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CN105629663B - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
CN105629663B
CN105629663B CN201510812533.4A CN201510812533A CN105629663B CN 105629663 B CN105629663 B CN 105629663B CN 201510812533 A CN201510812533 A CN 201510812533A CN 105629663 B CN105629663 B CN 105629663B
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resin composition
group
compound
photosensitive resin
weight
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CN105629663A (en
Inventor
许槿
罗钟昊
权真
李垠泳
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Dupont Special Materials Korea Co ltd
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Rohm and Haas Electronic Materials Korea Ltd
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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
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • 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
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a positive photosensitive resin composition and a cured film prepared therefrom. The photosensitive resin composition comprises (A) a siloxane polymer containing at least one structural unit derived from a silane compound represented by formula (I), (B) an epoxy compound and (C) a 1, 2-diazidoquinone compound, which can maintain the advantages of conventional compositions containing siloxane polymers, such as high transparency, while having improved chemical resistance; therefore, it can provide a cured film or a planarization film with improved stability during post-processing.

Description

Photosensitive resin composition
Technical Field
The present invention relates to a positive photosensitive resin composition and a cured film prepared therefrom. In particular, it relates to a positive photosensitive resin composition which can form a cured film having high transparency and excellent chemical resistance and can be used in a Liquid Crystal Display (LCD) or an Organic Light Emitting Diode (OLED).
Background
It has been reported that the method of increasing the aperture ratio of the display device can produce an LCD or OLED having higher accuracy/resolution characteristics. According to this method, a transparent planarization film is disposed as a protective film on a Thin Film Transistor (TFT) substrate, which allows a data line and a pixel electrode to overlap, thereby improving an aperture ratio compared to a conventional method. To prepare such transparent planarization films, several processing steps are employed to impart a specific pattern. A positive photosensitive resin composition is widely used in this method because it requires fewer process steps. Specifically, a positive photosensitive resin composition containing a siloxane polymer is known for its high heat resistance, high transparency, and low dielectric constant.
Korean laid-open patent publication No. 2006-59202 discloses a composition comprising a siloxane polymer containing phenolic hydroxyl groups in an amount of 20 mol% or less, a diazidoquinone compound containing no methyl group at the ortho-or para-position with respect to the phenolic hydroxyl groups therein, and an alcoholic hydroxyl group-containing compound and/or a carbonyl group-containing cyclic compound as a solvent. Also disclosed is a cured film prepared from the composition, which satisfies specific chromaticity coordinates and has a light transmittance of at least 95%.
Korean laid-open patent publication No. 2010-43259 discloses a siloxane photosensitive resin composition comprising a siloxane polymer, an acrylic resin, a diazidoquinone compound, and a solvent. The composition has excellent adhesion properties to a substrate by employing a silicone polymer and an acrylic resin in combination.
However, a planarization film prepared from a conventional positive type photosensitive composition including such a siloxane polymer or a display device employing the same may have problems such as swelling or film-to-substrate delamination when the cured film is immersed in or contacted with a solvent, an acid, a base, or the like.
Disclosure of Invention
Accordingly, it is an object of the present invention to obtain a photosensitive resin composition which can form a cured film having high transparency and excellent chemical resistance and can be used in an LCD or an OLED.
According to an aspect of the present invention, there is provided a photosensitive resin composition comprising:
(A) a siloxane polymer containing at least one structural unit derived from a silane compound represented by formula (I),
(B) an epoxy compound, and
(C)1, 2-diazidoquinone compound:
(R1)nSi(R2)4-n (I)
wherein R is1Is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or an alkylaryl group having 7 to 12 carbon atoms, and at a plurality of R1In the case of (b), they may be the same as or different from each other; r2Is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, an amino group, an acyloxy group having 2 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atomsOxy, and at a plurality of R2In the case of (b), they may be the same as or different from each other; and n is an integer from 0 to 3.
The photosensitive resin composition of the present invention can maintain the advantages of conventional compositions containing siloxane polymers, such as high transparency, while having improved chemical resistance; therefore, it can provide a cured film or a planarization film with improved stability during post-processing.
Detailed Description
According to an embodiment of the present invention, a photosensitive resin composition includes (a) a siloxane polymer, (B) an epoxy compound, and (C) a 1, 2-diazidoquinone compound, and optionally (D) a solvent, (E) a surfactant, and/or (F) an additive.
Hereinafter, each component of the photosensitive resin composition will be described in detail.
In the present specification, "(meth) acryloyl" means "acryloyl" and/or "methacryloyl", and "(meth) acrylate" means "acrylate" and/or "methacrylate".
(A) Siloxane polymers
The siloxane polymer (or polysiloxane) of the present invention comprises a condensate of a silane compound and/or a hydrolysis product thereof. The silane compound or its hydrolyzate may be a silane compound having 1 to 4 functional groups.
Thus, the siloxane polymer may comprise siloxane structural units selected from the group consisting of the following Q, T, D and M types:
-Q-type siloxane structural units refer to siloxane structural units containing a silicon atom and four adjacent oxygen atoms; for example, it may be derived from a tetrafunctional silane compound or a hydrolysate of a silane compound having four hydrolyzable groups.
-T-type siloxane structural unit refers to a siloxane structural unit containing a silicon atom and three adjacent oxygen atoms; for example, it may be derived from a trifunctional silane compound or a hydrolysate of a silane compound having three hydrolyzable groups.
-D-type siloxane structural units refer to siloxane structural units containing a silicon atom and two adjacent oxygen atoms (i.e. linear siloxane structural units); for example, it may be derived from a bifunctional silane compound or a hydrolysate of a silane compound having two hydrolyzable groups.
