TW202024793A - Chemically amplified positive photosensitive resin composition and application thereof - Google Patents

Abstract

A chemically amplified positive photosensitive resin composition is provided, in which the composition includes resin (A), a photoacid generator (B) and solvent (C). A protective film formed by the chemically amplified positive photosensitive resin composition and an element including the protective film are also provided. The protective film has sufficient sensitivity and sufficient chemical resistance. The protective film may be applied to form a planarization film of a thin-film transistor, an interlayer insulating film, or a core material or a coating layer of an optical waveguide.

Description

Chemically amplified positive photosensitive resin composition and the same application

The invention relates to a chemically amplified positive photosensitive resin composition, a protective film formed therefrom, and an element with a protective film. Among them, in particular, it provides a positive photosensitive resin composition for a protective film with characteristics such as good sensitivity and chemical resistance after exposure and development. This protective film is suitable for thin film transistor (Thin Film Transistor; TFT) substrates of liquid crystal display elements, organic EL display elements, etc., as flattening films, interlayer insulating films, or core materials or cladding materials for optical waveguides.

Display elements such as thin-film transistor-type liquid crystal display elements or organic electroluminescence devices (organic electroluminescence devices, organic EL elements) generally include insulating films such as interlayer insulating films or planarization films. Such an insulating film is usually formed using a radiation-sensitive composition. From the viewpoint of patterning performance, conventionally known positive radiation-sensitive resin compositions using acid generators such as naphthoquinone diazide (naphthoquinone diazide) are used (refer to Japanese Patent Laid-Open No. 2001-354822). for Such a radiation-sensitive composition, but a variety of radiation-sensitive compositions have been proposed in recent years.

For example, a positive type chemical amplification material is proposed, the purpose of which is to form a display element with a higher sensitivity than the aforementioned positive type radiation-sensitive resin composition using acid generators such as naphthoquinone diazide The cured film used (see Japanese Patent Laid-Open No. 2004-4669). The positive chemical amplification material contains a crosslinking agent, an acid generator and an acid dissociable resin. The acid-dissociable resin has a protective group that can be dissociated by the action of an acid. Although the acid-dissociable resin itself is insoluble or hardly soluble in an alkaline aqueous solution, the protective group is dissociated by the action of an acid and becomes soluble in alkali Sexual aqueous solution. In addition, a positive radiation-sensitive composition containing a resin having an acetal structure and/or a ketal structure and an epoxy group and an acid generator has also been proposed (see Japanese Patent Laid-Open No. 2004-264623 and Japanese Patent Laid-Open 2011-215596 and Japanese Patent Laid-Open No. 2008-304902).

In these radiation-sensitive resin compositions, in addition to high radiation sensitivity, storage stability that does not change in viscosity even after long-term storage is required, so that the cured film formed by these radiation-sensitive resin compositions can achieve high radiation sensitivity. Chemical resistance to swelling due to developer etc. Furthermore, the pattern formed by the cured film can also achieve: after development, the pattern and the substrate are sufficiently adhered to be difficult to peel off; the cured film has sufficient transparency; and even if it is left after exposure, the pattern is The substrate adheres sufficiently to be difficult to peel off.

However, the sensitivity and chemical resistance of current photosensitive resin compositions are still unacceptable in the industry.

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 resin (A), photoacid generator (B) and solvent (C), which will be described in detail below.

Resin (A)

Resin (A) is obtained by copolymerization of the mixture. This mixture includes at least polymerizable monomers and thiol compounds with specific structures. The polymerizable monomer includes unsaturated carboxylic acid monomer (a-1), acid-dissociable group-containing monomer (a-2) with a specific structure, monomer (a-1), monomer (a -2) Other unsaturated monomers (a-3).

Polymerizable monomer Unsaturated carboxylic acid monomer (a-1)

The unsaturated carboxylic acid monomer (a-1) of the present invention refers to a compound containing a carboxylic acid group or carboxylic acid anhydride structure and an unsaturated bond used for polymerization. The structure is not particularly limited, and may include, but is not limited to, an unsaturated monomer Carboxylic acid compound, unsaturated dicarboxylic acid compound, unsaturated acid anhydride compound, polycyclic unsaturated carboxylic acid compound, polycyclic unsaturated dicarboxylic acid compound, polycyclic unsaturated acid anhydride compound.

