CN111381442A - Chemically amplified positive photosensitive resin composition and use thereof - Google Patents

Chemically amplified positive photosensitive resin composition and use thereof Download PDF

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CN111381442A
CN111381442A CN201911267123.0A CN201911267123A CN111381442A CN 111381442 A CN111381442 A CN 111381442A CN 201911267123 A CN201911267123 A CN 201911267123A CN 111381442 A CN111381442 A CN 111381442A
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group
weight
resin composition
photosensitive resin
unsaturated
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刘骐铭
施俊安
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Chi Mei Corp
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Chi Mei Corp
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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
    • G03F7/039—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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a chemical amplification type positive photosensitive resin composition, which comprises a resin (A), a photoacid generator (B), a solvent (C) and an unsaturated group-containing polyurethane compound (D). The invention also comprises a protective film prepared by applying the chemical amplification type positive photosensitive resin composition and a component comprising the protective film. The protective film has good development adhesion and transparency, and can be used as a planarization film for a thin film transistor substrate, an interlayer insulating film, or a core material or a coating material of an optical waveguide.

Description

Chemically amplified positive photosensitive resin composition and use thereof
Technical Field
The invention relates to a chemical amplification type positive photosensitive resin composition, a protective film formed by the same and a component with the protective film. In particular, a positive photosensitive resin composition for a protective film which is formed after exposure and development and has the characteristics of good development adhesion, good transparency and the like is provided. The protective Film is suitable for a planarizing Film for a Thin Film Transistor (TFT) substrate of a liquid crystal display device, an organic EL display device, or the like, an interlayer insulating Film, or a core material or a coating material of an optical waveguide.
Background
Display devices such as thin film transistor-type liquid crystal display devices and organic electroluminescence devices (organic EL devices) generally include an insulating film such as an interlayer insulating film or a planarizing film. Such an insulating film is generally formed using a radiation-sensitive composition. In view of patterning performance, a positive radiation-sensitive resin composition using an acid generator such as naphthoquinone diazide (refer to japanese patent laid-open No. 2001-354822) has been widely used as such a radiation-sensitive composition, but in recent years, various radiation-sensitive compositions have been proposed.
For example, a positive type chemical amplification material is proposed, which aims to: the cured film for display device is formed with higher sensitivity than the positive radiation-sensitive resin composition using an acid generator such as naphthoquinone diazide (see Japanese patent laid-open No. 2004-4669). The positive type chemical amplification material contains a crosslinking agent, an acid generator and an acid-dissociable resin. The acid-dissociable resin has a protecting group that can be dissociated by the action of an acid, and although the acid-dissociable resin itself is insoluble or poorly soluble in an aqueous alkaline solution, the protecting group is dissociated by the action of an acid to become soluble in an aqueous alkaline solution. In addition, positive radiation-sensitive compositions containing a resin having an acetal structure and/or a ketal structure and an epoxy group and an acid generator have also been proposed (see Japanese patent laid-open Nos. 2004-264623, 2011-215596 and 2008-304902).
These radiation-sensitive resin compositions are required to have high radiation sensitivity and storage stability such that the viscosity does not change even after long-term storage, and further, cured films formed from these radiation-sensitive resin compositions are required to have resistance to swelling caused by a developer or the like. Furthermore, the hardened film may be formed in a pattern of: after development, the pattern and the substrate are sufficiently adhered and difficult to peel; the hardened film has sufficient transparency; and, even in the case of being left to stand after exposure, the pattern is sufficiently adhered to the substrate and is difficult to peel off.
However, the development adhesion and transparency of the cured film (or protection film) formed by the current photosensitive resin composition are still unacceptable.
Disclosure of Invention
One aspect of the present invention is to provide a chemically amplified positive photosensitive resin composition. In some embodiments, the chemically amplified positive photosensitive resin composition may include a resin (a), a photoacid generator (B), a solvent (C), and an unsaturated group-containing polyurethane compound (D), which is described in detail below.
Resin (A)
The resin (A) is obtained by copolymerization of the mixture. In some embodiments, the mixture includes at least the unsaturated carboxylic acid monomer (a-1) and the acid dissociable group-containing monomer (a-2).
Unsaturated carboxylic acid monomer (a-1)
The unsaturated carboxylic acid monomer (a-1) of the present invention is a compound having a carboxylic acid group or carboxylic acid anhydride structure and an unsaturated bond for polymerization, and the structure thereof is not particularly limited, and may include, but is not limited to, an unsaturated monocarboxylic acid compound, an unsaturated dicarboxylic acid compound, an unsaturated acid anhydride compound, a polycyclic unsaturated carboxylic acid compound, a polycyclic unsaturated dicarboxylic acid compound, and a polycyclic unsaturated acid anhydride compound.
Specific examples of the unsaturated monocarboxylic acid compound include (meth) acrylic acid, crotonic acid, α -chloroacrylic acid, ethacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethoxy succinate, 2- (meth) acryloyloxyethoxy hexahydrophthalic acid ester, 2- (meth) acryloyloxyethoxy phthalic acid ester, and omega-carboxy polycaprolactone monoacrylate (trade name: ARONIX M-5300, manufactured by Toyo Seiya).
Specific examples of the aforementioned unsaturated dicarboxylic acid compounds are: maleic acid, fumaric acid, mesaconic acid, itaconic acid, citraconic acid, and the like. In the specific embodiment of the present invention, the unsaturated dicarboxylic acid anhydride compound is an anhydride compound of the above unsaturated dicarboxylic acid compound.
Specific examples of the foregoing polycyclic unsaturated carboxylic acid compounds are: 5-carboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene.
Specific examples of the foregoing polycyclic unsaturated dicarboxylic acid compounds are: 5, 6-dicarboxylic acid bicyclo [2.2.1] hept-2-ene.
The polycyclic unsaturated dicarboxylic acid anhydride compound is an anhydride compound of the polycyclic unsaturated dicarboxylic acid compound.
Preferred examples of the unsaturated carboxylic acid monomer (a-1) are acrylic acid, methacrylic acid, maleic anhydride, 2-methacryloyloxyethylsuccinate, 2-methacryloyloxyethylhexahydrophthalic acid, or a combination thereof.
The unsaturated carboxylic acid monomer (a-1) may be used alone or in combination of plural kinds. The unsaturated carboxylic acid monomer (a-1) is used in an amount of 5 to 95 parts by weight based on 100 parts by weight of the mixture of the synthetic resin (a); preferably 5 to 80 parts by weight; more preferably 5 to 70 parts by weight.
Monomer (a-2) containing acid dissociable group
The mixture of the present invention includes the acid-dissociable group-containing monomer (a-2). Preferably, the acid dissociable group-containing monomer (a-2) has an acid dissociable group represented by the following structural formula (i).
Figure BDA0002313165110000031
Since the acid dissociable group of the monomer (a-2) containing an acid dissociable group dissociates by the action of an acid generated from the photoacid generator (B) described later during exposure to light, and a polar group is generated, the resin (a) which is originally insoluble or poorly soluble in an aqueous alkali solution becomes soluble in an aqueous alkali solution.
The acid-dissociable group-containing monomer (a-2) is not particularly limited as long as it has the structure of formula (I). The acid-dissociable group-containing monomer (a-2) of formula (I) can be readily dissociated by an acid. In the above formula (I), R1And R2Each independently represents a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, wherein a part or all of the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group or the aryl group may be substituted;and, R1And R2Not being hydrogen atoms at the same time; r3Is alkyl, alicyclic hydrocarbon group, aralkyl or aryl; wherein R is3A part or all of the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, the aralkyl group and the aryl group of (a) may be substituted; r1And R3May be linked to form a cyclic ether structure. For example: r1And R3Can be bonded to each other with R1The carbon atom and R bonded3The bonded oxygen atoms together form a cyclic ether structure.