-siloxane structural units of the M-type mean siloxane structural units containing a silicon atom and one adjacent oxygen atom; for example, it may be derived from a monofunctional silane compound or a hydrolysate of a silane compound having one hydrolyzable group.
The siloxane polymer contains at least one structural unit derived from a silane compound represented by formula (I). For example, the siloxane polymer may be a condensate of a silane compound represented by formula (I) and/or a hydrolysis product thereof:
(R1)nSi(R2)4-n (I)
wherein R is1Is a non-hydrolyzable organic radical having from 1 to 12 carbon atoms, R2Is a hydrolyzable group, and n is an integer of 0 to 3.
From R1Examples of the non-hydrolyzable organic group represented may include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, and an alkylaryl group having 7 to 12 carbon atoms. It may be linear, branched or cyclic. In addition, a plurality of R exist in the same molecule1May be the same or different from each other and may be substituted and/or unsubstituted. R1Structural units having hetero atoms such as ethers, esters, and thioethers may be contained. R1The desired non-hydrolyzable character means that the compound is in the hydrolyzable R2It must remain stable under the conditions under which hydrolysis occurs.
From R2The hydrolyzable group represented generally refers to any group of the compound that is capable of forming a silanol group upon hydrolysis or a condensate when the compound is heated in the presence of excess water in the absence of a catalyst at a temperature of 25 ℃ to 100 ℃. Examples of the hydrolyzable group may include a hydrogen atom, a halogen atom, having 1Alkoxy group having up to 12 carbon atoms, amino group, acyloxy group having 2 to 12 carbon atoms and aryloxy group having 6 to 12 carbon atoms. Multiple R's in the same molecule2In this case, they may be the same as or different from each other.
The silane compound represented by formula (I) may be, for example, a silane compound substituted with four hydrolyzable groups (i.e., n ═ 0), a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups (i.e., n ═ 1), a silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups (i.e., n ═ 2), or a silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group (i.e., n ═ 3).
Representative examples of the silane compound may include silane compounds substituted with four hydrolyzable groups, such as tetrachlorosilane, tetraaminosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraphenoxymosilane and tetrapropoxysilane; silane compounds substituted by one non-hydrolyzable and three hydrolyzable groups, e.g. methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, pentafluorophenyl trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, d-hydrolyzable groups3-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-hydroxyphenyl trimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilaneAlkyl, 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) methoxysilane]Propyltrimethoxysilane, [ (3-ethyl-3-oxetanyl) methoxy]Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-trimethoxysilylpropylsuccinic acid; silane compounds substituted with two non-hydrolyzable and two hydrolyzable groups, for example dimethyldichlorosilane, dimethyldiaminosilane, dimethyldiacetoxysilane, dimethyldimethoxysilandiphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane, cyclohexyldimethoxymethylsilane, diethoxymethylvinylsilane, di-methoxyvinylsilane, di-methoxysilane, di, Dimethoxymethylvinylsilane and dimethoxydi-p-tolylsilane; and silane compounds substituted with three non-hydrolyzable groups and one hydrolyzable group, such as trimethylchlorosilane, hexamethyldisilazane, trimethylsilane, tributylsilane, trimethylmethoxysilane, tributylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, and (3-glycidoxypropyl) dimethylethoxysilane.
Preferred among the silane compounds substituted with four hydrolyzable groups are tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane; preferred among the silane compounds substituted with one non-hydrolyzable group and three hydrolyzable groups are methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane and butyltrimethoxysilane; preferred among the silane compounds substituted with two non-hydrolyzable and two hydrolyzable groups are dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane and dimethylethoxysilane.
These silane compounds may be used alone or in combination of two or more thereof.
The conditions for preparing the hydrolyzate of the silane compound represented by the formula (I) or the condensate thereof are not particularly limited. For example, the hydrolysis product of the silane compound represented by the formula (I) or the condensate thereof may be prepared by the following manner, if necessary: diluting the silane compound of formula (I) in a solvent such as ethanol, 2-propanol, acetone, butyl acetate, etc.; to this, water necessary for the reaction is added, and as a catalyst, an acid (e.g., hydrochloric acid, acetic acid, nitric acid, etc.) or a base (e.g., ammonia, triethylamine, cyclohexylamine, tetramethylammonium hydroxide, etc.); and then the mixture thus obtained is stirred to complete the hydrolytic polymerization reaction.
Preferably, the weight average molecular weight (Mw) of a condensate (i.e., a siloxane polymer) obtained by hydrolytic polymerization of the silane compound of formula (I) is in the range of 5,000 to 50,000. Within this range, the photosensitive resin composition may have desirable film formation characteristics, solubility, and dissolution rate in a developer.
The kind of the solvent and the acid or base catalyst used for the preparation and the amount thereof are not particularly limited. The hydrolytic polymerization may be carried out at a low temperature of 20 ℃ or less, but the reaction may also be promoted by heating or refluxing. The time required for the reaction may vary depending on the kind and concentration of the silane monomer, the reaction temperature, and the like. Conventionally, the reaction time required to obtain a condensate having a weight average molecular weight of 5,000 to 50,000 is in the range of 15 minutes to 30 days; however, the reaction time in the present invention is not limited thereto.