Specific examples of the aforementioned unsaturated monocarboxylic acid compounds: (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-(meth)acrylic acid ethoxy succinate, 2 -(Meth)acrylic acid ethoxy hexahydrophthalate, 2-(meth)acrylic acid ethoxy phthalate, omega-carboxyl polycaprolactone polyol monoacrylate (trade name For ARONIX M-5300, manufactured by East Asia Synthesis).

Specific examples of the aforementioned unsaturated dicarboxylic acid compound include maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, citraconic acid and the like. In the specific example of the present invention, the unsaturated dicarboxylic acid anhydride compound is the acid anhydride compound of the aforementioned unsaturated dicarboxylic acid compound.

Specific examples of the aforementioned polycyclic unsaturated carboxylic acid compounds: 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 aforementioned polycyclic unsaturated dicarboxylic acid compound are: 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene.

The aforementioned polycyclic unsaturated dicarboxylic acid anhydride compound is an acid anhydride compound of the aforementioned polycyclic unsaturated dicarboxylic acid compound.

Preferred specific examples of the above-mentioned unsaturated carboxylic acid monomer (a-1) are acrylic acid, methacrylic acid, maleic anhydride, 2-methacrylic acid ethoxy succinate, and 2-methacrylic acid ethoxylate. Oxyhexahydrophthalic acid or a combination thereof.

The above-mentioned unsaturated carboxylic acid monomer (a-1) can be used singly or as a mixture of plural kinds. Based on 100 parts by weight of the polymerizable monomer, the unsaturated carboxylic acid monomer (a-1) is used in an amount of 1 to 50 parts by weight; preferably 3 to 40 parts by weight; more preferably 5 Parts by weight to 30 parts by weight.

Monomers containing acid dissociable groups (a-2)

The acid-dissociable group-containing monomer (a-2) of the present invention has an acid-dissociable group represented by the following formula (1).

The acid-dissociable group of the acid-dissociable group-containing monomer (a-2) is dissociated by the action of the acid generated from the photoacid generator (B) described later during exposure to generate polar groups, so it is originally insoluble Or the resin (A) that is hardly soluble in the aqueous alkali solution becomes soluble in the aqueous alkali solution.

The acid dissociable group-containing monomer (a-2) is not particularly limited as long as it has a structure as in formula (1). The monomer (a-2) containing the acid dissociable group of formula (1) can be easily dissociated by acid. In the above formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or an aryl group, wherein part or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group or aryl group May be substituted; and R ¹ and R ^{2 are} not hydrogen atoms at the same time; R ³ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, or an aryl group; wherein R ³ is an alkyl group, an alicyclic hydrocarbon group, or an aralkyl group And part or all of the hydrogen atoms of the aryl group may be substituted; R ¹ and R ³ may be linked to form a cyclic ether structure. For example: R ¹ and R ³ can be bonded to each other to form a cyclic ether structure together with the carbon atom bonded to R ¹ and the oxygen atom bonded to R ³ .

Examples of the alicyclic hydrocarbon group represented by R ¹ and R ² 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, and adamantyl.

Examples of the aryl group represented by R ¹ and R ² include aryl groups having 6 to 14 carbon atoms. The above-mentioned aryl group having 6 to 14 carbon atoms may be a monocyclic ring, a structure formed by connecting monocyclic rings, or a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include phenyl and naphthyl.

