants and fluorine surfactants are preferable, and a combination of a fluorine surfactant and a nonionic silicone surfactant having an HLB value of 0.5 to 5 is more preferable.

  The content of the surfactant (E-4) in the curable resin composition for organic insulating films of the present invention is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total solid content. preferable.

(F) Organic solvent The curable resin composition for organic insulating films of the present invention usually contains (F) an organic solvent. That is, each of the above-described components is usually prepared on a substrate by using an organic solvent so that the solid concentration is 5 to 60% by weight, preferably 10 to 50% by weight. -After being developed, it is thermoset to form an organic insulating film.

The organic solvent is not particularly limited as long as it can dissolve and disperse the above-described components and has good handleability. Specifically, for example, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, chloroform, dichloromethane, acetic acid Ethyl, methyl lactate, ethyl lactate, 3-methoxymethyl propionate, 3-ethoxyethyl propionate, propylene glycol monomethyl ether, methanol, ethanol, propanol, butanol, tetrahydrofuran, diethylene glycol dimethyl ether, methoxybutyl acetate, Solvesso , Carbitol and the like. These organic solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The boiling point of the organic solvent is preferably in the range of 100 to 200 ° C, more preferably in the range of 120 to 170 ° C.

[Method for forming protective film (cured product)]
Next, regarding a method for forming a cured product using the curable resin composition for organic insulating films of the present invention, the curable resin composition for organic insulating films of the present invention is applied to the substrate on which the TFT array is formed for protection. An example of forming a film will be described. The curable resin composition for organic insulating films of the present invention is used for liquid crystal panels such as liquid crystal displays of liquid crystal display devices, such as overcoats and organic insulating films (interlayer insulating films made of organic compounds as materials). It is useful for formation, and the effect is particularly remarkable when it is used for forming an organic insulating film.

[1] Coating process First, a spinner, a wire bar, a flow coater, a die coater, a roll coater, a spray or the like is applied to the above-described curable resin composition for an organic insulating film on a substrate on which a TFT array is formed. Apply using equipment.
The coating film thickness of the curable resin composition for organic insulating films is usually 0.5 to 5 μm.

[2] Drying step The coating film is dried to remove volatile components and form a dry coating film. For drying, vacuum drying, hot plate, IR oven, convection 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. In addition, a method of performing heat drying with a hot plate after vacuum drying is preferable because a film with less coating unevenness can be formed. In this case, preferable vacuum drying conditions are a pressure of 10 to 10000 Pa and a drying time of 30 seconds to 10 minutes, and preferable heating and drying conditions are a temperature of 60 to 120 ° C. and a time of 30 seconds to 10 minutes.

[2] Exposure / Development Step Next, a photomask is placed on the dried coating film of the curable resin composition for organic insulating films, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel.

  Examples of the light source used in the exposure process of the dried coating film include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, and the like, an argon ion laser, and a YAG laser. And laser light sources such as excimer laser and nitrogen laser. When only light of a specific wavelength is used, an optical filter can be used.

  The solvent used for the development treatment is not particularly limited as long as it is a solvent capable of dissolving the coating film of the uncured part, but it is possible to increase the difference in solubility between the cured part and the uncured part. In view of obtaining a good pattern shape, an alkali developer is preferably used.

  Examples of such alkali developer include inorganic alkali compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethylamine, An aqueous solution containing an organic alkali compound such as ethanolamine or tetramethylammonium hydroxide can be mentioned.

  The alkaline 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, etc., if necessary. In particular, it is preferable to add surfactants because many surfactants have an improving effect on developability, resolution, and residues.

  Examples of the surfactant used in the developer include an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a tetraalkylammonium group. And cationic surfactants.

  Although there is no particular limitation on the development processing method, it is usually carried out by a method such as immersion development, paddle development, spray development, brush development, ultrasonic development at a development temperature of 10 to 50 ° C., preferably 15 to 45 ° C. Is called.

[4] Thermosetting process The film on which an image has been formed by the exposure / development process then becomes a cured product (thermosetting film) through a thermosetting (hard baking) process. In addition, after the development, the entire surface exposure may be performed for the purpose of suppressing the generation of outgas during the hard baking before the hard baking.

  When performing full exposure before hard baking, ultraviolet light or visible light is used as the light source. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp. And a laser light source such as an argon ion laser, a YAG laser, an excimer laser, and a nitrogen laser.