The siloxane polymer (a) may comprise a structural unit derived from a silane compound represented by formula (I) wherein n is 0 (i.e., a Q-type structural unit). Preferably, the siloxane polymer (a) contains a structural unit derived from a silane compound represented by formula (I) in an amount of 10 to 60 mol% based on the total moles of Si atoms, wherein n is 0. As used herein, the term "mole%" based on the total moles of Si atoms "refers to the percentage of the moles of Si atoms contained in a particular structural unit based on the total moles of Si atoms contained in all structural units constituting the siloxane polymer (a). When the amount is within the preferred range, the photosensitive resin composition can maintain its solubility in an alkaline aqueous solution during pattern formation in an appropriate range, thereby preventing any defects caused by a decrease in solubility or a sharp increase in solubility of the composition.
Further, the siloxane polymer (a) may comprise a structural unit derived from a silane compound represented by formula (I) wherein n is 1 (i.e., T-type structural unit). Preferably, the siloxane polymer (a) contains a structural unit derived from the silane compound represented by formula (I) in an amount of 30 to 90 mol%, more preferably in an amount of 50 to 80 mol%, based on the total moles of Si atoms, wherein n is 1. Within this preferable range, the photosensitive resin composition can form a cured film having a more precise pattern.
Specifically, from the viewpoint of hardness, sensitivity and retention rate of the cured film, the siloxane polymer may preferably comprise a structural unit derived from a silane compound represented by the formula (I) wherein n is 1 and R is1Is an aryl group, preferably a phenyl group (i.e.T-phenyl type building block). Preferably, the siloxane polymer (a) comprises T-phenyl type structural units derived from said compound in an amount of from 30 to 70 mol%, more preferably in an amount of from 35 to 60 mol%, based on the total number of moles of Si atoms. Within this preferred range, the siloxane polymer and the 1, 2-diazidonaphthoquinone compound may have desirable compatibility, thereby improving the transparency of the cured film and preventing sensitivity from being lowered.
The siloxane polymer (a) may comprise a structural unit derived from a silane compound represented by formula (I) wherein n is 2 (i.e., D-type structural unit). Preferably, the siloxane polymer (a) contains a structural unit derived from the silane compound represented by formula (I) in an amount of 0.1 to 60 mol%, more preferably in an amount of 1 to 50 mol%, based on the total moles of Si atoms, wherein n is 2.
Within this range, the cured film will maintain appropriate hardness and have some flexibility, thereby resisting cracking due to external stress.
The photosensitive resin composition of the present invention may include the siloxane polymer (a) in an amount of 50 to 95% by weight, preferably 65 to 90% by weight, based on the total weight of the solid content of the solvent-free composition. Within this preferred amount range, the resin composition can maintain its developability at a suitable level, thereby producing a cured film having improved film retention and pattern resolution.
(B) Epoxy compound
In the photosensitive resin composition of the present invention, an epoxy compound and a siloxane polymer are used to increase the internal density of a siloxane binder, thereby improving the chemical resistance of a cured film prepared therefrom.
The epoxy compound may be, for example, a compound containing a structural unit represented by the formula (II):
Figure BDA0000852962890000061
wherein
R3Is H or C1-C2Alkyl, preferably H;
R4is H, or a straight or branched chain C1-C5Alkyl, preferably straight or branched C1-C5An alkyl group; and
m is an integer from 1 to 10, preferably an integer from 1 to 5.
The epoxy compound may be, for example, a high oligomer having the structural unit of formula (II) described above.
The compounds having the structural unit of formula (II) can be synthesized by any conventional method well known in the art.
Examples of commercially available compounds having a structural unit of formula (II) may include GHP03 (glycidyl methacrylate homopolymer, miton Commercial co., Ltd.)) having a repeating unit of formula (III):
Figure BDA0000852962890000071
the epoxy compound (B) may further comprise a structural unit derived from a monomer, which is different from the structural unit of formula (II).
Representative examples of structural units derived from monomers other than structural units of formula (II) may include any structural units derived from: styrene; styrene having an alkyl substituent such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, etc.; styrene having halogen such as fluorostyrene, chlorostyrene, bromostyrene, iodostyrene, etc.; styrene having an alkoxy substituent such as methoxystyrene, ethoxystyrene, propoxystyrene and the like; p-hydroxy-alpha-methylstyrene, acetyl styrene; ethylenically unsaturated compounds having an aromatic ring such as divinylbenzene, vinylphenol, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether; unsaturated carboxylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, methyl a-hydroxymethylmethacrylate, ethyl a-hydroxymethylacrylate, propyl a-hydroxymethylacrylate, butyl a-hydroxymethylacrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene 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, and mixtures thereof, Dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclopentyloxyethyl (meth) acrylate, and the like; tertiary amines having an N-vinyl group such as N-vinylpyrrolidone, N-vinylcarbazole, N-vinylmorpholine and the like; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and the like; unsaturated ethers having an epoxy group such as allyl glycidyl ether, 2-methallyl glycidyl ether and the like; unsaturated imides such as N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. The structural units derived from the above-mentioned exemplary compounds may be contained in the epoxy compound (B) in the form of a single compound or in combination of two or more thereof.
Styrene-based compounds are preferred in these examples for the polymerizability of the composition. In particular, for chemical resistance, epoxy compounds (B) containing no carboxyl group are preferred, which can be obtained by not using a structural unit derived from a carboxyl group-containing monomer in these compounds.
The structural unit derived from a monomer other than the structural unit of the formula (II) may be used in an amount of 0 to 70 mol%, preferably 10 to 60 mol%, based on the total number of moles of the structural units constituting the epoxy compound (B). Within this preferred amount range, the cured film can have a desired hardness.
