Patent Application
20200209750
The present invention relates to a positive-type photosensitive resin composition capable of forming a cured film that is excellent in sensitivity, resolution, and film retention rate, and a cured film prepared therefrom to be used in a liquid crystal display, an organic EL display, and the like.
In general, a positive-type photosensitive resin composition that requires fewer processing steps is widely employed in liquid crystal display devices, organic EL display devices, and the like.
However, a planarization film or a display element using a conventional positive-type photosensitive resin composition has lower sensitivity than a planarization film and a display element using a negative-type photosensitive resin composition. Therefore, the sensitivity of the former needs to be improved.
Meanwhile, conventional positive photosensitive resin compositions generally comprise an alkali-soluble resin such as a siloxane polymer and an acrylic polymer as a binder resin, along with a photosensitive agent such as a quinonediazide-based compound, an aromatic aldehyde, or the like (see Japanese Laid-open Patent Publication No. 1996-234421).
However, when a cured film is formed using such a positive-type photosensitive resin composition, the rate of loss in the thickness of the cured film by a developer during the developing step is large, and there is a limit to achieving sufficiently satisfying film retention rate, sensitivity, resolution, and the like.
Meanwhile, the cured film requires a small size of a pattern and a high edge angle of the pattern in order to obtain a high resolution. Specifically, in order to obtain a high resolution, it is important that the size of holes in a mask applied at the time of forming a cured film reaches the target level of critical dimension (CD). At the same time, in order to prevent electrical interference between the lower and upper wirings, the edge angle of a pattern should be close to 90°.
Meanwhile, in order to enhance the edge angle of a pattern, there has been proposed a method of increasing the content of a photosensitive agent such as a quinonediazide-based compound or the like, which is widely used in the field of photoresist compositions, or a method of elevating the temperature during the pre-baking. However, although these methods can enhance the edge angle of a pattern, they have the disadvantage that the sensitivity is deteriorated.
Accordingly, the present invention aims to provide a positive-type photosensitive resin composition capable of forming a cured film that is excellent in the edge angle of a pattern without deteriorating such physical properties as sensitivity, resolution, and the like, and a cured film prepared therefrom to be used in a liquid crystal display, an organic EL display, and the like.
In order to accomplish the above object, the present invention provides a positive-type photosensitive resin composition, which comprises (A) a siloxane copolymer; and (B) a photoactive compound comprising a compound containing a repeat unit represented by the following Formula 1:
A1 and A2 are each independently hydrogen, a hydroxyl group, a phenol group, a C1-4 alkyl group, a C6-15 aryl group, or a C1-4 alkoxy group,
R1 is hydrogen or
and n is an integer of 3 to 15.
In order to accomplish another object, the present invention provides a cured film prepared using the positive-type photosensitive resin composition.
The positive-type photosensitive resin composition according to the present invention comprises a photoactive compound of a polymer, and/or a photoactive compound of a monomer, containing a repeat unit having a specific structure. Thus, the exposed portion (i.e., the portion exposed to light) is increased by the interaction between the binder resin (i.e., siloxane copolymer) and the photoactive compound, which increases the solubility in a developer, whereby the sensitivity can be enhanced. In addition, since the composition comprises the photoactive compound in a proper amount, it is possible to form a cured film capable of achieving a high edge angle of a pattern.
The present invention provides a positive-type photosensitive resin composition, which comprises (A) a siloxane copolymer; and (B) a photoactive compound.
It may optionally further comprise (C) an epoxy compound; (D) a surfactant; (E) an adhesion supplement; and/or (F) a solvent.
Hereinafter, each component of the positive-type photosensitive resin composition will be explained in detail.
As used herein, the term “(meth)acryl” refers to “acryl” and/or “methacryl,” and the term “(meth)acrylate” refers to “acrylate” and/or “methacrylate.”
The weight average molecular weight (g/mole, Da) of each component as described below is measured by gel permeation chromatography (GPC, eluent: tetrahydrofuran) referenced to a polystyrene standard.
(A) Siloxane Copolymer
The photosensitive resin composition comprising the siloxane copolymer (siloxane polymer; A) can be formed into a positive-type pattern by a process proceeding from exposure to light to development.