R is as defined above1And R2Examples of the alicyclic hydrocarbon group include alicyclic hydrocarbon groups having 3 to 20 carbon atoms. In addition, the alicyclic hydrocarbon group having 3 to 20 carbon atoms may be polycyclic. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include: cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bornyl, norbornyl, adamantyl, and the like.
R is as defined above1And R2Examples of the aryl group include aryl groups having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms may have a monocyclic ring, a structure in which monocyclic rings are linked, or a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include phenyl and naphthyl.
R is as defined above1And R2Examples of the substituent for the alkyl group, alicyclic hydrocarbon group and aryl group which may be substituted include: halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, carbonyl group, alicyclic hydrocarbon group (for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, bornyl group, norbornyl group, adamantyl group and the like), aryl group (for example, phenyl group, naphthyl group and the like), alkoxy group (for example, alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, propoxy group, n-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like), acyl group (for example, acyl group having 2 to 20 carbon atoms such as acetyl group, propionyl group, butyryl group, isobutyryl group and the like), acyloxy group (for example, acyloxy group having 2 to 10 carbon atoms such as acetoxy group, propionyloxy group, butyryloxy group, third valeryloxy group and the like), alkoxycarbonyl group (for example, alkoxycarbonyl group having 2 to 20 carbon atoms such as methoxycarbonyl) A haloalkyl group (e.g., a linear alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group, a n-dodecyl group, a n-tetradecyl group, or a n-octadecyl group), or an alkyl group such as a branched alkyl group such as an isopropyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a 2-hexyl group, or a 3-hexyl group; alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, and adamantyl groups, groups obtained by substituting a part or all of the hydrogen atoms of the above groups with halogen atoms), hydroxyalkyl groups (for example, hydroxymethyl groups), and the like.
R is as defined above3As the alkyl group, alicyclic hydrocarbon group and aryl group represented by the formula R1And R2Description of each group represented. Further, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group and an n-propyl group. R is as defined above3As the aralkyl group represented, there can be mentioned: benzyl, phenethyl, naphthylmethyl, naphthylethyl and the like.
R is as defined above1And R3The cyclic ether structures which may be bonded to each other are preferably cyclic ether structures having a ring member number of 3 to 20, more preferably cyclic ether structures having a ring member number of 5 to 8, and still more preferably tetrahydrofuran and tetrahydropyran.
Examples of the group represented by the above formula (I) include groups represented by the following formulae.
Figure BDA0002313165110000041
Examples of the acid-dissociable group-containing monomer (a-2) include: 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1- (2-chloroethoxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, Tetrahydrofurfuryl methacrylate (tetrahydrofuryl methacrylate), 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, n-butoxyethyl methacrylate, 1-isobutoxyethyl acrylate, 1-t-butoxyethyl acrylate, 1- (2-chloroethoxy) ethyl acrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, 5, 6-bis (1-methoxyethoxycarbonyl) -2-norbornene, 5, 6-bis (1- (cyclohexyloxy) ethoxycarbonyl) -2-norbornene, 5, 6-bis (1- (benzyloxy) ethoxycarbonyl) -2-norbornene, p-1-ethoxyethoxystyrene or m-1-ethoxyethoxystyrene, n-ethylhexylstyrene, n-ethylhexyloxy, P-1-methoxyethoxystyrene or m-1-methoxyethoxystyrene, p-1-n-butoxyethoxystyrene or m-1-n-butoxyethoxystyrene, p-1-isobutoxyethoxystyrene or m-1-isobutoxyethoxystyrene, p-1- (1, 1-dimethylethoxy) ethoxystyrene or m-1- (1, 1-dimethylethoxy) ethoxystyrene, p-1- (2-chloroethoxy) ethoxystyrene or m-1- (2-chloroethoxy) ethoxystyrene, p-1- (2-ethylhexyloxy) ethoxystyrene or m-1- (2-ethylhexyloxy) ethoxystyrene, p-1- (2-ethylhexyloxy) ethoxystyrene, m-1- (2-ethylhexyloxy) ethoxystyrene, p-1- (1-n-butylethoxystyrene, p-1-n-butylethoxystyrene, P-1-n-propoxyethoxystyrene or m-1-n-propoxyethoxystyrene, p-1-cyclohexyloxyethoxystyrene or m-1-cyclohexyloxyethoxystyrene, p-1- (2-cyclohexylethoxy) ethoxystyrene or m-1- (2-cyclohexylethoxy) ethoxystyrene, p-1-benzyloxyethoxystyrene or m-1-benzyloxyethoxystyrene, and the like.
The acid-dissociable group-containing monomer (a-2) is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, tetrahydrofurfuryl methacrylate, more preferably 2-tetrahydropyranyl methacrylate and tetrahydrofurfuryl methacrylate.
The acid-dissociable group-containing monomer (a-2) is used in an amount of 5 to 95 parts by weight, preferably 10 to 80 parts by weight, and more preferably 15 to 70 parts by weight, based on 100 parts by weight of the mixture. If the acid-dissociable group-containing monomer (a-2) is not used, the development adhesion is not good and the transparency is not good.
Further, when the dissociative group of the acid-dissociative group-containing monomer (a-2) has the structure of the formula (I), the development adhesion of the protective film can be further improved.
Epoxy group-containing unsaturated monomer (a-3)
In some embodiments, the mixture used for synthesizing the resin (a) of the chemically amplified positive photosensitive resin composition of the present invention may further include an unsaturated monomer (a-3) having an epoxy group.
The epoxy group-containing unsaturated monomer (a-3) may include, but is not limited to, an epoxy group-containing (meth) acrylate compound, an epoxy group-containing α -alkylacrylate compound, a glycidylether compound, an ethylenically unsaturated monomer having an oxetanyl group as shown in formula (ii), and any combination thereof.
Figure BDA0002313165110000061
In formula (II), R4Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; r5Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; r6、R7、R8And R9Each independently represents a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms; and a represents an integer of 1 to 6.
Specific examples of the aforementioned epoxy group-containing (meth) acrylate compound include: glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, and 3, 4-epoxycyclohexylmethyl (meth) acrylate.
Specific examples of the above-mentioned epoxy group-containing α -alkylacrylate compounds include α -epoxypropyl ethacrylate, α -epoxypropyl n-propylacrylate, α -epoxypropyl n-butylacrylate, and α -6, 7-epoxyheptyl ethacrylate.
Specific examples of the aforementioned glycidyl ether compounds include: o-vinylbenzylglycidyl ether (o-vinylbenzylglycidyl ether), m-vinylbenzylglycidyl ether (m-vinylbenzylglycidyl ether), p-vinylbenzylglycidyl ether (p-vinylbenzylglycidyl ether).
Specific examples of the aforementioned ethylenically unsaturated monomer having an oxetanyl group represented by the formula (II) may include, but are not limited to, methacrylate compounds, acrylate compounds or unsaturated monomers having structures represented by the following formulae (II-1) to (II-4).