The Mw of the epoxy compound (B) may be in the range of 100 to 30,000, preferably 1,000 to 15,000. If the Mw of the epoxy compound is at least 100, the cured film may have increased hardness. In addition, if the Mw of the epoxy compound is 30,000 or less, the cured film may have a uniform thickness, which is suitable for leveling any step difference. The weight average molecular weight is determined by gel permeation chromatography (GPC, eluent: tetrahydrofuran) using polystyrene standards.
In the photosensitive resin composition of the present invention, the weight ratio of the siloxane polymer (A) to the epoxy compound (B), i.e., A: B, may be 99.5: 0.5 to 50: 50, preferably 98: 2 to 60: 40, more preferably 97:3 to 70:30, based on the total weight of the solid content. Within the above range, the photosensitive resin composition may have improved sensitivity.
(C)1, 2-diazidoquinone compounds
The photosensitive resin composition of the present invention contains a 1, 2-diazidoquinone compound (C).
The 1, 2-diazidoquinone compound can be any compound used as a photosensitizer in the field of photoresists. Representative examples include esters of phenol compounds with 1, 2-diazido-benzoquinone-4-sulfonic acid or 1, 2-diazido-benzoquinone-5-sulfonic acid; esters of phenol compounds with 1, 2-diazido naphthoquinone-4-sulfonic acid or 1, 2-diazido naphthoquinone-5-sulfonic acid; sulfonamide of a phenol compound whose hydroxyl group is substituted with an amino group and 1, 2-diazido-benzoquinone-4-sulfonic acid or 1, 2-diazido-benzoquinone-5-sulfonic acid; and sulfonamides of phenol compounds in which the hydroxyl group thereof is replaced with an amino group and 1, 2-diazido naphthoquinone-4-sulfonic acid or 1, 2-diazido naphthoquinone-5-sulfonic acid. The above-mentioned compounds may be used in the form of a single compound or in the form of a combination of two or more compounds.
Examples of the phenol compound include 2, 3, 4-trihydroxybenzophenone, 2, 4, 6-trihydroxybenzophenone, 2 ', 4, 4 ' -tetrahydroxybenzophenone, 2, 3, 3 ', 4-tetrahydroxybenzophenone, 2, 3, 4, 4 ' -tetrahydroxybenzophenone, bis (2, 4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1, 1, 1-tris (p-hydroxyphenyl) ethane, bis (2, 3, 4-trihydroxyphenyl) methane, 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 ] ethylene ] bisphenol, bis (2, 5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3, 3, 3 ', 3' -tetramethyl-1, 1 '-spirobisindane-5, 6,7, 5', 6 ', 7' -hexanol and 2, 2, 4-trimethyl-7, 2 ', 4' -trihydroxyflavan. The above-mentioned compounds may be used in the form of a single compound or in the form of a combination of two or more compounds.
More specific examples of the 1, 2-diazidoquinone compound include an ester of 2, 3, 4-trihydroxybenzophenone with 1, 2-diazidonaphthoquinone-4-sulfonic acid, an ester of 2, 3, 4-trihydroxybenzophenone with 1, 2-diazidonaphthoquinone-5-sulfonic acid, an ester of 4, 4 '- [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol with 1, 2-diazidonaphthoquinone-4-sulfonic acid, and an ester of 4, 4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol with 1, 2-diazidonaphthoquinone-5-sulfonic acid. The above-mentioned compounds may be used in the form of a single compound or in the form of a combination of two or more compounds.
The 1, 2-diazidoquinone compound can improve the transparency of the positive photosensitive resin composition.
The 1, 2-diazidoquinone compound (C) may be used in an amount in the range of 2 to 50 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the solid content of the siloxane polymer (a). When the 1, 2-diazidoquinone compound is used in the above amount range, the resin composition can easily form a pattern having no defects such as a rough surface of a cured film and scum at the bottom of the pattern after development.
(D) Solvent(s)
The photosensitive resin composition of the present invention can be prepared in the form of a liquid composition by mixing the above components in a solvent. The amount of the solvent in the photosensitive resin composition according to the present invention is not particularly limited; however, for example, the resin composition may contain the solvent in an amount such that the solid content thereof is in the range of 10 to 70% by weight, preferably 15 to 60% by weight, more preferably 20 to 40% by weight, based on the total weight of the resin composition. By solids content is meant all components included in the resin composition of the present invention excluding any solvent.
The solvent is not particularly limited as long as it can dissolve each component of the composition and is chemically stable. Examples of the solvent may include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones, and esters. Specific examples of the solvent include methanol, ethanol, tetrahydrofuran, dioxane, methyl 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, methyl cellosolve acetate, ethylene glycol monomethyl ether acetate, propylene glycol butyl ether acetate, propylene glycol, Gamma-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, methyl 2-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and the like. Preferred among these exemplary solvents are ethylene glycol alkyl ether acetates, diethylene glycol, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, and ketones. Specifically, 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, and 4-hydroxy-4-methyl-2-pentanone are preferable.
The above-mentioned compounds may be used alone or in combination with two or more thereof.
(E) Surface active agent
The photosensitive resin composition of the present invention may further contain a surfactant as necessary in order to improve coatability thereof.
The surfactant is not limited to a specific kind. Preferred are fluorine-based surfactants, silicon-based surfactants, nonionic surfactants, and the like.