Examples of the substituents of the substituted alkyl group, alicyclic hydrocarbon group, and aryl group represented by R ¹ and R ² include halogen atoms, hydroxyl groups, nitro groups, cyano groups, carboxyl groups, carbonyl groups, and alicyclic hydrocarbon groups ( For example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bornyl, norbornyl, adamantyl, etc.), aryl (such as phenyl, naphthyl, etc.), alkoxy (such as Methoxy, ethoxy, propoxy, n-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and other alkoxy groups with 1 to 20 carbon atoms, etc.), acyl groups (e.g. Acetyl, propionyl, butyryl, isobutyryl and other carbon numbers of 2 to 20 acyl groups, etc.), acyloxy groups (e.g., acetoxy, propoxy, butoxy, tertiary butoxy) Group, tertiary pentyloxy group and the like having 2 to 10 carbon atoms, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc., carbon number 2 to 20) Alkoxycarbonyl), haloalkyl (e.g. methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl, n-octadecyl Alkyl groups and other linear alkyl groups, isopropyl, isobutyl, tertiary butyl, neopentyl, 2-hexyl, 3-hexyl and other branched alkyl groups; cyclopropyl, cyclobutyl, Cyclopentyl, norbornyl, adamantyl and other alicyclic hydrocarbon groups, groups obtained by substituting part or all of the hydrogen atoms of the above groups with halogen atoms), hydroxyalkyl groups (for example, hydroxymethyl, etc.), etc. .

Represented by R ³ above alkyl group, alicyclic hydrocarbon group, an aryl group described above can be applied to each of the groups R ¹ and R ² is represented. In addition, the above-mentioned alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, and an n-propyl group. Examples of the aralkyl group represented by R ³ include benzyl, phenethyl, naphthylmethyl, and naphthylethyl.

The cyclic ether structure formed by bonding R ¹ and R ³ to each other is preferably a cyclic ether structure having 3 to 20 ring members, more preferably a cyclic ether structure having 5 to 8 ring members, and more Preferred are tetrahydrofuran and tetrahydropyran.

Examples of the group represented by the above formula (1) include groups represented by the following formula.

Examples of the acid-dissociable group-containing monomer (a-2) include: 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate Ester, 1-isobutoxyethyl methacrylate, 1-tert-butoxyethyl methacrylate, 1-(2-chloroethoxy)ethyl methacrylate, 1-(2 methacrylate) -Ethylhexyloxy)ethyl, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1-(2-cyclohexylethoxy)ethyl methacrylate , 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, tetrahydrofurfuryl methacrylate (tetrahydrofurfuryl methacrylate), 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-third butoxyethyl acrylate Ester, 1-(2-chloroethoxy)ethyl acrylate, 1-(2-ethylhexyloxy)ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexoxyethyl 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)ethoxy Carbonyl)-2-norbornene, p-1-ethoxyethoxystyrene or m-1-ethoxyethoxystyrene, p-1-methoxyethoxystyrene or m- 1-Methoxyethoxystyrene, p-1-n-butoxyethoxystyrene or m-1-n-butoxyethoxystyrene, p-1-isobutoxyethoxy Styrene or m-1-isobutoxyethoxystyrene, p-1-(1,1-dimethylethoxy)ethoxystyrene or m-1-(1,1-dimethyl Ethoxy)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-n-propoxyethoxystyrene or m -1-n-propoxyethoxystyrene, p-1-cyclohexoxyethoxystyrene or m-1-cyclohexoxyethoxystyrene, p-1-(2-cyclohexyl Ethoxy)ethoxystyrene or m-1-(2-cyclohexylethoxy)ethoxystyrene, p-1-benzyloxyethoxystyrene or m-1-benzyloxyethyl Oxystyrene and so on.

The acid dissociable group-containing monomer (a-2) is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate , 1-benzyloxyethyl methacrylate, methacrylic acid 1-cyclohexyloxyethyl, tetrahydrofurfuryl methacrylate, more preferably 2-tetrahydropyranyl methacrylate and tetrahydrofurfuryl methacrylate.

Based on the total usage amount of the polymerizable monomer being 100 parts by weight, the content of the acid dissociable group-containing monomer (a-2) is 5 parts by weight to 90 parts by weight, preferably 10 parts by weight to 80 parts by weight , More preferably 15 parts by weight to 70 parts by weight. If the monomer (a-2) containing an acid dissociable group is not used, there will be problems of poor sensitivity and chemical resistance.

Other unsaturated monomers (a-3)

The other unsaturated monomer (a-3) in the present invention means an unsaturated monomer other than the monomer (a-1) and the monomer (a-2). In some embodiments, this other unsaturated monomer (a-3) includes an epoxy-containing unsaturated monomer (a-3-1), alkyl (meth)acrylate, and (meth)acrylate Cyclic ester, aryl (meth)acrylate, diester of unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, polyether of (meth)acrylate, aromatic vinyl compound and other unsaturated Compound.