The siloxane polymer (A) is an alkali-soluble resin for materializing developability in the development step and also plays the role of a base for forming a film upon coating and a structure and a binder for forming a final pattern.
The siloxane polymer (A) includes a condensate of a silane compound and/or a hydrolysate thereof. In such event, the silane compound or the hydrolysate thereof may be a monofunctional to tetrafunctional silane compound. As a result, the siloxane polymer is may comprise a siloxane structural unit selected from the following Q, T, D, and M types:
Specifically, the siloxane polymer (A) may comprise a structural unit derived from a silane compound represented by the following Formula 2:
(R2)mSi(OR3)4-m [Formula 2]
In the above Formula 2, m is an integer of 0 to 3; R2 is each independently C1-12 alkyl, C2-10 alkenyl, C6-15 aryl, 3- to 12-membered heteroalkyl, 4- to 10-membered heteroalkenyl, or 6- to 15-membered heteroaryl; and R3 is each independently hydrogen, C1-6 alkyl, C2-6 acyl, or C6-15 aryl, wherein the heteroalkyl, the heteroalkenyl, and the heteroaryl groups each independently have at least one heteroatom selected from the group consisting of O, N, and S.
The compound may be a tetrafunctional silane compound where m is 0, a trifunctional silane compound where m is 1, a difunctional silane compound where m is 2, or a monofunctional silane compound where m is 3.
Particular examples of the silane compound may include, e.g., as the tetrafunctional silane compound, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, and tetrapropoxysilane; as the trifunctional silane compound, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, d3-methyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic acid; as the difunctional silane compound, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane, cyclohexyldimethoxymethylsilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, and dimethoxydi-p-tolylsilane; and as the monofunctional silane compound, trimethylsilane, tributylsilane, trimethylmethoxysilane, tributylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane.
Preferred among the tetrafunctional silane compounds are tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane; preferred among the trifunctional silane compounds are methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; preferred among the difunctional silane compounds are dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, and dimethyldiethoxysilane.
The conditions for obtaining a hydrolysate or a condensate of the silane compound of the above Formula 2 are not particularly limited.
The weight average molecular weight of the condensate (i.e., siloxane polymer) obtained by the hydrolytic polymerization of the silane compound of the above Formula 2 may be 500 to 50,000 Da, 1,000 to 50,000 Da, 3,000 to 30,000 Da, or 5,000 to 20,000 Da. If the weight average molecular weight of the siloxane polymer is within the above range, it is more preferable in terms of the film formation properties, solubility, dissolution rates in a developer, and the like.
The siloxane polymer (A) may comprise a structural unit derived from a silane compound represented by the above Formula 2 where m is 0 (i.e., Q-type structural unit). Specifically, the siloxane polymer may comprise the structural unit derived from the silane compound represented by the above Formula 2 where m is 0 in an amount of 10 to 50% by mole or 15 to 40% by mole based on an Si atomic mole number. If the amount of the Q-type structural unit is within the above range, the photosensitive resin composition may maintain its solubility to an aqueous alkaline solution at a proper level during the formation of a pattern, thereby preventing any defects caused by a reduction in the solubility or a drastic increase in the solubility of the composition.
The siloxane polymer (A) may comprise a structural unit derived from a silane compound represented by the above Formula 2 where m is 1 (i.e., T-type structural unit). For example, the siloxane polymer may comprise the structural unit derived from the silane compound of the above Formula 2 where m is 1 in an amount ratio of 40 to 99% by mole or 50 to 95% by mole based on an Si atomic mole number. If the amount of the T-type structural unit is within the above range, it is more preferable to form a more precise pattern profile.
In addition, in consideration of the hardness, sensitivity, and retention rate of a cured film, it is preferable that the siloxane polymer (A) comprises a structural unit derived from a silane compound having an aryl group. For example, the siloxane polymer may comprise a structural unit derived from a silane compound having an aryl group in an amount of 20 to 80% by mole, 30 to 70% by mole, or 30 to 50% by mole, based on an Si atomic mole number. If the amount of the structural unit derived from a silane compound having an aryl group is within the above range, the compatibility of the siloxane polymer (A) with the photoactive compound (B) is excellent, which may prevent an excessive decrease in sensitivity while attaining more favorable transparency of a cured film.