The aforementioned methacrylate-based compounds may include, but are not limited to, 3- (methacryloylmethoxy) oxetane [3- (methacryloyloxy) oxirane; OXMA), 3- (methacryloylmethoxy) -3-ethyloxetane [3- (methacryloyloxy) -3-ethylxetane; EOXMA ], 3- (methacryloylmethoxy) -3-methyloxetane [3- (methacryloyloxy) -3-methylxetane; MOXMA ], 3- (methacryloylmethoxy) -2-methyloxetane, 3- (methacryloylmethoxy) -2-trifluoromethyloxetane, 3- (methacryloylmethoxy) -2-pentafluoroethyloxetane, 3- (methacryloylmethoxy) -2-phenyloxetane, 3- (methacryloylmethoxy) -2, 2-difluorooxetane, 3- (methacryloylmethoxy) -2,2, 4-trifluorooxetane, 3- (methacryloylmethoxy) -2,2,4, 4-tetrafluorooxetane, 3- (methacryloylethoxy) oxetane, 3- (methacryloylethoxy) -3-ethyloxetane, 2-ethyl-3- (methacryloylethoxy) oxetane, 3- (methacryloylethoxy) -2-trifluoromethyloxetane, 3- (methacryloylethoxy) -2-pentafluoroethyloxetane, 3- (methacryloylethoxy) -2-phenyloxetane, 2-difluoro-3- (methacryloylethoxy) oxetane, 3- (methacryloylethoxy) -2,2, 4-trifluorooxetane or 3- (methacryloylethoxy) -2,2,4, 4-tetrafluorooxetane, and the like.
The above-mentioned acrylate compounds may include, but are not limited to, 3- (acryloylmethoxy) oxetane, 3- (acryloylmethoxy) -3-ethyloxetane, 3- (acryloylmethoxy) -3-methyloxetane, 3- (acryloylmethoxy) -2-trifluoromethyloxetane, 3- (acryloylmethoxy) -2-pentafluoroethyloxetane, 3- (acryloylmethoxy) -2-phenyloxetane, 3- (acryloylmethoxy) -2, 2-difluorooxetane, 3- (acryloylmethoxy) -2,2, 4-trifluorooxetane, 3- (acryloylmethoxy) -2,2,4, 4-tetrafluorooxetane, 3- (acryloylethoxy) oxetane, 3- (acryloylethoxy) -3-ethyloxetane, 2-ethyl-3- (acryloylethoxy) oxetane, 3- (acryloylethoxy) -2-trifluoromethyloxetane, 3- (acryloylethoxy) -2-pentafluoroethyloxetane, 3- (acryloylethoxy) -2-phenyloxetane, 2-difluoro-3- (acryloylethoxy) oxetane, 3- (acryloylethoxy) -2,2, 4-trifluorooxetane or 3- (acryloylethoxy) -2,2,4, 4-tetrafluorooxetane, and the like.
The aforementioned unsaturated monomers having the structures represented by the formulae (II-1) to (II-4) are shown below.
Figure BDA0002313165110000071
Figure BDA0002313165110000081
In some embodiments, the epoxy group-containing unsaturated monomer (a-3) may further include other ethylenically unsaturated monomers having an oxetanyl group, such as: 3-methyl-3- (vinylmethoxy) oxetane [3-methyl-3- (vinyloxy) oxirane; MOXV), 3-ethyl-3- (vinylmethoxy) oxetane [3-ethyl-3- (vinyloxy) oxirane; EOXV ], 3-propyl-3- (ethylenemethoxy) oxetane, 3-methyl-3- (2-ethyleneethoxy) oxetane, 3-ethyl-3- (2-ethyleneethoxy) oxetane, 3-propyl-3- (2-ethyleneethoxy) oxetane, 3-methyl-3- (3-ethylenepropoxy) oxetane, 3-ethyl-3- (3-ethylenepropoxy) oxetane, 3-propyl-3- (3-ethylenepropoxy) oxetane, 3-methyl-3- (3-ethylenebutoxy) oxetane, 3-ethyl-3- (3-ethylenebutoxy) oxetane, vinyl ether compounds having an oxetanyl group such as 3-propyl-3- (3-vinylbutoxy) oxetane, ethylene glycol [ (3-ethyl-3-oxetanyl) methyl ] vinyl ether, propylene glycol [ (3-ethyl-3-oxetanyl) methyl ] vinyl ether and 3, 3-bis [ (vinyloxy) methyl ] oxetane.
Preferably, the epoxy group-containing unsaturated compound (a-3) may be, for example, glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 6, 7-epoxyheptyl methacrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, 3- (methacryloylmethoxy) oxetane or p-vinylbenzylglycidyl ether.
The epoxy group-containing unsaturated compound (a-3) is used in an amount of 5 to 90 parts by weight, preferably 10 to 80 parts by weight, more preferably 15 to 75 parts by weight, based on 100 parts by weight of the mixture. When the epoxy group-containing unsaturated compound (a-3) is used, there is an advantage that the developability adhesiveness is excellent.
Other unsaturated monomer (a-4)
The mixture for forming the resin (A) may further contain other unsaturated monomer (a-4). In some embodiments, the other unsaturated monomer (a-4) may include, but is not limited to, alkyl (meth) acrylates, alicyclic (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic diesters, hydroxyalkyl (meth) acrylates, polyethers of (meth) acrylates, aromatic vinyl compounds, and other unsaturated compounds other than the foregoing.
Specific examples of the aforementioned alkyl (meth) acrylate include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate.
Specific examples of the aforementioned alicyclic (meth) acrylate are: cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02，6]Decyl-8-yl (methyl) propaneAlkenoic acid esters (otherwise known as dicyclopentanyl (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.
Specific examples of the aforementioned aryl (meth) acrylate include: phenyl (meth) acrylate, benzyl (meth) acrylate.
Specific examples of the aforementioned unsaturated dicarboxylic acid diester are: diethyl maleate, diethyl fumarate and diethyl itaconate.
Specific examples of the aforementioned hydroxyalkyl (meth) acrylate include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate.
Specific examples of the polyether of the aforementioned (meth) acrylate are: polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate.
Specific examples of the aromatic vinyl compound include styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene and p-methoxystyrene.
Specific examples of unsaturated compounds other than the foregoing include: acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1, 3-butadiene, isoprene, 2, 3-dimethyl 1, 3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide.
The other unsaturated monomer (a-4) is used in an amount of 0 to 85 parts by weight, preferably 0 to 75 parts by weight, more preferably 0 to 65 parts by weight, based on 100 parts by weight of the mixture.
Preparation of resin (A)
The solvent used in the manufacture of the resin (a) of the present invention may include, but is not limited to, alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbons, ketones, esters.
Specific examples of the aforementioned alcohols are: methanol, ethanol, benzyl alcohol, 2-phenethyl alcohol and 3-phenyl-1-propanol. Specific examples of the aforementioned ethers include: tetrahydrofuran. Specific examples of the aforementioned glycol ethers include: ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Specific examples of the above-mentioned glycol alkyl ether acetate include: ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate. Specific examples of the aforementioned diethylene glycol include: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether. Specific examples of the aforementioned dipropylene glycol include: dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether. Specific examples of the aforementioned propylene glycol monoalkyl ethers include: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. Specific examples of the propylene glycol alkyl ether acetate include: propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate. Specific examples of the aforementioned propylene glycol alkyl ether propionate are: propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate. Specific examples of the aforementioned aromatic hydrocarbons include: toluene, xylene. Specific examples of the aforementioned ketones: methyl ethyl ketone, cyclohexanone and diacetone alcohol. Specific examples of the aforementioned esters are: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxylacetate, ethyl propoxylacetate, butyl propoxylacetate, methyl butoxyacetate, methyl propoxyphyllacetate, ethyl propoxyphyllacetate, butyl propoxyacetate, methyl butoxyacetate, methyl 2-hydroxy-2-methylpropionate, Butoxyacetic acid ethyl ester, butoxyacetic acid propyl ester, butoxyacetic acid butyl ester, 3-methoxybutyl acetate, 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2-methoxypropionic acid butyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid propyl ester, 2-ethoxypropionic acid butyl ester, 2-butoxypropionic acid methyl ester, 2-butoxypropionic acid ethyl ester, 2-butoxypropionic acid propyl ester, 2-butoxypropionic acid butyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate.