Unsaturated monomers containing epoxy groups (a-3-1)

The epoxy-containing unsaturated monomer (a-3-1) may include, but is not limited to, epoxy-containing (meth)acrylate compounds, epoxy-containing α-alkyl acrylate compounds, ring An oxypropyl ether compound, an ethylenically unsaturated monomer having an oxetanyl group represented by formula (4), and any combination of the above.

In formula (4), R ⁸ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; R ⁹ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; R ¹⁰ , R ¹¹ , R ¹² and R ¹³ Each independently represents a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group with a carbon number of 1 to 4, or a perfluoroalkyl group with a carbon number of 1 to 4; and a represents an integer of 1 to 6.

Specific examples of the aforementioned epoxy group-containing (meth)acrylate compound are: glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-(meth)acrylate Epoxybutyl ester, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate.

Specific examples of the aforementioned epoxy-containing α-alkyl acrylate compounds are: α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, α -6,7-Ethoxyheptyl acrylate.

Specific examples of the aforementioned glycidyl ether compound include o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, and p-vinylbenzylglycidylether. -Based glycidyl ether (p-vinylbenzylglycidylether).

Specific examples of the aforementioned ethylenically unsaturated monomer having an oxetanyl group as shown in formula (4) may include, but are not limited to, methacrylate compounds, acrylate compounds or have the following formula (4-1 ) To an unsaturated monomer of the structure represented by formula (4-4).

The aforementioned methacrylate compounds may include, but are not limited to, 3-(methacryloyloxymethyl)oxetane [3-(methacryloyloxymethyl)oxetane; OXMA], 3-(methacryloyloxymethyl)oxetane; (Methyl)-3-ethyloxetane [3-(methacryloyloxymethyl)-3-ethyloxetane; EOXMA], 3-(methacryloyloxymethyl)-3-methyloxetane [3-(methacryloyloxymethyl)-3-methyloxetane; MOXMA], 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3- (Methacryloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 3-(methyl (Methacryloxymethyl)-2,2-difluorooxetane, 3-(methacryloxymethyl)-2,2,4-trifluorooxetane, 3- (Methacryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloxyethyl)oxetane, 3-(methyl Allyloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl) Ethyl)-2-trifluoromethyloxetane, 3-(methacryloxyethyl)-2-pentafluoroethyloxetane, 3-(methacryloxyethyl) Ethyl)-2-phenyloxetane, 2,2-difluoro-3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl) )-2,2,4-trifluorooxetane or 3-(methacryloxyethyl)-2,2,4,4-tetrafluorooxetane and other compounds.

The aforementioned acrylate compounds may include, but are not limited to, 3-(acryloxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3- (Acryloxymethyl)-3-Methyloxetane, 3-(Acryloxymethyl)-2-Methyloxetane, 3-(Acryloxymethyl) -2-Trifluoromethyloxetane, 3-(acryloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloxymethyl)-2-benzene Oxetane, 3-(propenyloxymethyl)-2,2-difluorooxetane, 3-(propylene Oxymethyl)-2,2,4-trifluorooxetane, 3-(propenoxymethyl)-2,2,4,4-tetrafluorooxetane, 3- (Acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-(acryloyloxyethyl) Oxetane, 3-(propenyloxyethyl)-2-trifluoromethyloxetane, 3-(propenyloxyethyl)-2-pentafluoroethyloxetane Alkyl, 3-(propenyloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(propenyloxyethyl)oxetane, 3-(propene Compounds such as oxyethyl)-2,2,4-trifluorooxetane or 3-(propenoxyethyl)-2,2,4,4-tetrafluorooxetane .

The aforementioned unsaturated monomers having the structures shown in formula (4-1) to formula (4-4) are as follows.