The structural unit derived from the silane compound having an aryl group may be, for example, a structural unit derived from a silane compound of the above Formula 2 where R2 is an aryl group, specifically a silane compound of the above Formula 2 where m is 1 and R2 is an aryl group, more specifically a silane compound of the above Formula 2 where m is 1 and R2 is a phenyl group (i.e., siloxane structural unit of T-phenyl type).
The term “% by mole based on an Si atomic molar number” as used herein refers to a percentage of the number of moles of Si atoms contained in a specific structural unit with respect to the total number of moles of Si atoms contained in all of the structural units constituting the siloxane polymer.
The molar amount of a siloxane unit in the siloxane polymer may be measured by the combination of Si-NMR, 1H-NMR, 13C-NMR, IR, TOF-MS, elementary analysis, measurement of ash, and the like. For example, in order to measure the molar amount of a siloxane unit having a phenyl group, an Si-NMR analysis is performed on the entire is siloxane polymer, followed by an analysis of the phenyl-bound Si peak area and the phenyl-unbound Si peak area. The molar amount can then be computed from the peak area ratio between them.
Meanwhile, the siloxane polymer of the present invention may be a mixture of two or more siloxane polymers having dissolution rates different from each other to an aqueous solution of tetramethylammonium hydroxide (TMAH). If a mixture of two or more siloxane polymers as described above is used as the siloxane polymer, it is possible to improve both of the sensitivity and the chemical resistance of the resin composition.
The photosensitive resin composition of the present invention may comprise the siloxane polymer (A) in an amount of 50 to 90% by weight or 65 to 90% by weight based on the total weight of the composition on the basis of the solids content excluding solvents. If the content of the siloxane polymer is within the above range, it is possible to maintain the developability of the composition at a suitable level, thereby producing a cured film that is excellent in the film retention and the pattern resolution.
(B) Photoactive Compound
The positive-type photosensitive resin composition according to the present invention may comprise (b-1) a compound containing a repeat unit represented by the following Formula 1 as the photoactive compound (B). It may optionally further comprise (b-2) a quinonediazide-based monomer.
(b-1) Compound Containing a Repeat Unit Represented by the Following Formula 1
The positive-type photosensitive resin composition according to the present invention may comprise a polymer compound containing an ortho-quinonediazide group as shown below as the photoactive compound (B).
Specifically, the photoactive compound (B) may comprise a compound (b-1) containing a repeat unit represented by the following Formula 1.
In the above Formula 1, A1 and A2 are each independently hydrogen, a hydroxyl is group, a phenol group, a C1-4 alkyl group, a C6-15 aryl group, or a C1-4 alkoxy group, R1 is hydrogen or
and n is an integer of 3 to 15.
More specifically, the compound (b-1) containing the repeat unit represented by the above Formula 1 may be an ester of 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-4-sulfonic acid, or the like, and/or a compound in which the hydroxyl group thereof is substituted with an amino group.
The compound (b-1) containing the repeat unit represented by the above Formula 1 may be used alone or in combination with an aromatic aldehyde-based alkali-soluble resin (e.g., a polyhydroxy aromatic compound).
For examples, a polyhydroxyalkyl compound such as glycerin, pentaerythritol, and the like, or a polyhydroxy aromatic compound such as a novolac resin, bisphenol A, a gallic acid ester, quercetin, morin, polyhydroxy benzophenone, or the like may be used in combination with an ester of 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-4-sulfonic acid, or the like. Preferably, a novolac resin and/or polyhydroxy benzophenone may be used in combination with an ester of 1,2-naphthoquinonediazide-5-sulfonic acid.
In such event, the substitution ratio (i.e., esterification ratio) of the novolac resin may be 10 to 70% or 25 to 60% (i.e., an esterified product of novolac resin/total novolac resin×100). The substitution ratio of the polyhydroxy benzophenone may be 50 to 95% (i.e., an esterified product of polyhydroxy benzophenone/total polyhydroxy benzophenone×100). Within the above ranges, the resolution and sensitivity of the composition can be further enhanced. If the substitution ratios are low, the resolution is deteriorated. If the substitution ratios are too high, the sensitivity may be deteriorated.
