KR20160104380A - Positive photosensitive resin composition, photosensitive resin film and display device using the same - Google Patents
Positive photosensitive resin composition, photosensitive resin film and display device using the same Download PDFInfo
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- KR20160104380A KR20160104380A KR1020150027327A KR20150027327A KR20160104380A KR 20160104380 A KR20160104380 A KR 20160104380A KR 1020150027327 A KR1020150027327 A KR 1020150027327A KR 20150027327 A KR20150027327 A KR 20150027327A KR 20160104380 A KR20160104380 A KR 20160104380A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
Abstract
Description
The present invention relates to a positive photosensitive resin composition, a photosensitive resin film using the positive photosensitive resin composition, and a display device.
In the case of a positive photosensitive material used as a protective film for a semiconductor device, an interlayer insulating film, or the like, a chemical change is made in a light receiving portion through a UV exposure to develop in an alkali solution. The film is then cured to make it firm. In this case, when the adhesion between the cured film and the lower substrate is poor, the reliability becomes poor. Particularly, during the manufacturing process of the insulating film, the high-temperature process of 200 占 폚 or more and the curing time of 30 minutes or more may cause a decrease in the adhesion of the display element to the lower insulating film substrate and the upper substrate due to continuous exposure at a high temperature.
Conventional techniques use a silane coupling agent to improve adhesion to the underlying film. The silane coupling agent has two or more different reactors in the molecule. One is a reactor that chemically bonds with inorganic materials (glass, metal, sand, etc.), and the other is a reactor that chemically bonds with organic materials (various synthetic resins). This typically acts as an intermediary linking the organic material with the inorganic material, which is highly difficult to bond. Among them, the silane coupling agent having an amino group at the terminal is excellent in adhesion to the lower substrate due to the alkoxysilyl group (methoxysilyl group, epoxysilyl group, etc.) bonding with the inorganic material and the amino group chemically bonding with the organic material, There is a problem that the sensitivity, which is a main characteristic of the photosensitive material, is lowered. Therefore, it is necessary to develop a novel silane coupling agent capable of increasing the adhesive strength without adversely affecting the sensitivity.
One embodiment is to provide a positive photosensitive resin composition comprising an organosilane compound excellent in adhesion and sensitivity.
Another embodiment is to provide a photosensitive resin film produced using the above positive photosensitive resin composition.
Another embodiment is to provide a display element comprising the photosensitive resin film.
One embodiment includes (A) an alkali soluble resin; (B) a photosensitive diazoquinone compound; (C) an organosilane compound represented by the following formula (1); And (D) a solvent.
[Chemical Formula 1]
In Formula 1,
R 1 to R 3 and R 5 are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C1 to C10 alkoxy group,
R 4 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,
L 1 is a substituted or unsubstituted C1 to C10 alkylene group.
Each of R 1 to R 3 may independently be a substituted or unsubstituted C1 to C10 alkoxy group.
And R < 4 > may be a substituted or unsubstituted C6 to C20 aryl group.
The R 5 may be a substituted or unsubstituted C1 to C10 alkoxy group.
The organosilane compound may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin.
The alkyllysoluble resin may be a polybenzoxazole precursor, a polyimide precursor, a novolac resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, or a combination thereof.
Wherein the positive photosensitive resin composition comprises 5 parts by weight to 100 parts by weight of the photosensitive diazoquinone compound per 100 parts by weight of the alkali-soluble resin, 1 to 30 parts by weight of the organosilane compound, To 200 parts by weight to 900 parts by weight.
The positive photosensitive resin composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.
Another embodiment provides a photosensitive resin film produced using the above positive photosensitive resin composition.
Another embodiment provides a display element comprising the photosensitive resin film.
Other aspects of the present invention are included in the following detailed description.
The positive photosensitive resin composition according to an embodiment provides a photosensitive resin film having excellent adhesion and sensitivity, including an organic silane compound having a specific structure, and a display device comprising the photosensitive resin film.
1 is a schematic diagram of a die shear tester device for evaluating the adhesive strength of the compositions according to Examples 1 to 5 and Comparative Examples 1 to 9.
Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, " alkenyl group " means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, "an aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the "alkoxysilylene group" means a C1 to C20 alkoxysilylene group.
Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, An ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1-C10 alkyl group, a C1- A C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkyl group, To C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, C3 to C20 heteroaryl groups, or combinations thereof.
Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.
&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.
"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.
Also, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.
The positive photosensitive resin composition according to one embodiment comprises (A) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) an organosilane compound represented by the following formula (1); And (D) a solvent.
[Chemical Formula 1]
In Formula 1,
R 1 to R 3 and R 5 are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C1 to C10 alkoxy group,
R 4 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,
L 1 is a substituted or unsubstituted C1 to C10 alkylene group.
Unlike the conventional amino silane coupling agents, the organosilane compound represented by the above formula (1) has a specific substituent (* -C (= O) R 5 ) other than an amino group at the terminal thereof to provide a photosensitive resin film A positive photosensitive resin composition which can be produced can be provided.
Hereinafter, each component of the positive photosensitive resin composition according to one embodiment will be described in detail.
(C) Organosilane compound
Since the organosilane compound is represented by the above formula (1), a positive photosensitive resin composition containing the organosilane compound can provide a photosensitive resin film or the like that exhibits excellent adhesion and sensitivity.
For example, each of R 1 to R 3 may independently be a substituted or unsubstituted C1 to C10 alkoxy group.
For example, R 4 may be a substituted or unsubstituted C6 to C20 aryl group. In this case, the tertiary amine having an aryl group may have a lower electron density than the primary amine or the secondary amine and can easily be desorbed at a low temperature. This is effective when it is desired to obtain adhesion at low temperature curing.
For example, R < 5 > may be a substituted or unsubstituted C1 to C10 alkoxy group. In this case, the organosilane compound has an ester group substituted with an alkyl group at the terminal, so that the sensitivity can be prevented from lowering and the adhesive strength to the lower substrate can be maintained. For example, R 5 may be a t-butoxy group.
The silane polymer compound may be included in an amount of 1 to 30 parts by weight, for example, 2 to 30 parts by weight, for example, 2 to 20 parts by weight, for example, 2 to 10 parts by weight based on 100 parts by weight of the alkali- have. When the silane polymer compound is contained in an amount of more than 30 parts by weight based on 100 parts by weight of the alkali-soluble resin, the sensitivity is lowered. When the silane polymer compound is contained in an amount less than 1 part by weight, the adhesive strength is lowered.
(A) an alkali-soluble resin
The alkali-soluble resin may be a polybenzoxazole precursor, a polyimide precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, or a combination thereof.
The polybenzoxazole precursor may include a structural unit represented by the following formula (2), and the polyimide precursor may include a structural unit represented by the following formula (3).
(2)
(In the formula (2)
X < 1 > may be a substituted or unsubstituted C6 to C30 aromatic organic group,
Y 1 is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group have.)
(3)
(3)
X 2 is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group However,
Y 2 is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted quadrivalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted quadrivalent to hexavalent C3 to C30 alicyclic organic group have.)
In Formula 2, X 1 may be a residue derived from an aromatic diamine as an aromatic organic group.
Examples of the aromatic diamine include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2- Hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2- (3-amino-4-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis , 2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2- rope (4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis Phenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- 2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- 2- (3-amino-4-amino-6-trifluoromethylphenyl) hexafluoropropane, 2- 2-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-2-trifluoromethylphenyl) Methylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane and 2- Hydroxy-6-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane may be used, It is not.
Examples of X 1 include functional groups represented by the following formulas (4) and (5), but are not limited thereto.
[Chemical Formula 4]
[Chemical Formula 5]
(In the formulas (4) and (5)
A 1 may be a single bond, O, CO, CR 47 R 48 , SO 2, or S, and R 47 and R 48 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, A C1 to C30 fluoroalkyl group,
Each of R 50 to R 52 independently represents a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxyl group or a thiol group,
n10 may be an integer of 0 to 2, and n11 and n12 may each be an integer of 0 to 3)
In Formula 2, Y 1 is an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent alicyclic group, and may be a residue of a dicarboxylic acid or a residue of a dicarboxylic acid derivative. Specifically, Y 1 may be an aromatic organic group or a divalent to hexavalent alicyclic organic group.