Preferred examples of the solvent used in the production of the resin (A) of the present invention are diethylene glycol dimethyl ether and propylene glycol methyl ether acetate. The above solvents may be used singly or in combination of plural kinds.
Specific examples of the polymerization initiator used in the production of the resin (A) of the present invention are azo compounds and peroxides. Specific examples of the foregoing azo compounds are: 2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2 '-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azobis (2-methylbutyronitrile), 4 '-azobis (4-cyanovaleric acid), 2' -azobis (dimethyl-2-methylpropionate). Specific examples of the aforementioned peroxides include: dibenzoyl peroxide, dilauroyl peroxide, tert-butylperoxypivalate, 1-di (tert-butylperoxy) cyclohexane, and hydrogen peroxide. The above polymerization initiators may be used singly or in combination of plural kinds.
In the polymerization reaction of the resin (a), a molecular weight regulator may be used for regulating the molecular weight, and examples of the molecular weight regulator include: chloroform, carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, iso-dodecyl mercaptan (tert-dodecyl mercaptan), thioglycolic acid (thioglycolic acid), 3-mercaptopropionic acid, and the like. The molecular weight modifier may be used in an amount of 1 to 15 parts by weight, preferably 1.5 to 14 parts by weight, more preferably 2 to 12 parts by weight, based on 100 parts by weight of the mixture.
The weight average molecular weight of the resin (A) of the present invention in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is usually 3000 to 100,000, preferably 4,000 to 80,000, more preferably 5,000 to 60,000. The molecular weight of the resin (A) of the present invention can be adjusted by using a single resin or by using two or more resins having different molecular weights.
Photoacid generators (B)
The photoacid generator (B) is a compound that generates an acid upon irradiation with radiation, and at least one selected from oxime sulfonate group compounds represented by the following formula (iii) and N-sulfonyloxyimide compounds can be used. The radiation may be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like. The chemically amplified positive photosensitive resin composition of the present invention contains the photoacid generator (B), so that the chemically amplified positive photosensitive resin composition can exhibit radiation-sensitive (or referred to as photosensitive) characteristics and can have good radiation sensitivity. The photoacid generator (B) in the chemically amplified positive photosensitive resin composition may be in the form of a compound as described later, may be incorporated in the resin (a) as a part of a polymer constituting the resin (a), or may be a combination of both forms. These photoacid generators (B) may be used alone, or 2 or more of them may be used in combination.
The photoacid generator (B) may contain, in addition to an oxime sulfonate compound containing an oxime sulfonate group and an N-sulfonyloxyimide compound: onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and the like.
The oxime sulfonate compound is a compound containing an oxime sulfonate group of the following formula (iii).
Figure BDA0002313165110000121
In formula (III), R10An alkyl group, an alicyclic hydrocarbon group, an aryl group having 1 to 20 carbon atoms, or a group in which hydrogen atoms of the above groups are partially or completely substituted; and, is a bond.
The R is10The alkyl group represented is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.
The R is10The monovalent alicyclic hydrocarbon group represented is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms.
The R is10The aryl group represented is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group.
Examples of the substituent include: alkyl groups having 1 to 5 carbon atoms, alkoxy groups, pendant oxy groups, halogen atoms, and the like.
Examples of the compound having an oxime sulfonate group represented by the formula (III) include: oxime sulfonate compounds represented by the following formulae (III-1) to (III-3), and the like.
Figure BDA0002313165110000122
In the formulae (III-1) to (III-3), R11With R of formula (III)10Are the same meaning. In the formulae (III-1) and (III-2), R12Is alkyl group having 1 to 12 carbon atoms or fluoroalkyl group having 1 to 12 carbon atoms. In the formula (III-3), X is an alkyl group, an alkoxy group, or a halogen atom. i is an integer of 0 to 3. Wherein, when i is 2 or 3, a plurality of xs may be the same or different.
The alkyl group represented by X is preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a straight or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.
Examples of the oxime sulfonate compound represented by the formula (III-3) include: and compounds represented by the following formulae (III-4) to (III-8), and the like.
Figure BDA0002313165110000131
The compounds represented by the formulae (III-4) to (III-8) are each: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, and commercially available compounds as described above can be used.
Examples of the N-sulfonyloxyimide compound include: n- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy), N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, 3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxy-2, 3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxy-2, 3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxy-2, 3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxy-2, 3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5, 6-oxy-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthalimide (N- ((trifluoromethylsulfonyloxy) oxy) naphthalimide), N- (camphorsulfonyloxy) naphthalimide, N- (4-methylphenylsulfonyloxy) naphthalimide, N- (phenylsulfonyloxy) naphthalimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthalimide, N- (4-trifluoromethylsulfonyloxy) naphthalimide, N- (4-fluorophenylsulfonyloxy) naphthalimide, N- (pentafluoroethylsulfonyloxy) naphthalimide, N- (heptafluoropropylsulfonyloxy) naphthalimide, N- (nonafluorobutylsulfonyloxy) naphthalimide, N- (ethylsulfonyloxy) naphthalimide, N- (propylsulfonyloxy) naphthalimide, N- (butylsulfonyloxy) naphthalimide, N- (pentylsulfonyloxy) naphthalimide, N- (hexylsulfonyloxy) naphthalimide, N- (heptylsulfonyloxy) naphthalimide, N- (octylsulfonyloxy) naphthalimide, N- (nonylsulfonyloxy) naphthalimide and the like.
As the onium salt, halogen-containing compound, diazomethane compound, sulfone compound, sulfonate compound, carboxylate compound and the like, compounds described in Japanese patent laid-open publication No. 2011-232632 can be used. For example: benzyl (4-hydroxyphenyl) methylthionium hexafluoroantimonate.
The photoacid generator (B) is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin (a). If the chemical amplification type positive photosensitive resin composition contains the oxime sulfonate group compound of the formula (III) as the photoacid generator (B), the obtained protective film has the advantage of excellent transparency.
Solvent (C)
The kind of the solvent (C) in the present invention is not particularly limited. Specific examples of the solvent (C) include a compound containing an alcoholic hydroxyl group (alcoholic hydroxyl group), a cyclic compound containing a carbonyl group (carbonyl group), and the like.
Specific examples of the compound having alcoholic hydroxyl group are acetol (acetol), 3-hydroxy-3-methyl-2-butanone (3-hydroxy-3-methyl-2-butanol), 4-hydroxy-3-methyl-2-butanone (4-hydroxy-3-methyl-2-butanol), 5-hydroxy-2-pentanone (5-hydroxy-2-pentanone), 4-hydroxy-4-methyl-2-pentanone (4-hydroxy-4-methyl-2-pentanone) (also called diacetone alcohol (DAA)), ethyl lactate (ethyl lactate), butyl lactate (butyl lactate), propylene glycol monomethyl ether (propylene glycol monomethyl ether), propylene glycol monoethyl ether (propylene glycol monoethyl ether), PGEE), Propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol mono-n-propyl ether (propylene glycol mono-n-propyl ether), propylene glycol mono-n-butyl ether (propylene glycol mono-n-butyl ether), propylene glycol mono-t-butyl ether (propylene glycol mono-t-butyl ether), 3-methoxy-1-butanol (3-methoxy-1-butanol), 3-methyl-3-methoxy-1-butanol (3-methyl-3-methoxy-1-butanol), or combinations thereof. It is noted that the compound having alcoholic hydroxyl group is preferably diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate or a combination thereof. The compound having an alcoholic hydroxyl group may be used alone or in combination of two or more.