In some embodiments, the epoxy-containing unsaturated monomer (a-3-1) may further include other ethylenically unsaturated monomers with oxetanyl groups, such as 3-methyl- 3-(vinyloxymethyl)oxetane [3-methyl-3-(vinyloxymethyl)oxetane; MOXV], 3-ethyl-3-(vinyloxymethyl)oxetane[3 -ethyl-3-(vinyloxymethyl)oxetane; EOXV], 3-propyl-3-(vinyloxymethyl)oxetane, 3-methyl-3-(2-vinyloxyethyl)oxy Etidine, 3-ethyl-3-(2-vinyloxyethyl)oxetane, 3-propyl-3-(2-vinyloxyethyl)oxetane, 3 -Methyl-3-(3-vinyloxypropyl)oxetane, 3-ethyl-3-(3-vinyloxypropyl)oxetane, 3-propyl-3- (3-vinyloxypropyl)oxetane, 3-methyl-3-(3-vinyloxybutyl)oxetane, 3-ethyl-3-(3-vinyloxy Butyl) oxetane, 3-propyl-3-(3-vinyloxybutyl) oxetane, ethylene glycol [(3-ethyl-3-oxetanyl) methyl Base] vinyl ether, propylene glycol [(3-ethyl-3-oxetanyl) methyl] vinyl ether or 3,3-bis[(vinyloxy) methyl] oxetane, etc. A vinyl ether compound having an oxetanyl group.

Based on 100 parts by weight of the total amount of polymerizable monomers used, the content of the epoxy group-containing unsaturated monomer (a-3-1) is 5 parts by weight to 80 parts by weight, preferably 10 parts by weight To 75 parts by weight, more preferably 15 parts by weight to 70 parts by weight. If the epoxy group-containing unsaturated monomer (a-3-1) is used, chemical resistance can be further improved.

Specific examples of the aforementioned alkyl (meth)acrylate are: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (methyl) ) N-butyl acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate.

Specific examples of the aforementioned alicyclic (meth)acrylate esters are: cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]dec-8 -Base (meth)acrylate (or dicyclopentyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofuran (meth)acrylate ester.

Specific examples of the aforementioned aryl (meth)acrylate are phenyl (meth)acrylate and benzyl (meth)acrylate.

Specific examples of the aforementioned unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, and diethyl itaconate.

Specific examples of the aforementioned hydroxyalkyl (meth)acrylate are: 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

Specific examples of the aforementioned (meth)acrylate polyether include polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate.

Specific examples of the aforementioned aromatic vinyl compounds are styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene.

Specific examples of other unsaturated compounds other than the foregoing: acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methyl Acrylamide, ethyl vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, N-cyclohexylmaleimide, N-phenyl Maleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-butanediimidate-4-male N-succinimidyl butyrate, N-succinimidyl-6-maleimidin caproate, N-succinimidyl-3-maleimidin propionate, N-( 9-acridinyl)maleimide.

The above-mentioned other unsaturated monomers (a-3) can be used singly or in mixture of plural kinds. Based on the total usage amount of the polymer monomer being 100 parts by weight, the content of the other unsaturated monomer (a-3) is 5 parts by weight to 94 parts by weight, preferably 10 parts by weight to 87 parts by weight, More preferably, it is 15 parts by weight to 80 parts by weight.

Thiol compound

The mixture for the synthetic resin (A) of the present invention contains a thiol compound, which has a structure represented by the following formula (2).

XR ⁴ -SH formula (2)

In the formula (2), X represents an ester group, a hydroxyl group, an amino group, or an alkoxysily group, and R ⁴ represents a substituted or unsubstituted alkylene or aryl group.

The alkylene group of R ⁴ may be a linear, branched or cyclic alkylene group. Examples of linear alkylene groups include methylene, ethylene, n-propyl, n-butyl, n-pentyl and n-hexylene. Examples of branched alkylene groups include isopropylidene and 2-ethylhexylene. Examples of cyclic alkylene groups include cycloalkylene and cyclobutylene. In addition, the alkylene group may have a substituent. From the viewpoint of making the present invention have a good effect, the alkylene group preferably has 1 to 20 carbon atoms, and more preferably, may have 2 to 18 carbon atoms.

Examples of the arylene group for R ⁴ include phenylene, tolylenyl, xylene, naphthylene, and biphenylene. The arylene group may have a substituent.

Examples of ester groups of X include groups represented by formula (2-1) or formula (2-2):

In formula (2-1), R ¹⁴ represents an alkyl group or an aryl group; or

In formula (2-2), R ¹⁵ represents a hydrogen atom, an alkyl group, or an aryl group.