Specific examples of the dicarboxylic acid derivative include 4,4'-oxydibenzoyl chloride, diphenyloxydicarbonyldichloride, bis (phenylcarbonyl chloride) sulfone, bis (phenylcarbonyl chloride) ether, bis (phenylcarbonyl chloride ) Phenone, phthaloyldichloride, terephthaloyldichloride, isophthaloyldichloride, dicarbonyldichloride, diphenyloxydicarboxylate dibenzotriazole, or combinations thereof, but is not limited thereto.
Examples of Y 1 include functional groups represented by the following formulas (6) to (8), but are not limited thereto.
[Chemical Formula 6]
(7)
[Chemical Formula 8]
(In the above Chemical Formulas 6 to 8,
Each of R 53 to R 56 may independently be a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group,
n13 and n14 may each be an integer of 0 to 4, n15 and n16 may each be an integer of 0 to 3,
A 2 may be a single bond, O, CR 47 R 48 , CO, CONH, S or SO 2 , and each of R 47 and R 48 may independently be a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group , Specifically a C1 to C30 fluoroalkyl group)
In Formula 3, X 2 is an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent alicyclic organic group. Specifically, X 2 may be an aromatic organic group or a divalent to hexavalent alicyclic organic group.
Specifically, X 2 may be a residue derived from an aromatic diamine, an alicyclic diamine or a silicone diamine. At this time, the aromatic diamine, alicyclic diamine and silicon diamine may be used singly or in combination of one or more thereof.
Examples of the aromatic diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine , Bis [4- (4-aminophenoxy) phenyl] sulfone, bis (4-aminophenoxy) ] Ether, 1,4-bis (4-aminophenoxy) benzene, compounds in which these aromatic rings are substituted with alkyl groups or halogen atoms, or combinations thereof, but are not limited thereto.
Examples of the alicyclic diamine include, but are not limited to, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine or a combination thereof.
Examples of the silicon diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p- aminophenyl) tetramethyldisiloxane, Bis (? -Aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (? -Aminopropyl) tetraphenyldisiloxane, 1,3- Methyldisiloxane, or combinations thereof, but are not limited thereto.
In the above formula (3), Y 2 is an aromatic organic group, a 4- to 6-valent aliphatic organic group, or a 4 to 6-membered alicyclic organic group. Specifically, Y 2 may be an aromatic organic group or a divalent to tetravalent alicyclic organic group.
The Y 2 may be an aromatic acid dianhydride, or a residue derived from an alicyclic acid dianhydride. At this time, the aromatic acid dianhydride and the alicyclic acid dianhydride may be used alone or in admixture of at least one thereof.
Examples of the aromatic acid dianhydride include pyromellitic dianhydride; Benzophenone tetracarboxylic dianhydride such as benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3'4,4'-tetracarboxylic dianhydride, ; Oxydiphthalic dianhydride such as 4,4'-oxydiphthalic dianhydride; Biphthalic dianhydride such as 3,3 ', 4,4'-biphthalic dianhydride (3,3', 4,4'-biphthalic dianhydride); (Hexafluoroisopropylidene) diphthalic dianhydride such as 4,4 '- (hexafluoroisopropylidene) diphthalic dianhydride (4,4' - (hexafluoroisopropylidene) diphthalic dianhydride) ; Naphthalene-1,4,5,8-tetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic dianhydride, and the like, but the present invention is not limited thereto.
Examples of the alicyclic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexane-1,2-dicarboxylic acid dianhydride (5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexane-1,2-dicarboxylic anhydride), 4- (2,5- dioxotetrahydrofuran-3-yl) -tetralin- (2,5-dioxotetrahydrofuran-3-yl) -tetralin-1,2-dicarboxylic anhydride, bicyclooctene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5,6-tetracarboxylic dianhydride, bicyclooctene-1,2,4,5-tetracarboxylic dianhydride, and the like. But is not limited thereto.
The alkali-soluble resin may have a weight average molecular weight (Mw) of 3,000 g / mol to 300,000 g / mol, and more specifically, a weight average molecular weight (Mw) of 5,000 g / mol to 30,000 g / mol. When the weight average molecular weight (Mw) is within the above range, a sufficient residual film ratio can be obtained in an unexposed area at the time of development with an aqueous alkali solution, and patterning can be efficiently performed.
(B) Photosensitive Diazoquinone compound
As the photosensitive diazoquinone compound, a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure can be preferably used.