Specific examples of the surfactant include fluorine-based or Silicon-based surfactants such as FZ-2122 (manufactured by Dow Corning Toray Silicon Co., Ltd.), BM-1000, BM-1100 (manufactured by BM CHEMIE Co., Ltd.), Megapack F-142D, Megapack F-172, Megapack F-173, and Megapack F-183 (manufactured by Dai Nippon Ink Chemical Kogyo Co., Ltd.), Florad FC-135, Florad FC-170C, Florad FC-430, Florad FC-431 (manufactured by Sumito 3M Co., Ltd., (Sumito 3M Ltd.), Florad S-112, Su S-113, Su S-131, Su-145S-145, and F-1000, Sufron S-382, Sufron SC-101, Sufron SC-102, Sufron SC-103, Sufron SC-104, Sufron SC-105, and Sufron SC-106 (manufactured by Asahi Glass Co., Ltd.), Eftop EF301, Eftop 303, and Eftop 352 (manufactured by Shinakida Kasei Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicon Co., Ltd.); nonionic surfactants such as polyoxyethylene alkyl ethers including polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and the like, polyoxyethylene aryl ethers including polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl 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.), copolymers Polyflow No. 57 and No. 95 based on (meth) acrylic esters (Kyoeisha Yuji Chemical co., Ltd.), and the like. They may be used alone or in a combination of two or more thereof.
The surfactant (E) may be used in an amount of 0.001 to 5 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the solid content of the siloxane polymer (a). When the amount of the surfactant is 0.05 parts by weight or more, the composition may have improved coatability without having cracks on the surface of a coating film formed from the composition. When the amount of the surfactant is 1 part by weight or less, the composition may have improved thermal stability at high temperatures and price advantages.
(F) Adhesion promoter
The photosensitive resin composition of the present invention may further comprise an adhesion promoter to improve the adhesion of the coating layer to the substrate.
The adhesion promoter may have at least one reactive group selected from the group consisting of: carboxyl, (meth) acryloyl, isocyanate, amino, mercapto, vinyl, and epoxy.
The adhesion promoter is not limited to a specific kind. Trimethoxysilanylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane and beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane are preferred. Preferably, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, or N-phenylaminopropyltrimethoxysilane can be used to obtain the desired film retention and adhesion of the coating to the substrate.
The adhesion promoter (F) may be used in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight (as solid content) of the silicone polymer (a). Within the preferred range, the composition can have improved adhesion to the substrate without impairing the resolution of the coated film.
The photosensitive resin composition of the present invention may further contain other additives as necessary, in addition to the above components, as long as the physical properties of the composition are not adversely affected.
The photosensitive resin composition of the present invention can be used as a positive photosensitive resin composition.
Specifically, the photosensitive resin composition of the present invention uses an epoxy compound and a siloxane polymer to increase the internal density of a siloxane adhesive. Accordingly, the present invention can provide a positive type resin composition that can form a cured film having improved chemical (solvent, acid, alkali, etc.) resistance during post-processing.
In addition, the present invention provides a cured film prepared from the photosensitive resin composition.
The cured film can be prepared by a conventional method well known in the art by, for example, coating a photosensitive resin composition on a substrate and subjecting it to a curing treatment.
The coating process may be performed with a desired thickness of, for example, 2 to 25 micrometers by means of a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, or the like.
To cure the photosensitive resin composition, for example, the composition coated on the substrate may be subjected to a prebaking at a temperature of, for example, 60 ℃ to 130 ℃ to remove any solvent; exposure to light with a photomask having a desired pattern; and developing with a developer such as a tetramethylammonium hydroxide (TMAH) solution to form a pattern on the coated film. The exposure may be performed at a wavelength in the range of 200 nm to 500 nm and an exposure rate of 10 mj/cm to 200 mj/cm (at a wavelength of 365 nm). As the light source for exposure, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon laser, or the like; and X-rays, electron rays, etc. may also be used as necessary.
Next, the coating film having the pattern is subjected to post-baking, if necessary, at a temperature of, for example, 150 to 300 ℃ for 10 minutes to 5 hours to prepare a desired cured film.
The cured film thus obtained has excellent physical properties in terms of heat resistance, transparency, dielectric constant, solvent resistance, acid resistance, and base resistance.
When the composition is subjected to heat treatment or immersed in or contacted with a solvent, acid, base or the like, the cured film has excellent light transmittance without surface expansion or roughness. Therefore, the cured film can be effectively used as a planarization film for a TFT substrate for an LCD or an OLED; a separator for the OLED; an interlayer dielectric of the semiconductor device; core or cladding materials for optical waveguides, and the like.
Further, the present invention provides an electronic component comprising 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 set forth to illustrate the invention, and the scope of the invention is not limited thereto.
In the following preparation examples, the weight average molecular weight was determined by Gel Permeation Chromatography (GPC) using polystyrene standards.
Preparation example 1: siloxane Polymer (a)
The reaction flask was charged with 0.07g (0.0019mol) of 0.1N hydrochloric acid and 40.57g (2.25mol) of deionized water, followed by stirring. Next, 92.45g (0.383mol) of phenyltriethoxysilane (Aldrich), 34.29g (0.192mol) of methyltriethoxysilane (Aldrich), 40.06g (0.192mol) of tetraethoxysilane (Aldrich), and 12g of propylene glycol monomethyl ether acetate (PGMEA, Aldrich) were added thereto, followed by stirring at room temperature for one hour. The reaction flask was equipped with a condenser and dean-stark trap, and the mixture was distilled at 105 ℃ for 2 hours, and then reacted at 100 ℃ for 3 hours. Subsequently, 6g PGMEA was added to the reaction mixture, and then the mixture was cooled. The remaining acid in the reaction mixture was removed by ion exchange column. The resultant mixture was charged into a reactor, and then water and alcohol were removed therefrom at 45 ℃ under reduced pressure to obtain a siloxane polymer having a Mw of about 4,000, to which PGMEA was then added to adjust its solid content to 40% by weight.