The compound (b-1) containing the repeat unit represented by the above Formula 1 may be employed in an amount of 1 to 100% by weight, 10 to 100% by weight, or 20 to 100% by weight, based on the total weight of the photoactive compound (B) on the basis of polymer content. Within the above content range, a pattern is more readily formed, the surface of a coating film is not roughened upon the formation thereof, and it is possible to suppress such a defective pattern shape as scum appearing at the bottom portion of the pattern upon development.
(b-2) Quinonediazide-Based Monomer
The positive-type photosensitive resin composition according to the present invention may further comprise a quinonediazide monomer (b-2), specifically, a 1,2-quinonediazide-based compound as the photoactive compound (B).
The 1,2-quinonediazide-based compound is not particularly limited as long as it is used as a photosensitive agent in the photoresist field and has a 1,2-quinonediazide-based structure.
Examples of the 1,2-quinonediazide-based compound include an ester compound of a phenolic compound and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid; an ester compound of a phenolic compound and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid; a sulfonamide compound of a phenolic compound in which the hydroxyl group is substituted with an amino group and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid; a sulfonamide compound of a phenolic compound in which the hydroxyl group is substituted with an amino group and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid. The above compounds may be used alone or in combination of two or more thereof.
Examples of the phenolic compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,3,3′,4-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4′-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3′,3′-tetramethyl-1,1′-spirobiindene-5,6,7,5′,6′,7′-hexanol, 2,2,4-trimethyl-7,2′,4′-trihydroxyflavane, bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-dimethylphenyl]methane, and the like.
More particular examples of the 1,2-quinonediazide-based compound (b-2) include an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-4-sulfonic acid, an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid, an ester of 4,4′-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-4-sulfonic acid, an ester of 4,4′-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid, and the like. If the compounds exemplified above are used as the 1,2-quinonediazide-based compound, the transparency of the photosensitive resin composition may be further enhanced.
The photoactive compound (B) may be employed in an amount of 1 to 40 parts by weight, 2 to 20 parts by weight, or 4 to 15 parts by weight, based on 100 parts by weight of the siloxane copolymer (A) on the basis of the solids content. If the amount of the photoactive compound (B) is within the above range, a pattern is more readily formed from the resin composition, and it is possible to prevent such defects as a rough surface of a coated film upon the formation thereof and such a pattern shape as scum appearing at the bottom portion of the pattern upon development.
(C) Epoxy Compound
The epoxy compound may increase the internal density of the resin composition, to thereby improve the chemical resistance of a cured film formed therefrom.
The epoxy compound (C) may be a homo-oligomer or a hetero-oligomer of an unsaturated monomer containing at least one epoxy group.
Examples of the unsaturated monomer containing at least one epoxy group may include glycidyl (meth)acrylate, 4-hydroxybutylacrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide, allyl glycidyl ether, 2-methylallyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. Specifically, glycidyl methacrylate may be used.
The epoxy compound may be synthesized by any conventional methods well known in the art. An example of the commercially available epoxy compound may be GHP03HP (glycidyl methacrylate homopolymer, Miwon Commercial Co., Ltd.).
The epoxy compound (C) may further comprise the following structural unit.
Particular examples thereof may include any structural unit derived from styrene;
a styrene having an alkyl substituent such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; a styrene having a halogen such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; a styrene having an alkoxy substituent such as methoxystyrene, ethoxystyrene, and propoxystyrene; p-hydroxy-α-methylstyrene, acetylstyrene; an ethylenically unsaturated compound having an aromatic ring such as divinylbenzene, vinylphenol, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, and p-vinylbenzyl methyl ether; an unsaturated carboxylic acid ester such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, propyl α-hydroxymethylacrylate, butyl α-hydroxymethylacrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxy diethylene glycol (meth)acrylate, methoxy triethylene glycol (meth)acrylate, methoxy tripropylene glycol (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxy diethylene glycol (meth)acrylate, p-nonylphenoxy polyethylene glycol (meth)acrylate, p-nonylphenoxy polypropylene glycol (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, tribromophenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; a tertiary amine having an N-vinyl group such as N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl morpholine; an unsaturated ether such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and 2-methylallyl glycidyl ether; an unsaturated imide such as N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide. The structural unit derived from the compounds exemplified above may be contained in the epoxy compound alone or in combination of two or more thereof.