Representative examples of the photosensitive diazoquinone compound include compounds represented by the following general formulas (9) and (11) to (13), but are not limited thereto.
[Chemical Formula 9]
In the above formula (9)
R 31 to R 33 each independently may be a hydrogen atom or a substituted or unsubstituted alkyl group, and may be specifically CH 3 ,
D 1 to D 3 each independently may be OQ, and Q may be a hydrogen atom, a functional group represented by the following formula (10a) or a functional group represented by the following formula (10b), wherein Q may not be a hydrogen atom at the same time,
n31 to n33 each independently may be an integer of 1 to 5;
[Chemical Formula 10a]
[Chemical Formula 10b]
(11)
In Formula 11,
R 34 may be a hydrogen atom or a substituted or unsubstituted alkyl group,
D 4 to D 6 each independently may be OQ, Q is the same as defined in Formula 9,
n34 to n36 each independently may be an integer of 1 to 5;
[Chemical Formula 12]
In Formula 12,
A 3 may be CO or CR 500 R 501 , each of R 500 and R 501 may independently be a substituted or unsubstituted alkyl group,
D 7 to D 10 are the same as those each independently may be a hydrogen atom, a substituted or unsubstituted alkyl, OQ, or NHQ, wherein Q is as defined in the formula (9),
n37, n38, n39 and n40 each independently may be an integer of 1 to 4,
n37 + n38 and n39 + n40 may each independently be an integer of 5 or less,
Provided that at least one of the D 7 to D 10 is OQ, and one aromatic ring there may be included the OQ 1 to 3, there is OQ can contain one to four and one of the aromatic ring.
[Chemical Formula 13]
In Formula 13,
R 35 to R 42 each independently may be a hydrogen atom or a substituted or unsubstituted alkyl group,
n41 and n42 each independently may be an integer of 1 to 5, and specifically may be an integer of 2 to 4,
Q is the same as defined in the above formula (9).
The photosensitive diazoquinone compound is preferably included in an amount of 5 parts by weight to 100 parts by weight, for example, 10 parts by weight to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the content of the photosensitive diazoquinone compound is within the above range, the pattern is formed well without residue by exposure, and there is no loss of film thickness during development, and a good pattern can be obtained.
(D) Solvent
The positive photosensitive resin composition may include a solvent capable of easily dissolving each component such as an alkali-soluble resin, a photosensitive diazoquinone compound, and an organosilane compound.
Examples of the solvent include organic solvents such as N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol di Propyleneglycol monomethyl ether, propyleneglycol monomethyl ether acetate, methyl lactate (methyl lactate), ethyl lactate (ethyl lactate), butyl lactate (butyl lactate), ethyl lactate (Methyl lactate), methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate (methyl pyruvate), ethyl pyruvate Ethoxypropionate, or a combination thereof may be used, but the present invention is not limited thereto.
The solvent may be appropriately selected and used depending on the step of forming a photosensitive resin film such as spin coating, slit die coating and the like.
The solvent may be used in an amount of 200 parts by weight to 900 parts by weight, for example, 200 parts by weight to 700 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the content of the solvent is within the above range, a film having a sufficient thickness can be coated, and the solubility and coatability can be excellent.
(E) Other additives
The positive photosensitive resin composition according to one embodiment may further include other additives.
The positive-working photosensitive resin composition may contain malonic acid or 3-amino-1,2-propanediol, a leveling agent, a coloring agent, or the like in order to prevent spots or spots during coating, A fluorine-based surfactant, a radical polymerization initiator, or a combination thereof. The amount of these additives to be used can be easily controlled depending on the desired physical properties.
The positive-working photosensitive resin composition may further contain an epoxy compound as an additive for the purpose of improving adhesion and the like. Examples of the epoxy compound include epoxy novolac acrylate carboxylate resin, orthocresol novolak epoxy resin, phenol novolak epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, or a combination thereof .
When the epoxy compound is further included, it may further include a radical polymerization initiator such as a peroxide initiator or an azobis-based initiator.
The epoxy compound may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the positive photosensitive resin composition. When the epoxy compound is contained within the above range, the adhesion and other properties can be improved in terms of storage stability and economy.