Preparation example 2: siloxane Polymer (b)
The reaction flask was charged with 0.07g (0.0019mol) of 0.1N hydrochloric acid and 40.57g (2.25mol) of deionized water, followed by stirring. Next, 46.224g (0.192mol) of phenyltriethoxysilane (Aldrich), 68.4g (0.383mol) of methyltriethoxysilane (Aldrich), 40.06g (0.192mol) of tetraethoxysilane (Aldrich), and 12g of propylene glycol monomethyl ether acetate (PGMEA, Aldrich) were added thereto, followed by stirring at room temperature for one hour. The reaction flask was equipped with a condenser and dean-stark trap, and the mixture was distilled at 105 ℃ for 2 hours, and then reacted at 100 ℃ for 3 hours. Subsequently, 6g PGMEA was added to the reaction mixture, and then the mixture was cooled. The remaining acid in the reaction mixture was removed by ion exchange column. The resultant mixture was charged into a reactor, and then water and alcohol were removed therefrom at 45 ℃ under reduced pressure to obtain a siloxane polymer having a weight average molecular weight of about 4,000, to which PGMEA was then added to adjust its solid content to 30% by weight.
Preparation example 3: epoxy Compound (a)
A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic temperature controller. 100 parts by weight of a monomer mixture comprising glycidyl methacrylate (50 mol%) and styrene (50 mol%), 10 parts by weight of 2, 2' -azobis (2-methylbutyronitrile) and 100 parts by weight of PGMEA were charged into a flask, and the flask was charged with nitrogen gas. The flask was heated to 80 ℃ while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an epoxy compound having a weight average molecular weight of about 12,000, to which PGMEA was then added to adjust its solid content to 20 wt%.
Preparation example 4: epoxy Compound (b)
A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic temperature controller. 100 parts by weight of a monomer including glycidyl methacrylate (100 mol%), 10 parts by weight of 2, 2' -azobis (2-methylbutyronitrile), and 100 parts by weight of PGMEA were charged into a flask, and nitrogen gas was charged into the flask. The flask was heated to 80 ℃ while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an epoxy compound having a weight average molecular weight of about 14,000, to which PGMEA was then added to adjust its solid content to 20 wt%.
Preparation example 5: acrylic Compound (a)
A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic temperature controller. 100 parts by weight of a monomer mixture comprising methacrylic acid (21 mol%), 3, 4-epoxycyclohexylmethyl methacrylate (15 mol%), methyl methacrylate (21 mol%) and styrene (43 mol%), 10 parts by weight of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and 100 parts by weight of methyl 3-methoxypropionate were charged into a flask, and the flask was charged with nitrogen gas. The flask was heated to 70 ℃ while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an acrylic compound having a weight average molecular weight of about 4,800, to which PGMEA was then added to adjust its solid content to 40% by weight.
Preparation example 6: acrylic acid series Compound (b)
A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic temperature controller. 100 parts by weight of a monomer mixture comprising methacrylic acid (22.5 mol%), 3, 4-epoxycyclohexylmethyl methacrylate (25 mol%), methyl methacrylate (9.5 mol%) and styrene (43 mol%), 10 parts by weight of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and 100 parts by weight of methyl 3-methoxypropionate were charged into a flask, and the flask was charged with nitrogen gas. The flask was heated to 70 ℃ while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an acrylic compound having a weight average molecular weight of about 6,700, to which PGMEA was then added to adjust its solid content to 40% by weight.
Preparation example 7: acrylic Compound (c)
A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic temperature controller. 100 parts by weight of a monomer mixture comprising methacrylic acid (24 mol%), 3, 4-epoxycyclohexylmethyl methacrylate (25 mol%) and styrene (51 mol%), 10 parts by weight of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and 100 parts by weight of methyl 3-methoxypropionate were charged into a flask, and the flask was charged with nitrogen gas. The flask was heated to 70 ℃ while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an acrylic compound having a weight average molecular weight of about 6, 800, to which PGMEA was then added to adjust its solid content to 40% by weight.
Preparation example 8: acrylic acid series Compound (d)
A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic temperature controller. 100 parts by weight of a monomer mixture comprising methacrylic acid (20 mol%), 3, 4-epoxycyclohexylmethyl methacrylate (20 mol%), styrene (55 mol%) and 4-hydroxybutyl acrylate glycidyl ether (4HBAGE, 5 mol%), 10 parts by weight of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and 100 parts by weight of methyl 3-methoxypropionate were charged into a flask, and the flask was charged with nitrogen gas. The flask was heated to 70 ℃ while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an acrylic compound having a weight average molecular weight of about 5,000, to which PGMEA was then added to adjust its solid content to 40% by weight.
Examples and comparative examples: preparation of photosensitive resin composition
The photosensitive resin compositions of examples and comparative examples were prepared by using the components obtained in the above-described preparation examples. In addition, the following compounds were used in the examples and comparative examples:
-1, 2-diazidoquinone compounds: TPA-523, Meiyuan Business corporation
-adhesion promoter: 3-glycidoxypropyltrimethoxysilane, GPTMS, Sigma-Aldrich
-a surfactant: leveling surfactant based on silicon FZ-2122, Dow Corning Dongli Si Ltd
-a solvent: propylene Glycol Monomethyl Ether Acetate (PGMEA)
Example 1
14.45g of the silicone polymer (a) obtained in production example 1, 1.66g of the epoxy compound (a) obtained in production example 3, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, the molar ratio of T-type structural units having phenyl residues (T-phenyl type) to T-type structural units having methyl residues (T-methyl type) to Q-type structural units is 50: 25.