Specific examples of the cyclic compound having a carbonyl group include γ -butyrolactone (γ -butyrolactone), γ -valerolactone (γ -valerolactone), δ -valerolactone (δ -valerolactone), propylene carbonate (propylene carbonate), N-methyl pyrrolidone (N-methyl pyrrolidone), cyclohexanone (cyclohexanone), cycloheptanone (cyclohexanone), and the like. Notably, the carbonyl-containing cyclic compound is preferably γ -butyrolactone, n-methylpyrrolidone, cyclohexanone, or a combination thereof. The carbonyl group-containing cyclic compounds may be used alone or in combination of two or more.
The compound having alcoholic hydroxyl group(s) may be used in combination with the cyclic compound having carbonyl group(s), and the weight ratio thereof is not particularly limited. The weight ratio of the compound having alcoholic hydroxyl group(s) to the cyclic compound having carbonyl group(s) is preferably 99/1 to 50/50; more preferably 95/5 to 60/40.
Other solvents may be contained within a range not impairing the effect of the present invention. Specific examples of other solvents are: (1) esters: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate or 3-methyl-3-methoxy-1-butyl acetate, etc.; (2) ketones: methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, or the like; or (3) ethers: diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, or the like.
The solvent (C) is used in an amount of 200 to 2000 parts by weight, preferably 200 to 1500 parts by weight, more preferably 200 to 1000 parts by weight, based on 100 parts by weight of the resin (a).
Unsaturated group-containing polyurethane Compound (D)
The unsaturated group-containing polyurethane compound (D) of the present invention can be obtained by a conventional method. Specific preparation methods may be, for example but not limited to: the unsaturated group-containing polyurethane compound (D) is prepared by reacting isocyanate with polyol and then reacting with hydroxyl group-containing (meth) acrylate; or the unsaturated group-containing polyurethane compound (D) is obtained by reacting an isocyanate with a hydroxyl group-containing (meth) acrylate and then reacting with a polyol. Preferably, the unsaturated group-containing polyurethane compound (D) is obtained by reacting a bifunctional isocyanate with a bifunctional polyol, followed by reacting with pentaerythritol tri (meth) acrylate. More preferably, the preparation method further comprises using a reaction catalyst, such as but not limited to a known urethanization catalyst such as dibutyltin dilaurate.
The above-mentioned hydroxyl group-containing (meth) acrylate may be exemplified by, but not limited to: 2-hydroxyethyl (meth) acrylate, hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl di (meth) acrylate, triglycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, epoxy acrylate, and the like, and may be used alone or in combination of 2 or more. Preferably, the hydroxyl group-containing (meth) acrylate is pentaerythritol tri (meth) acrylate.
Preferably, the isocyanate is an isocyanate having 2 or more isocyanate groups in the molecule, and can be exemplified by, but not limited to: aromatic system such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, toluidine diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate (hexamethylene diisocyanate), isophorone diisocyanate (isophorone diisocyanate), tolylene diisocyanate (hexamethylene diisocyanate), hydrogenated tolylene diisocyanate (dimethylhexamethylene diisocyanate), and dicyclohexylmethane diisocyanate; the isocyanate may be used singly or in admixture of 2 or more.
Preferably, the polyol may be, for example, but not limited to: poly (propylene oxide) diol, poly (propylene oxide) triol, copoly (ethylene oxide-propylene oxide) diol, poly (tetrahydrofuran) diol, ethoxylated bisphenol a, ethoxylated bisphenol S, spiroglycol, caprolactone-modified diol, carbonate diol, trimethylolpropane, pentaerythritol, and the like; the polyols may be used singly or in admixture of 2 or more.
The unsaturated group-containing polyurethane compound (D) has a polystyrene-equivalent weight-average molecular weight of 3500 to 30000 as measured by Gel Permeationchromatography (GPC).
If the weight average molecular weight of the unsaturated group-containing polyurethane compound (D) is not within the above range, the photosensitive resin composition obtained therefrom has a problem of poor development adhesion and transparency.
Preferably, the weight average molecular weight of the unsaturated group-containing polyurethane compound (D) is 4000 to 20000, more preferably 4500 to 10000. When the weight average molecular weight of the unsaturated group-containing polyurethane compound (D) is within the above range, the transparency of the photosensitive resin composition obtained therefrom is better.
Commercially available products of the unsaturated group-containing polyurethane compound (D) having a specific weight average molecular weight may be exemplified by, but not limited to:
(1) an unsaturated group-containing polyurethane compound (D) having two unsaturated groups per molecule: UX-3204 (weight-average molecular weight 13000), UX-4101 (weight-average molecular weight 6500), UXT-6000 (weight-average molecular weight 6000), UXT-6000-M30 (weight-average molecular weight 6000), UX-6101 (weight-average molecular weight 6500), UX-7101 (weight-average molecular weight 5500), UX-0937 (weight-average molecular weight 4000), UXF-4001-M3 (weight-average molecular weight 30000), UXF-4002 (weight-average molecular weight 12000), UV-2000B (weight-average molecular weight 13000), UV-3000B (weight-average molecular weight 18000), UV-3200B (weight-average molecular weight 10000), UV-3210EA (weight-average molecular weight 9000), UV-3300B (weight-average molecular weight 13000), manufactured by Nippon Kagaku (Kagaku Co., Ltd.), and, UV-3310B (weight-average molecular weight 5000), UV-3500BA (weight-average molecular weight 13000), UV-3520TL (weight-average molecular weight 14000), UV-6640B (weight-average molecular weight 5000), UN-350 (weight-average molecular weight 12500), UN-352 (weight-average molecular weight 5000), UN-353 (weight-average molecular weight 5000), UN-1255 (weight-average molecular weight 8000), UN-6060PTM (weight-average molecular weight 6000), UN-6200 (weight-average molecular weight 6500), UN-6202 (weight-average molecular weight 11000), UN-6303 (weight-average molecular weight 4000), UN-6304 (weight-average molecular weight 13000), UN-6305 (weight-average molecular weight 27000), UN-7600 (weight-average molecular weight 11500), UN-7700 (weight 20000) UN-9000PEP (weight average molecular weight 5000), UN-9200A (weight average molecular weight 15000), UA-W2A (weight average molecular weight 3500) manufactured by Mitsukamura chemical, EBECRYL 230 (weight average molecular weight 5000) manufactured by DAICEL-CYTEC, EBECRYL 4491 (weight average molecular weight 7000), EBECRYL 8307 (weight average molecular weight 3500), EBECRYL 8411 (weight average molecular weight 12000), KRM 8961 (weight average molecular weight 10000);
(2) an unsaturated group-containing polyurethane compound (D) having three unsaturated groups per molecule: UV-7510B (weight average molecular weight 3500) manufactured by Nippon synthetic chemistry (Strand);
(3) unsaturated group-containing polyurethane compound (D) having six unsaturated groups per molecule: UX-5002D-M20 (weight average molecular weight 3500), UX-5002D-P20 (weight average molecular weight 3500), UX-5003D (weight average molecular weight 7000) manufactured by Kakkiso Kagaku K;
(4) unsaturated group-containing polyurethane compound (D) having seven unsaturated groups per molecule: UV-6300B (weight-average molecular weight 3700) manufactured by Nippon synthetic chemistry (Strand);
(5) unsaturated group-containing polyurethane compound (D) having nine unsaturated groups per molecule: UX-5005 (weight average molecular weight 4500) manufactured by Nippon Chemicals (Strand), UV-7610B (weight average molecular weight 11000) manufactured by Nippon synthetic chemistry (Strand), UV-7620EA (weight average molecular weight 4100), UN-901T (weight average molecular weight 4000) manufactured by Neuro chemical (Strand);
(6) unsaturated group-containing polyurethane compound (D) having ten unsaturated groups per molecule: UX-3204 (weight-average molecular weight 13000) manufactured by Nippon Kagaku (Strand), UN-904 (weight-average molecular weight 4900) manufactured by Nippon Kagaku (Strand), UN-952 (weight-average molecular weight 6500 to 11000); and
(7) unsaturated group-containing polyurethane compound (D) having fifteen unsaturated groups per molecule: UN-3320HS (weight average molecular weight 5000) manufactured by ROOT CHEMICAL (STRAND).