The positive photosensitive resin composition may further comprise a thermal latent acid generator. Examples of the thermal latent acid generator include arylsulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid and the like; Perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid, trifluorobutanesulfonic acid and the like; Methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid and the like; Or combinations thereof, but are not limited thereto.
The thermal latent acid generator is a catalyst for the dehydration reaction of the phenolic hydroxyl group-containing polyamide of the polybenzoxazole precursor and the cyclization reaction, and the cyclization reaction can proceed smoothly even if the curing temperature is lowered.
The step of forming a pattern using the positive photosensitive resin composition includes a step of applying a positive photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing or the like; Drying the applied positive photosensitive resin composition to form a positive photosensitive resin composition film; Exposing the positive photosensitive resin composition film; Developing the exposed positive photosensitive resin composition film with an alkali aqueous solution to produce an insulating film; And a step of heat-treating the insulating film. The conditions of the process for forming the pattern, and the like are well known in the art, so that detailed description thereof will be omitted herein.
According to another embodiment, there is provided a photosensitive resin film produced using the above positive photosensitive resin composition.
According to another embodiment, there is provided a display element comprising the photosensitive resin film. The display device may be a liquid crystal display, a light emitting diode, a plasma display, or an organic light emitting diode.
The positive photosensitive resin composition may be useful for forming an insulating film, a passivation layer or a buffer coating layer in a display device. That is, since the positive photosensitive resin composition has a high refractive index, it can be usefully used for forming a surface protective film and an interlayer insulating film of a display device.
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are only the preferred embodiments of the present invention, and the present invention is not limited to the following Examples.
( Example )
( Organosilane Compound Preparation)
Manufacturing example One
0.06 mol of the compound represented by the formula (A) and 26 g of GBL (? -Butyrolactone) are placed in a 100 mL flask and stirred at 60 占 폚. A solution obtained by dissolving 0.05 mol of the compound represented by the formula (B) in 38 g of GBL (? -Butyrolactone) is added dropwise over 30 minutes. After the dropwise addition, the mixture was stirred at room temperature for 24 hours, evaporated to remove impurities, and an organosilane compound was prepared.
(A)
[Chemical Formula B]
(Preparation of alkali-soluble resin)
(3-amino-4-hydroxy-phenyl) -1,1,1,3,3,3-tetra-naphthalen-2-ol was obtained by passing nitrogen through a four-necked flask equipped with a stirrer, a temperature controller, 12.4 g of 3-hexafluoropropane and 125 g of N-methyl-2-pyrrolidone (NMP) were added and dissolved.
When the solid is completely dissolved, 4.2 g of pyridine is added as a catalyst, and 9.4 g of 4,4'-oxydibenzoyl chloride is dissolved in 100 g of NMP while maintaining the temperature at 0 to 5 ° C. Gt; After completion of the dropwise addition, the reaction was carried out at 0 ° C to 5 ° C for 1 hour, the temperature was raised to room temperature and the reaction was allowed to proceed for 1 hour.
After 1.1 g of 5-norbornene-2,3-dicarboxyanhydride was added thereto, the mixture was stirred at 70 ° C for 24 hours, and the reaction was terminated. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate. The precipitate was filtered and sufficiently washed with water, and then dried at 80 DEG C under vacuum for 24 hours to obtain a polybenzoxazole precursor .
(Production of positive-type photosensitive resin composition)
Example One
10 g of the polybenzoxazole precursor was added to and dissolved in 35 g of? -Butyrolactone (GBL). Then, 3.0 g of the photosensitive diazoquinone compound having the structure represented by the following formula (C) as an acid generator, 0.2 g of the silane compound was added and dissolved, followed by filtration with a 0.45 占 퐉 fluorine resin filter to obtain a positive photosensitive resin composition.
≪ RTI ID = 0.0 &
(In the above formula (C), among Q 1 , Q 2 and Q 3 ,
Example 2
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that 0.5 g of the organosilane compound was used instead of 0.2 g.
Example 3
A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 1.0 g of the organosilane compound was used instead of 0.2 g of the above-mentioned Example 1.
Example 4
A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 2.0 g of the organosilane compound was used instead of 0.2 g of the above-mentioned Example 1.
Example 5
A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 3.0 g of the organosilane compound was used instead of 0.2 g of the above-mentioned Example 1.
Comparative Example One
In Example 1, a positive photosensitive resin composition was prepared in the same manner as in Example 1, except that the organosilane compound was not used.