Specifically, the styrene compounds are preferred among these examples from the viewpoint of polymerizability of the composition. In particular, it is more preferable in terms of the chemical resistance that the epoxy compound does not contain a carboxyl group by way of not using a structural unit derived from a monomer containing a carboxyl group among these compounds.
The weight average molecular weight of the epoxy compound (C) may be 100 to 30,000 Da, 1,000 to 20,000, 1,000 to 15,000, or 6,000 to 10,000 Da. If the weight average molecular weight of the epoxy compound is at least 100 Da, the hardness of a cured film may be more favorable. If it is 30,000 Da or less, the cured film may have a uniform thickness, which is suitable for planarizing any steps thereon.
The epoxy compound (C) may be employed in an amount of 0 to 40 parts by weight or 5 to 20 parts by weight based on 100 parts by weight of the siloxane copolymer (A) on the basis of the solids content. Within the above content range, the sensitivity and the chemical resistance of the photosensitive resin composition are more favorable. If it is used in a smaller amount than the above range, the chemical resistance is significantly deteriorated. If it is used in an excessive amount, the sensitivity is significantly deteriorated.
(D) Surfactant
The positive-type photosensitive resin composition of the present invention may further comprise a surfactant (D) to enhance its coatability, if desired.
The kind of the surfactant (D) is not particularly limited. Examples thereof may include fluorine-based surfactants, silicon-based surfactants, non-ionic surfactants, and the like.
Specific examples of the surfactant (D) may include fluorine- and silicon-based surfactants such as FZ-2122 supplied by Dow Corning Toray Co., Ltd., BM-1000 and BM-1100 supplied by BM CHEMIE Co., Ltd., Megapack F-142 D, F-172, F-173, and F-183 supplied by Dai Nippon Ink Chemical Kogyo Co., Ltd., Florad FC-135, FC-170 C, FC-430, and FC-431 supplied by Sumitomo 3M Ltd., Sufron S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, and SC-106 supplied by Asahi Glass Co., Ltd., Eftop EF301, EF303, and EF352 supplied by Shinakida Kasei Co., Ltd., SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, and DC-190 supplied by Toray Silicon Co., Ltd.; non-ionic surfactants such as polyoxyethylene alkyl ethers including polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like; polyoxyethylene aryl ethers including polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and the like; and polyoxyethylene dialkyl esters including polyoxyethylene dilaurate, polyoxyethylene distearate, and the like; and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylate-based copolymer Polyflow Nos. 57 and 95 (manufactured by Kyoei Yuji Chemical Co., Ltd.), and the like. They may be used alone or in combination of two or more thereof.
The surfactant (D) may be employed in an amount of 0.001 to 5 parts by weight, 0.05 to 3 parts by weight, or 0.2 to 2 parts by weight, based on 100 parts by weight of the siloxane copolymer (A) on the basis of the solids content. Within the above content range, the coating and leveling characteristics of the composition may be good.
(E) Adhesion Supplement
The photosensitive resin composition of the present invention may further comprise an adhesion supplement (E) to enhance the adhesiveness to a substrate.
The adhesion supplement (E) may have at least one reactive group selected from the group consisting of a carboxyl group, a (meth)acryloyl group, an isocyanate group, an amino group, a mercapto group, a vinyl group, and an epoxy group.
The kind of the adhesion supplement (E) is not particularly limited. For example, it may be at least one selected from the group consisting of trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-isocyanate propyl triethoxysilane, and a mixture thereof.
Preferred is γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-isocyanate propyl triethoxysilane, or N-phenylaminopropyltrimethoxysilane, which is capable of enhancing the film retention rate and the adhesiveness to a substrate.
The adhesion supplement (E) may be employed in an amount of 0.001 to 5 parts by weight or 0.01 to 4 parts by weight based on 100 parts by weight of the siloxane copolymer (A) on the basis of the solids content. Within the above content range, the adhesiveness to a substrate may be further enhanced.
(F) Solvent
The positive-type photosensitive resin composition of the present invention may be prepared in the form of a liquid composition in which the above components are mixed with a solvent (F). The solvent (F) may be, for example, an organic solvent.