The alkyl group of R ¹⁴ or R ¹⁵ may be a linear, branched, or cyclic alkyl group. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl. Examples of branched alkyl groups include isopropyl, isobutyl, and 2-ethylhexyl. Examples of cyclic alkyl groups include cyclopropyl and cyclobutyl. In addition, the alkyl group may have a substituent. From the viewpoint of making the present invention have a good effect, the alkyl group preferably has 1 to 20 carbon atoms, and more preferably, may have 2 to 18 carbon atoms.

Examples of the above-mentioned aryl group for R ¹⁴ or R ¹⁵ include phenyl, tolyl, xylyl, naphthyl, and biphenyl. The aryl group may be a group formed by substituting a hydrogen atom of the group.

Examples of the amino group of X include the group represented by formula (2-3):

In formula (2-3), R ¹⁶ and R ¹⁷ each represent a hydrogen atom, an alkyl group or an aryl group, and R ¹⁶ and R ¹⁷ may form a cyclic structure.

Examples of the alkyl group and aryl group for R ¹⁶ and R ¹⁷ include those mentioned for R ¹⁴ or R ¹⁵ . Whereas in the case where R ¹⁶ and R ¹⁷ form a cyclic structure, R ¹⁶ and R ¹⁷ may form a pyrrole ring with N as shown in formula (2-3), for example. From the viewpoint of making the present invention effective, the alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 4 carbon atoms; and the aryl group preferably has 6 to 18 carbon atoms , And more preferably have 6 to 8 carbon atoms.

Examples of the alkoxysilyl group of X include the group represented by formula (2-4): (R ¹⁸ O) _p (R ¹⁹ ) _3-p Si- formula (2-4)

In formula (2-4), R ¹⁸ represents an alkyl group, R ¹⁹ represents a hydrogen atom or an alkyl group, and p represents an integer of 1 to 3.

Examples of the alkyl group of R ¹⁸ or R ¹⁹ include the examples of the alkyl group mentioned in R ¹⁴ or R ¹⁵ . From the viewpoint of giving the present invention a good effect, the alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 4 carbon atoms.

Specific examples of the compound represented by formula (2) include: compounds in which X is an ester group such as 2-ethylhexyl 3-mercaptopropionate and 2-mercaptoethyl octanoate; compounds in which X is a hydroxyl group such as 9-mercapto- 1-nonanol and 11-mercapto-1-undecyl alcohol; compounds in which X is an amino group such as 11-amino-1-undecanethiol and 1H-pyrrole-1-undecanethiol; and, wherein X is an alkane Oxysilyl compounds such as 3-mercaptopropyl triethoxy silane and 3-mercaptopropyl (dimethoxy 基)methylsilane.

Based on the total usage amount of the polymerizable monomer being 100 parts by weight, the content of the thiol compound having the structure of formula (2) is 1 part by weight to 15 parts by weight, preferably 1.5 parts by weight to 14 parts by weight , More preferably 2 parts by weight to 12 parts by weight. If the thiol compound having the structure of formula (2) is not used, there will be a problem of poor sensitivity.

Synthetic method of resin (A)

For example, by using a radical polymerization initiator, a monomer corresponding to a predetermined structural unit can be polymerized in an appropriate solvent to produce the resin (A). For example, it is preferable to synthesize by the following method: a solution containing a monomer and a radical polymerization initiator is dropped into a solution containing a reaction solvent or a monomer to carry out a polymerization reaction; a solution containing a monomer, And a method in which a solution containing a radical polymerization initiator is added dropwise to a solution containing a reaction solvent or a monomer to carry out the polymerization reaction; multiple solutions containing each monomer and a solution containing a radical polymerization initiator , The method of performing polymerization reaction by adding dropwise to the solution containing the reaction solvent or monomer.

Examples of the solvent used in the polymerization reaction of the resin (A) include the same solvents as those shown in the solvent (C) described below.

Common free radical polymerization initiators can be used as the polymerization initiators for the polymerization reaction, for example, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis Isobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile) , 2,2'-Azobis (methyl 2-methylpropionate) and other azo compounds; benzyl peroxide, lauryl peroxide, tertiary butyl peroxide trimethyl acetic acid Ester, 1,1'-bis-(the Tributyl peroxide) cyclohexane and other organic peroxides; hydrogen peroxide, etc.