  For the hard baking, a hot plate, an IR oven, a convection oven or the like can be used. The hard baking conditions are usually 200 to 300 ° C. and a drying time of 30 seconds to 90 minutes.

  Usually, an image obtained after thermosetting tends to require higher-definition contact hole reproducibility in order to realize a high-quality display. In order to stably reproduce a high-definition contact hole, a rectangular shape having a clear contrast between the non-image area and the image area is preferable as the cross-sectional shape of the contact hole after development.

  The thickness of the protective film thus formed is usually 0.5 to 5 μm.

[TFT active matrix substrate and liquid crystal display device (panel)]
Next, a manufacturing method of the TFT active matrix substrate and the liquid crystal display device (panel) according to the present invention including the protective film formed as described above will be described.
The liquid crystal display device of the present invention usually comprises a TFT active matrix substrate.

  First, 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 forming an ITO wiring using a photolithography method. It is formed by.

The liquid crystal display device of the present invention can be completed by bonding the TFT active matrix substrate to the counter substrate to form a liquid crystal cell, injecting liquid crystal into the formed liquid crystal cell, and further connecting the counter electrode. .
In general, a color filter substrate having an alignment film is preferably used as the counter substrate.

As the alignment film, a resin film such as polyimide is suitable.
For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted. Note that 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 varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin.

  As such a sealing material, a material that can be cured by UV irradiation and / 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 is reduced in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. Can do.

The degree of vacuum in the liquid crystal cell is usually 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. It is. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction. The heating temperature in this case 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 condition during decompression is 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 into which the liquid crystal is injected cures the UV curable resin and seals the liquid crystal injection port. In this way, a liquid crystal display device (panel) can be completed.

  In addition, there is no restriction | limiting in particular in the kind of liquid crystal, A liquid crystal conventionally known, such as an aromatic type, an aliphatic type, a polycyclic compound, can be used, Any of a lyotropic liquid crystal, a thermotropic liquid crystal, etc. may be sufficient. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, unless this summary is exceeded, this invention is not limited to a following example.
In the following, “part” means “part by weight”.

[Synthesis Example 1]
A separable flask equipped with a cooling tube was prepared as a reaction tank, and 20 parts of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “MD”) was used as a monomer dropping tank. Methacrylic acid (hereinafter referred to as “MAA”) 32 parts, methyl methacrylate (hereinafter referred to as “MMA”) 78 parts, styrene (hereinafter referred to as “St”) 70 parts, t-butylperoxy-2-ethylhexa A mixture prepared by thoroughly stirring and mixing 10 parts of noate (“Perbutyl O” manufactured by NOF Corporation; hereinafter referred to as “PBO”) and 40 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMAc”) was prepared.

  After charging 275 parts of PGMAc in the reaction vessel and purging with nitrogen, the reaction vessel was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, it was cooled to room temperature to obtain a polymer solution (I) having a concentration of 40% by weight. The weight average molecular weight of the specific resin contained in the polymer liquid (I) was 7100, and the acid value was 104 mg-KOH / g.

[Synthesis Example 2]
A separable flask equipped with a cooling tube was prepared as a reaction tank, while a monomer dropping tank was prepared by thoroughly stirring and mixing 20 parts of MD, 38 parts of MAA, 72 parts of MMA, 70 parts of StO, 6 parts of PBO, and 40 parts of PGMAc.

  The reaction vessel was charged with 310 parts of PGMAc and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a polymer solution (II) having a concentration of 37% by weight. The weight average molecular weight of the specific resin contained in the polymer (II) was 11900, and the acid value was 120 mg-KOH / g.

[Synthesis Example 3]
A separable flask with a cooling tube was prepared as a reaction tank, and a monomer dropping tank was prepared by thoroughly stirring and mixing 10 parts of MD, 38 parts of MAA, 72 parts of MMA, 80 parts of StO, 6 parts of PBO, and 40 parts of PGMAc.

  The reaction vessel was charged with 310 parts of PGMAc and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a polymer solution (III) having a concentration of 37% by weight. The weight average molecular weight of the specific resin contained in the polymer (III) was 11300, and the acid value was 124 mg-KOH / g.

[Examples 1 to 5, Comparative Example 1]
<Preparation of curable resin composition for organic insulating film>
A curable resin composition for an organic insulating film was prepared according to the formulation shown in Table 1.
In addition, each compound in Table 1 is as follows.