Preferably, the unsaturated group-containing polyurethane compound (D) has at least six unsaturated groups per molecule, more preferably at least nine unsaturated groups per molecule. When the unsaturation per molecule of the unsaturated group-containing polyurethane compound (D) is within the above range, the resultant photosensitive resin composition is more excellent in development adhesion.
The unsaturated group-containing polyurethane compound (D) is used in an amount of 1 to 20 parts by weight, preferably 2 to 15 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the resin (a). If the polyurethane compound (D) does not contain an unsaturated group, the photosensitive resin composition obtained therefrom has a problem of poor development adhesion and transparency.
Other additives (E)
Optionally, the chemically amplified positive photosensitive resin composition of the present invention may contain other additives (E). Specific examples of the other additives (E) are a sensitizer (sensitizer), an adhesion promoter (adhesion promoter), a surfactant (surfactant), a solubility promoter (solubility promoter), an antifoaming agent (defoamer), or a combination thereof.
The kind of sensitizer is not particularly limited. The sensitizer is preferably a compound containing a phenolic hydroxyl group (phenolichthyxy), and specific examples thereof are:
(1) triphenol type compounds (trisphenol type compounds): such as tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-2, 3, 5-trimethylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -3-hydroxyphenyl methane, bis (4-hydroxy-3, 5-methylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -3-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -3-hydroxyphenyl methane, bis (4-hydroxy-, Bis (4-hydroxy-2, 5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3, 5-dimethylphenyl) -3, 4-dihydroxyphenylmethane, bis (4-hydroxy-2, 5-dimethylphenyl) -2, 4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3-hydroxyphenyl-methyl-2-methyl-phenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3, 5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2, 5-methyl, Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane or bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3, 4-dihydroxyphenylmethane and the like;
(2) biphenol-type compound (bisphenol type compound): such as bis (2,3, 4-trihydroxyphenyl) methane, bis (2, 4-dihydroxyphenyl) methane, 2,3, 4-trihydroxyphenyl-4 ' -hydroxyphenyl methane, 2- (2,3, 4-trihydroxyphenyl) -2- (2',3',4' -trihydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl) -2- (2',4' -dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4' -hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3' -fluoro-4 ' -hydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl) -2- (4' -hydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl) propane, 2- (4' -hydroxyphenyl) propane, and mixtures thereof, 2- (2,3, 4-trihydroxyphenyl) -2- (4 '-hydroxyphenyl) propane, 2- (2,3, 4-trihydroxyphenyl) -2- (4' -hydroxy-3 ',5' -dimethylphenyl) propane, or the like;
(3) polynuclear branched compounds (polynuclear branched compounds): such as 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene or 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (3-methyl-4-hydroxyphenyl) ethyl ] benzene;
(4) condensed type phenol compound (condensation type phenol compound): such as 1, 1-bis (4-hydroxyphenyl) cyclohexane, etc.;
(5) polyhydroxy benzophenones (polyhydroxybenzophenones): such as 2,3, 4-trihydroxybenzophenone, 2,4,4' -trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2,3, 4-trihydroxy-2 ' -methylbenzophenone, 2,3,4,4' -tetrahydroxybenzophenone, 2,4,2',4' -tetrahydroxybenzophenone, 2,4,6,3',4' -pentahydroxybenzophenone, 2,3,4,2',5' -pentahydroxybenzophenone, 2,4,6,3',4',5' -hexahydroxybenzophenone, 2,3,4,3',4',5' -hexahydroxybenzophenone, etc.; or
(6) Combinations of the above various phenolic hydroxyl group-containing compounds.
The sensitizer is used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the resin (a); preferably 8 to 40 parts by weight; and more preferably 10 to 35 parts by weight.
Specific examples of the adhesion promoter include melamine (melamine) compounds and silane-based compounds. The adhesion promoter serves to increase the adhesion between the film formed from the photocurable polysiloxane composition and the component or substrate.
Specific examples of commercially available melamine products include those manufactured by Mitsui chemical under the trade names Cymel-300 and Cymel-303; or the trade names MW-30MH, MW-30, MS-11, MS-001, MX-750, MX-706, etc., manufactured by Sanhe Chemicals.
When a melamine compound is used as an adhesion promoter, the melamine compound is used in an amount of 0 to 20 parts by weight based on 100 parts by weight of the resin (a); preferably 0.5 to 18 parts by weight; and more preferably 1.0 to 15 parts by weight.
Specific examples of the silane-based compound are vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like, 3-mercaptopropyltrimethoxysilane, a commercially available product (trade name: KBM403) manufactured by shin-Etsu chemical company, and the like.
When a silane-based compound is used as the adhesion promoter, the silane-based compound is used in an amount of 0 to 2 parts by weight based on 100 parts by weight of the resin (a); preferably 0.05 to 1 part by weight; and more preferably 0.1 to 0.8 parts by weight.
Specific examples of the surfactant are an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a polysiloxane surfactant, a fluorine surfactant, or a combination thereof.
Examples of the surfactant include (1) polyethylene glycol alkyl ethers (polyoxyyethylene ethers): polyethylene glycol dodecyl ether, and the like; (2) polyethylene glycol alkyl phenyl ethers (polyoxyyethylene alkyl ethers): polyethylene glycol octyl phenyl ether, polyethylene glycol nonyl phenyl ether, and the like; (3) polyethylene glycol diesters (polyethylene glycol diesters): polyethylene glycol dilaurate, polyethylene glycol distearate, and the like; (4) sorbitan fatty acid esters (sorbitan fat acid esters); and (5) fatty acid modified polyesters; and (6) tertiary amine modified polyurethanes and the like. Specific examples of commercially available surfactants are KP (manufactured by shin-Etsu chemical industry), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Cogrong oil and fat chemical industry), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by big Japan ink chemical industry (DIC)), Fluorade (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Nippon glass), SINOPOL E8008 (manufactured by Mitsui synthetic chemistry), F-475 (manufactured by big Japan ink chemical industry), or a combination thereof.
The base resin (A) is used in an amount of 100 parts by weight, and the surfactant is used in an amount of 0.5 to 50 parts by weight; preferably 1 to 40 parts by weight; and more preferably 3 to 30 parts by weight.