The amount of the solvent (F) in the photosensitive resin composition according to the present invention is not particularly limited. For example, the solvent may be employed such that the solids content is 10 to 70% by weight or 15 to 60% by weight based on the total weight of the composition. The solid content refers to the components constituting the resin composition of the present invention, excluding solvents. If the amount of the solvent is within the above range, the coating of the composition can be readily carried out, while the flowability thereof can be maintained at a proper level.
The solvent (F) of the present invention is not particularly limited as long as it can dissolve the above-mentioned components and is chemically stable. For example, the solvent may be an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate, diethylene glycol, a propylene glycol monoalkyl ether, a propylene glycol alkyl ether acetate, a propylene glycol alkyl ether propionate, an aromatic hydrocarbon, a ketone, an ester, and the like.
Particular examples of the solvent (F) include methanol, ethanol, tetrahydrofuran, dioxane, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol butyl ether acetate, toluene, xylene, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 2-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.
Preferred among the above are ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, ketones, and the like. In particular, preferred are diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, methyl 2-methoxypropionate, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and the like. The solvents exemplified above may be used alone or in combination of two or more thereof.
In addition, the photosensitive resin composition of the present invention may further comprise other additives as long as the physical properties of the photosensitive resin composition are not adversely affected.
The photosensitive resin composition according to the present invention may be used as a positive-type photosensitive resin composition.
In particular, the positive-type photosensitive resin composition according to the present invention comprises a photoactive compound of a polymer, and/or a photoactive compound of a monomer, containing a repeat unit having a specific structure. Thus, the exposed portion (i.e., the portion exposed to light) is increased by the interaction between the binder resin (i.e., siloxane copolymer) and the photoactive compound, which increases the solubility in a developer, whereby the sensitivity can be enhanced. In addition, it is possible to form a cured film capable of achieving a high edge angle of a pattern by way of employing the photoactive compound in a proper amount.
The present invention provides a cured film formed from the photosensitive resin composition.
The cured film may be formed by a method known in the art, for example, a method in which the photosensitive resin composition is coated on a substrate and then cured. More specifically, in the curing step, the photosensitive resin composition coated on a substrate may be subjected to pre-bake at a temperature of, for example, 60 to 130° C. remove solvents; then exposed to light using a photomask having a desired pattern; and subjected to development using a developer, for example, a tetramethylammonium hydroxide (TMAH) solution to form a pattern on the coating layer. Thereafter, the patterned coating layer, if necessary, is subjected to post-bake, for example, at a temperature of 150 to 300° C. for 10 minutes to 5 hours to prepare a desired cured film. The exposure to light may be carried out at an exposure rate of 10 to 200 mJ/cm2 based on a wavelength of 365 nm in a wavelength band of 200 to 500 nm. According to the process of the present invention, it is possible to easily form a desired pattern from the viewpoint of the process.
The coating of the photosensitive resin composition onto a substrate may be carried out by a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like, in a desired thickness of, e.g., 2 to 25 μm. In addition, as a light source used for the exposure (irradiation), a low-pressure mercury lamp, a high-pressure mercury lamp, an extra high-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like may be used. X-ray, electronic ray, or the like may also be used, if desired. The photosensitive resin composition of the present invention is capable of forming a cured film that is excellent in terms of the heat resistance, transparency, dielectric constant, solvent resistance, acid resistance, and alkali resistance. Therefore, the cured film of the present invention thus formed has excellent light transmittance devoid of surface roughness when it is subjected to heat treatment or is immersed in, or comes into contact with a solvent, an acid, a base, or the like. Thus, the cured film can be effectively used as a planarization film for a thin-film transistor (TFT) substrate of a liquid crystal display or an organic EL display; a partition of an organic EL display; an interlayer dielectric of a semiconductor device; a core or cladding material of an optical waveguide, or the like. Further, the present invention provides an electronic part that comprises the cured film as a protective film.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto only. In the following preparation examples, the weight average molecular weight is determined by gel permeation chromatography (GPC, eluent: tetrahydrofuran) referenced to a polystyrene standard.