(A) Resin P1: Styrene / Methyl methacrylate / Methacrylic acid (Molar ratio: 45/35/25)
Copolymer resin Weight average molecular weight = 10,000
Acid value = 113 mg-KOH / g
Concentration = 40% by weight (PGMAc solution)

(C) Compound having a radical polymerizable double bond C1: DPHA (manufactured by Nippon Kayaku Co., Ltd.) Dipentaerythritol hexaacrylate C2: NP-A (manufactured by Kyoeisha Chemical Co.) Neopentyl glycol diacrylate

    C4: PM-21 (manufactured by Nippon Kayaku Co., Ltd.) ethylene oxide modified phosphoric dimethacrylate

(D) Thermal crosslinking agent

(E) Other ingredients

(F) Solvent PGMAc: Propylene glycol monomethyl ether acetate

<Insulating protective film formation procedure>
The obtained curable resin composition for organic insulating films was applied onto a glass substrate by a spin coating method, and dried on a hot plate at 100 ° C. for 90 seconds to obtain a coating film having a dry film thickness of 4 μm. Then, it exposed using the 3kW high pressure mercury lamp through the mask which has a contact hole pattern of 10 micrometers-50 micrometers from the coating film side. As the exposure conditions, the image plane illuminance measured with an illuminometer with a wavelength of 365 nm was 15 mW / cm ² , and the exposure amount was the optimum exposure amount described later.
Next, a 2.38% by weight tetramethylammonium hydroxide aqueous solution was used as a developing solution, and the substrate was immersed in the developing solution for 60 seconds at 24 ° C., followed by rinsing with pure water and exposure film. Got. The obtained exposed film was further heated in a convection oven at 220 ° C. for 1 hour to obtain an organic insulating film.

  The following evaluation was performed about the said curable resin composition for organic insulating films, an exposure film | membrane, and an insulating protective film, and the result was put together in Table 1. FIG.

(1) Optimum exposure amount and level difference forming property In the above-described organic insulating film formation procedure, a mask having a halftone portion with a transmittance of 20% and a total transmission portion is placed on the coating film before exposure, and a high-pressure mercury lamp is used. It exposed with the illumination intensity of 15 mW / cm < ² >. As the exposure conditions, the exposure energy amount was in the range from 4 mJ / cm ² to 100 mJ / cm ² , and the exposure energy amount was set at intervals of 2 ^1/2 times for exposure. After exposure, the film was immersed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 24 ° C. for 60 seconds, rinsed with pure water, and the film thickness of the remaining cured film (exposure film) was measured.
The film thickness of the obtained cured film is plotted against the exposure amount, and the minimum exposure amount at which the difference in the exposure film thickness between a certain exposure amount and 2 ^1/2 times the exposure amount is within 10%. Was the optimum exposure (mJ / cm ² ).
The level difference forming property was evaluated by measuring the difference ΔH between the thinnest film thickness remaining in the halftone part having a transmittance of 20% and the film thickness of the entire transmissive part at the optimum exposure amount.
As ΔH is larger, a higher step can be formed.

(2) Resolution The image of the organic insulating film obtained by the procedure for forming the organic insulating film is observed with an optical microscope, and the resolution of the minimum contact hole mask size (μm) that is resolved. did.

(3) Residue A 15 μm contact hole pattern of the organic insulating film obtained by the procedure for forming the organic insulating film was observed with an optical microscope, and the presence or absence of a residue in the hole portion was evaluated.

  From Table 1, by using the curable resin composition for an organic insulating film of the present invention, the organic insulation having good sensitivity, resolving power, transparency, step forming property, and no generation of residue even in a fine contact hole. It can be seen that a film can be obtained.

Claims (6)

(A) a resin obtained by (co) polymerizing a monomer component containing a compound represented by the following general formula (I) as an essential component;
(B) a photopolymerization initiator,
And (C) a curable resin composition for organic insulating films, comprising a compound having a radical polymerizable double bond.

(In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)   The curable resin composition for an organic insulating film according to claim 1, wherein the (B) photopolymerization initiator is an oxime ester-based compound.   The curable resin composition for organic insulating films according to claim 1, further comprising (D) a thermal crosslinking agent.   A cured product formed using the curable resin composition for an organic insulating film according to any one of claims 1 to 3.   A TFT active matrix substrate comprising the cured product according to claim 4.   A liquid crystal display device comprising the cured product according to claim 4.