Examples of the defoaming agent include Surfynol MD-20, Surfynol MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol DF110D, Surfynol 104E, Surfynol 420, Surfynol DF37, Surfynol DF58, Surfynol DF66, Surfynol DF70, and Surfynol DF210 (manufactured by Air products), and the like.
The defoaming agent is used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the resin (a); preferably 2 to 9 parts by weight; and more preferably 3 to 8 parts by weight.
Examples of the dissolution accelerating agent include a nitrogen-hydroxy dicarboxyiimide compound (N-hydroxydicarboxyiimide) and a compound containing a phenolic hydroxyl group. Specific examples of the dissolution accelerating agent are compounds containing a phenolic hydroxyl group used in the o-naphthoquinone diazide sulfonate (B).
The amount of the dissolution accelerator used is 1 to 20 parts by weight based on 100 parts by weight of the resin (a); preferably 2 to 15 parts by weight; and more preferably 3 to 10 parts by weight.
Specific examples of the chemically amplified positive photosensitive resin composition are prepared in the following manner: the resin (a), the photoacid generator (B), the solvent (C), and the unsaturated group-containing polyurethane compound (D) are stirred in a stirrer to be uniformly mixed into a solution state, and if necessary, other additives (E) may be added.
The invention also provides a protective film, which is formed by coating the chemical amplification type positive photosensitive resin composition on a substrate, and then carrying out prebaking, exposure, development and postbaking treatment.
The invention further provides a component with the protective film, which comprises a substrate and the protective film.
Method for forming protective film
In some embodiments, the chemically amplified positive photosensitive resin composition of the present invention can be used as a material for forming a protective film of a display device. The present invention also includes a protective film for a display module, which is suitably formed from a chemically amplified positive photosensitive resin composition.
The method for forming the protective film comprises the following steps:
(1) a step of forming a coating film on a substrate using a chemically amplified positive photosensitive resin composition (hereinafter also referred to as "step (1)");
(2) a step of irradiating at least a part of the coating film with radiation (hereinafter also referred to as "step (2)");
(3) a step of developing the coating film after the irradiation with the radiation (hereinafter, also referred to as "step (3)"); and
(4) a step of heating the developed coating film (hereinafter also referred to as "step (4)").
According to the forming method, the protective film for the display module with excellent surface hardness, solvent resistance, heat resistance and voltage holding ratio can be formed. In addition, by using the chemically amplified positive photosensitive resin composition having good sensitivity, a protective film for display module having a fine and delicate pattern can be easily formed. Therefore, the formed protective film for a display device is suitable for a display device such as a liquid crystal display device or an organic EL display device.
[ step (1) ]
In this step, a chemically amplified positive photosensitive resin composition is applied to a substrate to form a coating film. Preferably, the solvent is removed by pre-bake coating.
Examples of the substrate include: glass, quartz, silicon substrates, resins, and the like. Examples of the resin include: polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, a hydride thereof, and the like. The prebaking conditions may vary depending on the kind of each component, the blending ratio, and the like, and may be set to about 70 ℃ to 120 ℃ and about 1 minute to 10 minutes.
[ step (2) ]
In this step, at least a part of the formed coating film is exposed to radiation. In exposure, exposure is usually performed through a mask having a predetermined pattern. The radiation used for the exposure is preferably radiation having a wavelength in the range of 190nm to 450nm, more preferably radiation containing ultraviolet rays of 365 nm. The exposure amount is a value obtained by measuring the intensity of radiation at 365nm wavelength by an illuminometer (OAI model356, manufactured by OAI Optical Association), and is preferably 500J/m2To 6,000J/m2More preferably 1,500J/m2To 1,800J/m2。
[ step (3) ]
In this step, the coating film irradiated with radiation is developed. By developing the exposed coating film, unnecessary portions (irradiated portions of radiation) are removed to form a predetermined pattern. The developing solution used in the developing step is preferably an alkaline aqueous solution. Examples of the base include: inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and amines; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and the like.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous alkali solution. From the viewpoint of obtaining appropriate developability, the concentration of the alkali in the aqueous alkali solution is preferably 0.1 mass% or more and 5 mass% or less. Examples of the developing method include: liquid coating method (puddlemethod), dipping method, shaking dipping method, spraying method, etc. The developing time varies depending on the composition of the chemically amplified positive photosensitive resin composition, and is about 10 seconds to 180 seconds. After the development treatment, the coating film is air-dried by performing, for example, running water washing for 30 to 90 seconds and then using, for example, compressed air or compressed nitrogen to form a desired pattern.
[ step (4) ]
In this step, the developed coating film is heated. In the heating, the patterned film is heated by using a heating device such as a hot plate or an oven to promote a hardening reaction of the resin (a) and obtain a hardened material. The heating temperature is, for example, about 120 ℃ to 250 ℃. The heating time varies depending on the type of heating machine, and is, for example, about 5 minutes to 30 minutes on a heating plate and about 30 minutes to 90 minutes in an oven. In addition, a step baking method in which 2 or more heating steps are performed may be used. In this way, a patterned thin film corresponding to the intended protective film for a display element can be formed on the surface of the substrate. The use of the cured film is not limited to the protective film for display modules, and the cured film may be used as a spacer or an interlayer insulating film.
The film thickness of the protective film for display element formed is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, still more preferably 0.1 μm to 4 μm.
Drawings
(none)
Detailed Description
The following describes the production method and application of the chemically amplified positive photosensitive resin composition of the present invention with reference to several preparation examples, examples and comparative examples.
Preparation of resin (A)
Preparation example A-1
A four-necked conical flask having a volume of 1000 ml was provided with a nitrogen inlet, a stirrer, a heater, a condenser tube and a thermometer, and after introducing nitrogen gas, 10 parts by weight of methacrylic acid (hereinafter referred to as MAA), 80 parts by weight of 1-ethoxyethyl methacrylate (a-2-1), 10 parts by weight of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 10 parts by weight of 2,2' -azobis (2, 4-dimethylvaleronitrile) (hereinafter referred to as ADVN), 9 parts by weight of isododecyl mercaptan (hereinafter referred to as TDM) and 240 parts by weight of diethylene glycol dimethyl ether (hereinafter referred to as Diglyme) solvent were added. Subsequently, the above ingredients were slowly stirred to warm the solution to 70 ℃ and polymerized for 6 hours at this temperature. Then, the solvent is devolatilized to obtain resin (A-1).
Preparation examples A-2 to A-10 and preparation comparative examples A '-1 to A' -2
The resins (A-2) to (A-10) and the preparation of comparative examples (A '-1) to (A' -2) were prepared similarly to the resin (A-1) preparation described above, wherein the kinds and amounts of the monomers used are shown in Table 1. Except that the amounts of the solvent, the catalyst and the molecular weight modifier used, the reaction temperature and the reaction time of the polycondensation were different from those of the resin (A-1), they are also shown in Table 1.
Example 1
Preparation of chemically amplified positive photosensitive resin composition
The chemically amplified positive photosensitive resin composition of example 1 was prepared by adding 100 parts by weight of the resin (A-1), 0.1 part by weight of benzyl (4-hydroxyphenyl) methylthionium hexafluoroantimonate (B-1) and 1 part by weight of UXF-4001-M3 (D-1; weight average molecular weight 30000, having 2 unsaturated groups) to 200 parts by weight of propylene glycol methyl ether acetate (C-1) and stirring the mixture uniformly with a shaking type stirrer.