Example 2
14.12g of the silicone polymer (a) obtained in production example 1, 2.22g of the silicone polymer (b) obtained in production example 2, 1.66g of the epoxy compound (a) obtained in production example 3, 0.83g of 1, 2-diazidoquinone compound, 0.15g of adhesion promoter, and 0.15g of surfactant were uniformly mixed, and then dissolved in 11.43g of a solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer was 47.4: 27.6: 25.
Example 3
13.29g of the silicone polymer (a) obtained in production example 1, 3.32g of the silicone polymer (b) obtained in production example 2, 1.66g of the epoxy compound (a) obtained in production example 3, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer was 46.1: 28.9: 25.
Example 4
16.11g of the silicone polymer (a) obtained in production example 1, 0.99g of the epoxy compound (a) obtained in production example 3, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Example 5
14.45g of the silicone polymer (a) obtained in production example 1, 2.22g of the silicone polymer (b) obtained in production example 2, 0.99g of the epoxy compound (a) obtained in production example 3, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer was 47.4: 27.6: 25.
Example 6
13.62g of the silicone polymer (a) obtained in production example 1, 3.32g of the silicone polymer (b) obtained in production example 2, 0.99g of the epoxy compound (a) obtained in production example 3, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer was 46.1: 28.9: 25.
Example 7
16.11g of the silicone polymer (a) obtained in production example 1, 0.99g of the epoxy compound (b) obtained in production example 4, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Example 8
15.78g of the silicone polymer (a) obtained in production example 1, 1.66g of the epoxy compound (b) obtained in production example 4, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Example 9
13.62g of the silicone polymer (a) obtained in production example 1, 3.32g of the epoxy compound (a) obtained in production example 3, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Example 10
14.12g of the silicone polymer (a) obtained in production example 1, 4.98g of the epoxy compound (a) obtained in production example 3, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Example 11
13.29g of the silicone polymer (a) obtained in production example 1, 6.64g of the epoxy compound (a) obtained in production example 3, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Example 12
11.63g of the silicone polymer (a) obtained in production example 1, 9.96g of the epoxy compound (a) obtained in production example 3, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Example 13
9.798g of the siloxane polymer (a) obtained in production example 1, 13.28g of the epoxy compound (a) obtained in production example 3, 13.28g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Comparative example 1
16.61g of the silicone polymer (a) obtained in preparation example 1, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Comparative example 2
15.78g of the silicone polymer (a) obtained in production example 1, 1.03g of the acrylic compound (a) obtained in production example 5, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Comparative example 3
15.78g of the silicone polymer (a) obtained in production example 1, 1.01g of the acrylic compound (b) obtained in production example 6, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Comparative example 4
15.78g of the silicone polymer (a) obtained in production example 1, 1g of the acrylic compound (c) obtained in production example 7, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Comparative example 5
15.78g of the silicone polymer (a) obtained in production example 1, 1.03g of the acrylic compound (d) obtained in production example 8, 0.83g of the 1, 2-diazidoquinone compound, 0.15g of the adhesion promoter, and 0.15g of the surfactant were uniformly mixed, and then dissolved in 11.43g of the solvent. The resulting solution was filtered through a membrane filter of 0.2 μm pore size to obtain a resin composition in the form of a solution having a solid content of 25% by weight. The molar ratio of T-phenyl to T-methyl to Q structural units in the siloxane polymer is 50: 25.
Experimental example 1: evaluation of chemical resistance
Each photosensitive resin composition obtained in example and comparative example was coated on a glass substrate using a spin coater. The coated substrate was pre-baked at 115 ℃ for 90 seconds on a hot plate to form a film with a thickness of 3.1 microns. The film was then developed by spraying an aqueous developer solution (2.38 wt% tetramethylammonium hydroxide) through a nozzle at 23 ℃ for 60 seconds. Subsequently, without using a pattern mask, the developed film was exposed to light (i.e., a bleaching method) at an exposure rate of 200 mj/cm for a certain period of time based on a wavelength of 365 nm by using an aligner (model name: MA6) that emits light having a wavelength of 200 nm to 450 nm. The film was then post-baked in a convection oven at 230 ℃ for 30 minutes to obtain a cured film. The thickness of the cured film (T1) was measured by using a non-contact type height measuring apparatus (SNU accuracy).
The rework chemical (product name: EP-6) was introduced into a constant temperature bath and then maintained at 50 ℃. The cured film was placed in a bath for 10 minutes, and heat curing was performed on a hot plate for 10 minutes. Then, the thickness of the cured film was measured (T2).
The chemical resistance value (%) of the cured film was calculated by using the following equation 1:
[ equation 1]
Chemical resistance (%) - [ (thickness after heat curing (T2)/(initial thickness before immersion in rework chemical (T1) ] × 100)
When the above chemical resistance value is close to 100% (i.e., the cured film returns to its original state after swelling), the chemical resistance of the cured film is considered satisfactory.
Experimental example 2: evaluation resolution (sensitivity)
Each of the compositions obtained in examples and comparative examples was coated on a glass substrate by using a spin coater, and the coated substrate was pre-baked and dried on a hot plate maintained at 110 ℃ for 90 seconds to form a film having a thickness of 3.1 μm. The film was exposed to light at an exposure rate of 0 to 200 mj/cm based on a wavelength of 365 nm for a certain period of time by passing the film through a mask having a pattern consisting of square holes having a size ranging from 2 to 25 μm using an aligner (model name: MA6) that emits light having a wavelength of 200 to 450 nm. The film was developed by spraying an aqueous developer solution (2.38 wt% tetramethylammonium hydroxide) through a nozzle at 23 ℃. The film was then heated at 230 ℃ for 30 minutes in a convection oven to obtain a cured film.