Comparative Example 2
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that 0.5 g of the compound represented by the following formula (B) was used instead of 0.2 g of the organosilane compound.
[Chemical Formula B]
Comparative Example 3
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that 1.0 g of the compound represented by the formula (B) was used instead of 0.5 g of the compound represented by the formula (B).
Comparative Example 4
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that 2.0 g of the compound represented by the formula (B) was used instead of 0.5 g of the compound represented by the formula (B).
Comparative Example 5
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that 3.0 g of the compound represented by the formula (B) was used instead of 0.5 g of the compound represented by the formula (B).
Comparative Example 6
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that 0.5 g of the compound represented by the following formula (D) was used instead of 0.2 g of the organosilane compound.
[Chemical Formula D]
Comparative Example 7
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that 1.0 g of the compound represented by the formula (D) was used instead of 0.5 g of the compound represented by the formula (D).
Comparative Example 8
A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 2.0 g of the compound represented by the formula (D) was used instead of 0.5 g of the compound represented by the formula (D).
Comparative Example 9
A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 3.0 g of the compound represented by the formula (D) was used instead of 0.5 g of the compound represented by the formula (D).
(evaluation)
The positive photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 9 were coated on an 8-inch wafer using K-SPINNER, a spin coater of SEMES Co., And heated for 3 minutes to form a photosensitive resin film. The photosensitive resin film was cured at 320 DEG C for 30 minutes in a nitrogen atmosphere.
The adhesive force was measured by a die shear tester (DAGE series 4000PXY, manufactured by DAGE) by EMC molding on the cured film, and the results are shown in Table 1 below.
In addition, sensitivity was evaluated by measuring CD with Hitachi S-9260, and the results are shown in Table 1 below.
As shown in Table 1, the positive photosensitive resin compositions of Examples 1 to 5 contained the organosilane compounds represented by the formula (1), and those of Comparative Examples 1 to 9 containing no organosilane compound It can be confirmed that a photosensitive resin film having excellent adhesion and sensitivity can be provided as compared with the positive photosensitive resin composition.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (7)
(B) a photosensitive diazoquinone compound;
(C) an organosilane compound represented by the following formula (1); And
(D) Solvent
A positive photosensitive resin composition comprising:
[Chemical Formula 1]
In Formula 1,
R 1 to R 3 and R 5 are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C1 to C10 alkoxy group,
R 4 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group,
L 1 is a substituted or unsubstituted C1 to C10 alkylene group.
Wherein the organosilane compound is contained in an amount of 1 part by weight to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin.
Wherein the alkyllysoluble resin is a polybenzoxazole precursor, a polyimide precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, or a combination thereof.
The positive photosensitive resin composition
With respect to 100 parts by weight of the alkali-soluble resin
And 5 parts by weight to 100 parts by weight of the photosensitive diazoquinone compound,
1 to 30 parts by weight of the organosilane compound,
Wherein the solvent is contained in an amount of 200 to 900 parts by weight.
Wherein the positive photosensitive resin composition further comprises additives such as malonic acid, 3-amino-1,2-propanediol, a leveling agent, a fluorinated surfactant, a radical polymerization initiator, or a combination thereof.
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| KR1020150027327A KR20160104380A (en) | 2015-02-26 | 2015-02-26 | Positive photosensitive resin composition, photosensitive resin film and display device using the same |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020150027327A KR20160104380A (en) | 2015-02-26 | 2015-02-26 | Positive photosensitive resin composition, photosensitive resin film and display device using the same |
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| KR20160104380A true KR20160104380A (en) | 2016-09-05 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190106410A (en) * | 2018-03-09 | 2019-09-18 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and electronic device |
| KR20200036573A (en) * | 2018-09-28 | 2020-04-07 | 삼성에스디아이 주식회사 | Positive photosensitive resin composition, photosensitive resin layer and electronic device using the same |
-
2015
- 2015-02-26 KR KR1020150027327A patent/KR20160104380A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190106410A (en) * | 2018-03-09 | 2019-09-18 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and electronic device |
| KR20200036573A (en) * | 2018-09-28 | 2020-04-07 | 삼성에스디아이 주식회사 | Positive photosensitive resin composition, photosensitive resin layer and electronic device using the same |
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