Forming a protective film
A coating film of about 3 μm was obtained by spin coating on a mother glass substrate (100 × 100 × 0.7.7 mm), prebaked at 110 ℃ for 2 minutes, and then a positive resist mask was placed between an exposure machine and the coating film, and the coating film was irradiated with ultraviolet light from the exposure machine at an energy of 800J/m2. The exposed coating film was immersed in a 2.38% aqueous TMAH solution at 23 ℃ for 70 seconds to remove the exposed portion, and then washed with clear waterAnd (5) cleaning. Finally, the substrate was post-baked at 220 ℃ for 45 minutes to obtain a protective film on the mother glass substrate of example 1.
Specific conditions and evaluation results of example 1 are shown in table 2.
Examples 2 to 20 and comparative examples 1 to 4
The chemically amplified positive photosensitive resin compositions and the protective films of examples 2 to 20 and comparative examples 1 to 4 were obtained in the same manner as in example 1. Except that the composition or the amount used was changed in examples 2 to 20 and comparative examples 1 to 4. Specific conditions and evaluation results for examples 2 to 20 and comparative examples 1 to 4 are shown in tables 2 and 3.
Evaluation method
(1) Development adhesion property:
after a coating film of a chemically amplified positive photosensitive resin composition is formed by the above method for forming a protective film, the coating film is irradiated with 1000J/m by a mercury lamp through a pattern resist having a line and space pattern with a width of 1 to 10 μm2Ultraviolet rays of (1). Subsequently, development treatment was performed at 25 ℃ for 70 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, and then washing was performed with flowing water for 1 minute using ultrapure water. The peeling of the line and space pattern having a width of 1 μm to 10 μm after cleaning was observed with a microscope as an evaluation of development adhesion.
◎ No Pattern peeling
○ slight pattern peeling
△ partial peeling of the Pattern
Gamma rays: the entire surface of the pattern is peeled off.
(2) Transparency of
The transparency referred to in the present invention is an evaluation of the transmittance of the cured film under light having a wavelength of 400 nm. The chemically amplified positive photosensitive resin compositions of examples and comparative examples were applied to a glass substrate using a spinner, and then prebaked at 90 ℃ for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. Then, the coating film was calcined for 30 minutes using an oven heated to 230 ℃ to form a cured film. Next, the transmittance of the cured film was measured at 25 ℃ using an ultraviolet-visible spectrophotometer ("V-670" by Japan Spectroscopy) as an index of transparency. The evaluation criteria for the transmittance at 400nm are as follows, wherein a higher transmittance means better transparency.
◎, the transmittance is more than 98%
○, the transmittance is more than 95 percent and less than 98 percent
△, the transmittance is more than 90 percent and less than 95 percent
Gamma rays: the transmittance is less than 90%.
Referring to table 2, when the mixture of the resin (a) in the chemical amplification type positive photosensitive resin composition includes the unsaturated carboxylic acid monomer (a-1) and the monomer (a-2) containing the acid dissociable group, and the chemical amplification type positive photosensitive resin composition includes the polyurethane compound (D) containing the unsaturated group and having the weight average molecular weight of 3500-30000, the protective film prepared from the composition has good development adhesion and transparency.
Further, when the mixture for forming the resin (a) includes the epoxy group-containing unsaturated monomer (a-3), and/or the unsaturated group-containing polyurethane compound (D) has at least six unsaturated groups per molecule, the development adhesion of the protective film can be further improved. When the photoacid generator (B) of the chemically amplified positive photosensitive resin composition comprises an oxime sulfonate group compound and/or the unsaturated group urethane compound (D) has a molecular weight of 4000 to 20000, the transparency of the protective film can be further improved.
On the other hand, as shown in table 3, when the mixture for forming the resin (a) in the chemical amplification type positive photosensitive resin composition does not use the monomer (a-2) containing an acid dissociable group, and/or the chemical amplification type positive photosensitive resin composition does not use the unsaturated group-containing urethane compound (D) having a weight average molecular weight of 3500 to 30000, the protective film obtained from the composition is poor in both development adhesion and transparency.
The invention provides a chemical amplification type positive photosensitive resin composition, which can ensure that a protective film prepared from the composition has good development adhesion and transparency by virtue of a specific composition.
While the invention has been described with reference to specific embodiments, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.
Figure BDA0002313165110000261
Figure BDA0002313165110000271
Figure BDA0002313165110000281
TABLE 3
Figure BDA0002313165110000291
Figure BDA0002313165110000301

Claims (13)

1. A chemically amplified positive photosensitive resin composition, comprising:
a resin (A) obtained by copolymerizing a mixture comprising an unsaturated carboxylic acid monomer (a-1) and a monomer (a-2) containing an acid dissociable group;
a photoacid generator (B);
a solvent (C); and
an unsaturated group-containing polyurethane compound (D), wherein the weight average molecular weight of the unsaturated group-containing polyurethane compound (D) is 3500 to 30000.
2. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the unsaturated group-containing polyurethane compound (D) is 4000 to 20000.
3. The chemically amplified positive photosensitive resin composition as claimed in claim 1, wherein the weight average molecular weight of the unsaturated group-containing polyurethane compound (D) is 4500 to 10000.
4. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the unsaturated group-containing polyurethane compound (D) has at least six unsaturated groups per molecule.
5. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the unsaturated group-containing polyurethane compound (D) has at least nine unsaturated groups per molecule.
6. The chemical amplification type positive photosensitive resin composition according to claim 1, wherein the acid-dissociable group has a structure represented by the following formula (I):
Figure FDA0002313165100000011
in the formula (I), each of R1 and R2 is independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or an aryl group, in which a part or all of the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, or the aryl group may be substituted; moreover, the R1 and the R2 are not both hydrogen atoms; r3 is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group or an aryl group; wherein a part or all of hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, the aralkyl group and the aryl group of the R3 may be substituted; the R1 and the R3 may be bonded to each other to form a cyclic ether structure together with the carbon atom to which the R1 is bonded and the oxygen atom to which the R3 is bonded.
7. The chemically amplified positive photosensitive resin composition of claim 1, wherein the mixture comprises an epoxy group-containing unsaturated monomer (a-3).
8. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the photoacid generator (B) is a compound containing an oxime sulfonate group represented by the formula (iii):
Figure FDA0002313165100000021
in the formula (III), R10 is an alkyl group, alicyclic hydrocarbon group, aryl group having 1 to 20 carbon atoms, or a group in which hydrogen atoms of the above groups are partially or completely substituted; and, the x is a bond.
9. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the photoacid generator (B) is used in an amount of 0.1 to 10 parts by weight, the solvent (C) is used in an amount of 200 to 2000 parts by weight, and the unsaturated group-containing polyurethane compound (D) is used in an amount of 1 to 20 parts by weight, based on 100 parts by weight of the resin (a).
10. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the unsaturated carboxylic acid monomer (a-1) is used in an amount of 5 to 95 parts by weight and the acid-dissociable group-containing monomer (a-2) is used in an amount of 5 to 95 parts by weight, based on 100 parts by weight of the mixture.
11. The chemically amplified positive photosensitive resin composition of claim 7, wherein the epoxy group-containing unsaturated monomer (a-3) is used in an amount of 5 to 90 parts by weight based on 100 parts by weight of the mixture.
12. A protective film, which is formed by coating the chemically amplified positive photosensitive resin composition of any one of claims 1 to 11 on a substrate, and then subjecting the coating to prebaking, exposure, development and postbaking.
13. An assembly with a protective film, comprising a substrate and the protective film of claim 12.
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