A reactor equipped with a reflux condenser was charged with 40% by weight of phenyltrimethoxysilane, 15% by weight of methyltrimethoxysilane, 20% by weight of tetraethoxysilane, and 20% by weight of distilled water and 5% by weight of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, followed by refluxing and vigorously stirring the mixture for 7 hours in the presence of 0.1% by weight of an oxalic acid catalyst. Then, the mixture was cooled and diluted with PGMEA such that the solids content was 40%. As a result, a siloxane copolymer (A) having a weight average molecular weight of 5,000 to 10,000 Da was prepared.
A three-necked flask was equipped with a cooling tube and placed on a stirrer equipped with a thermostat. The flask was charged with 100 parts by weight of a monomer composed of 100% by mole of glycidyl methacrylate, 10 parts by weight of 2,2′-azobis(2-methylbutyronitrile), and 100 parts by weight of PGMEA, followed by charging nitrogen thereto. Thereafter, the temperature of the solution was raised to 80° C. while the solution was stirred slowly, and the temperature was maintained for 5 hours. Next, the resultant was diluted with PGMEA such that the solids content was 20% by weight. As a result, an epoxy compound (C) having a weight average molecular weight of 6,000 to 10,000 Da was prepared.
The photosensitive resin compositions of the following Examples and Comparative Examples were each prepared using the compounds prepared in the above Preparation Examples.
The components used in the following Examples and Comparative Examples are as follows.
100 parts by weight of the siloxane copolymer (A) prepared in Preparation Example 1, 13.7 parts by weight of Polymer PAC (MCAD1040) (B-1) as the photoactive compound (B), 12.4 parts by weight of the epoxy compound (C) prepared in Preparation Example 2, and 0.1 part by weight of FZ-2122 as the surfactant (D) were homogeneously mixed. The mixture was dissolved in a mixed solvent of PGMEA and GBL (PGMEA:GBL=93:7) such that the solids content of the mixture was 17% by weight. The resultant was stirred for 2 hours and filtered through a membrane filter having a pore size of 0.2 μm to obtain a photosensitive resin composition solution having a solids content of 17% by weight.
Photosensitive resin composition solutions were each prepared in the same manner as in Example 1, except that the kinds and/or the contents of the respective components were changed as shown in Table 2 below.
The compositions prepared in the Examples and the Comparative Examples were each coated onto a glass substrate by spin coating. The coated substrate was then pre-baked on a hot plate kept at 105° C. for 90 seconds to form a dry film. A mask having a pattern of square holes in a size ranging from 2 μm to 25 μm was placed on the dried film. The film was then exposed to light at an exposure rate of 0 to 200 mJ/cm2 based on a wavelength of 365 nm for a certain time period using an aligner (model name: MA6) that emits light having a wavelength of 200 nm to 450 nm (i.e., bleaching step). The exposed film was developed with an aqueous developer of 2.38% by weight of tetramethylammonium hydroxide through puddle nozzles at 23° C. for 80 seconds. The exposed film thus obtained was heated in a convection oven at 230° C. for 30 minutes to prepare a cured film having a thickness of 3 μm (i.e., hard-bake step).
The thickness of the film upon the coating and that of the film upon the curing (or hard-bake) were measured using a non-contact-type thickness measurement equipment (SNU Precision). The film retention rate (%) was obtained as a percent of the ratio of the thickness of the film upon the curing to the thickness of the film upon the coating (i.e., (thickness upon curing/thickness upon coating)×100).
A cured film was obtained in the same manner as in Evaluation Example 1, except that exposure rate was 100 mJ/cm2 at the time of exposure to light. For the hole pattern formed per a size of the mask of 10 μm in the above procedure, the size of CD (critical dimension; unit: μm) was measured. If it is at least 10 μm, the sensitivity was good (∘). If it is less than 10 μm, the sensitivity was poor (x).
A cured film was obtained in the same manner as in Evaluation Example 1. A transversal cross-sectional view was taken with a scanning electron microscope (S-4300, manufacturer: Hitachi) for holes of 4 μm in the pattern of the cured film. The angle between the edge of the pattern and the substrate side at the interface between the edge of the pattern and the substrate was measured using a micro-optical microscope (STM6-LM, manufacturer: OLYMPUS). It was evaluated according to the following criteria.
Evaluation criteria: ◯ (70° or more), x (less than 70°)
As shown in Table 3 and
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0171927 | Dec 2018 | KR | national |
| 10-2019-0133919 | Oct 2019 | KR | national |