The amount of exposure dose required to reach a critical dimension (CD, unit: micrometer) of 19 micrometers was measured for a hole pattern formed through a mask having a square hole pattern with a size of 20 micrometers. The lower the exposure dose, the better the resolution (sensitivity) of the cured film.
Experimental example 3: evaluation of developability (scum at development)
Each of the compositions obtained in examples and comparative examples was coated on a silicon substrate by using a spin coater, and the coated substrate was pre-baked and dried on a hot plate maintained at 110 ℃ for 90 seconds to form a film having a thickness of 3.1 μm. The film was exposed to light at an exposure rate of 100 mj/cm through a pattern mask for a certain period of time based on a wavelength of 365 nm by using an aligner (model name: MA6) that emits light at a wavelength of 200 nm to 450 nm. The film was developed by spraying a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as a developer through a nozzle at 25 ℃. The film was then heated at 200 ℃ for 30 minutes in a convection oven to obtain a heat-cured film.
The developability of the thermosetting film was evaluated based on the shape of the developed pattern. Specifically, by observing a pattern formed in a contact hole having a line width of 20 μm in a thermosetting film using a scanning electron microscope, the shape of the developed pattern was evaluated according to the following criteria.
Very good: the rectangular shape was clear and no bottom tailing was observed.
O: the rectangular shape is clear, but the surface is not smooth.
Δ: the rectangle is clear in shape but the surface is not smooth or leaves a spotted residual film.
X: the rectangular shape was unclear, or no cured film was produced.
Experimental example 4: evaluation of film holding ratio
The same procedure as in experimental example 3, including pre-baking, exposure through a mask, development, and post-baking was repeated for each composition obtained in examples and comparative examples to prepare a heat-cured film. Film retention was obtained from the final thickness of the heat-set film relative to the thickness of the set film immediately after the prebake process as measured by a non-contact type thickness measuring device (SNU accuracy).
Experimental example 5: evaluation of light transmittance
Each of the compositions obtained in examples and comparative examples was coated on a silicon substrate by using a spin coater. The same procedure as in experimental example 3 was repeated, including pre-baking, exposure through a mask, development, and post-baking to prepare a thermally cured film having a thickness of about 3 μm.
The light transmittance of the heat-cured film in a wavelength range of 400 nm to 800 nm was measured using an ultraviolet/visible spectrophotometer.
The results of the above experimental examples are shown in the following table.
[ Table 1]
Chemical resistance (%) Developability Film holding ratio (%) Light transmittance (%)
Example 1 100 ◎ 93 95
Example 2 100 ◎ 92 95
Example 3 100 ◎ 91 95
Example 4 102 ◎ 95 95
Example 5 101 ◎ 92 95
Example 6 100 ◎ 91 95
Example 7 101 ◎ 98 95
Example 8 100 ○ 97 95
Example 9 100 ◎ 98 95
Example 10 100 ○ 98 95
Example 11 100 ○ 98 95
Example 12 100 ○ 99 95
Example 13 100 ○ 99 96
Comparative example 1 89 ◎ 96 96
Comparative example 2 57 Δ 96 93
Comparative example 3 78 ○ 95 93
Comparative example 4 70 ◎ 95 93
Comparative example 5 73 Δ 95 93
[ Table 2]
Sensitivity (millijoule/square centimeter)
Example 1 35
Example 2 35
Example 3 30
Example 4 30
Example 5 30
Example 6 25
Example 7 40
Example 8 60
Example 9 90
Example 10 150
Example 11 150
Example 12 200
Example 13 240
As shown in tables 1 and 2 above, the compositions obtained in the examples of the present invention have equally good chemical resistance, sensitivity, developability, and light transmittance. In contrast, at least one of the above properties of the compositions obtained in the comparative examples is not satisfactory.

Claims (5)

1. A photosensitive resin composition comprising:
(A) siloxane polymer containing at least one structural unit derived from silane compound represented by formula (I)
(B) An epoxy compound comprising a structural unit represented by formula (II):
Figure FDA0002664673710000011
wherein
R3Is H or C1-C2An alkyl group;
R4is H, or a straight or branched chain C1-C5An alkyl group; and
m is an integer from 1 to 10, and
(C)1, 2-diazidoquinone compound:
(R1)nSi(R2)4-n (I)
wherein R is1Is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or an alkylaryl group having 7 to 12 carbon atoms, and at a plurality of R1In the case ofWhich may be the same or different from each other;
R2is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, an amino group, an acyloxy group having 2 to 12 carbon atoms or an aryloxy group having 6 to 12 carbon atoms, and2in the case of (b), they may be the same as or different from each other; and
n is an integer from 0 to 3.
2. The photosensitive resin composition according to claim 1, wherein the epoxy compound (B) does not contain a carboxyl group.
3. The photosensitive resin composition according to claim 1 or 2, wherein the weight ratio of the siloxane polymer (a) to the epoxy compound (B), i.e., a: B, is 97:3 to 70:30 based on the total weight of solid content.
4. The photosensitive resin composition according to claim 3, wherein the siloxane polymer (A) comprises a structural unit derived from a silane compound represented by formula (I) wherein n is 0.
5. The photosensitive resin composition according to claim 4, wherein the siloxane polymer (A) comprises 10 to 60 mol% of the structural unit derived from the silane compound represented by formula (I) where n is 0, based on the total moles of Si atoms.
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