In the polymerization reaction of the resin (A), in order to adjust the molecular weight, the thiol compound having the structure of the formula (2) is used as the molecular weight modifier. However, other molecular weight modifiers can also be used in an appropriate amount without affecting the overall physical properties. The other molecular weight modifiers include, for example, chloroform, carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan (tert-dodecyl mercaptan) , Thioglycolic acid (thioglycolic acid), 3-mercaptopropionic acid, etc. When a thiol compound having a structure of formula (2) is used as a molecular weight regulator, the sensitivity is better.

The polystyrene conversion weight average molecular weight (Mw) of the resin (A) obtained by Gel Penetration Chromatography (GPC) is 4000 to 38000, preferably 5000 to 28000, more preferably 6000 to 18000.

Photo acid generator (B)

The photoacid generator (B) is a compound that generates an acid by irradiation with radiation, and a compound selected from the oxime sulfonate group represented by the following formula (3), and an N-sulfonyloxyimide compound can be used At least one of them. As the radiation, for example, visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays, etc. can be used. Since the chemically amplified positive photosensitive resin composition of the present invention contains the photoacid generator (B), the chemically amplified positive photosensitive resin composition can exhibit radiation-sensitive (or photosensitivity) characteristics and can have good properties. Radiation sensitivity. As the photoacid generator (B) in the chemically amplified positive photosensitive resin composition, as described later, it may be in the form of a compound or as a part of the polymer constituting the resin (A) Incorporate resin (A) form, It can also be a combination of these two forms. These photoacid generators (B) may be used alone or in combination of two or more kinds.

The photoacid generator (B) may contain an oxime sulfonate compound containing an oxime sulfonate group and an N-sulfonyloxyimide compound, as well as an onium salt, a halogen-containing compound, and a diazomethane compound , Chlorine compounds, sulfonate compounds, carboxylate compounds, etc.

The oxime sulfonate compound is a compound containing an oxime sulfonate group of the following formula (3).

In formula (3), R ⁵ is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group, an aryl group, or the aforementioned groups (alkyl, monovalent alicyclic hydrocarbon group, aryl group) ) Has a group in which the hydrogen atom is partially or fully substituted; and, * is the bonding site.

The alkyl group represented by R ⁵ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.

The monovalent alicyclic hydrocarbon group represented by R ⁵ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms.

The aryl group represented by R ⁵ is preferably an aryl group having 6 to 20 carbon atoms, more preferably phenyl, naphthyl, tolyl, and xylyl.

Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a pendant oxy group, and a halogen atom.

Examples of the compound containing the oxime sulfonate group represented by formula (3) include oxime sulfonate compounds represented by the following formulas (3-1) to (3-3).

In the formulas (3-1) to (3-3), R ⁶ has the same meaning as R ^{5 in the} structural formula (3). In the formulas (3-1) and (3-2), R ⁷ is an alkyl group having 1 to 12 carbons, and a fluoroalkyl group having 1 to 12 carbons. In the formula (3-3), X is an alkyl group, an alkoxy group, or a halogen atom. i is an integer from 0 to 3. However, when i is 2 or 3, multiple Xs may be the same or different.

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear 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.

The oxime sulfonate compound represented by the formula (3-3) can be The compounds etc. represented by following formula (3-4)-formula (3-8) are mentioned.

The compounds represented by formula (3-4) to formula (3-8) are: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methyl Phenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-camphorsulfonyloxyimino- 5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thio Phen-2-ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, 4-methylbenzene As the sulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile, the above-mentioned commercially available compounds can be used.

The above-mentioned N-sulfonyloxyimide compounds include, for example, N-(trifluoromethylsulfonyloxy) succinimide, N-(camphorsulfonyloxy) succinimide, N- (4-Methylphenylsulfonyloxy) butanedioximine, N-(2-trifluoromethylphenylsulfonyloxy)butanedioximine, N-(4-fluorophenylsulfonyloxy) Oxy) succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2 -Trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy) Oxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenyl cis Butylene diamide, N-(2-trifluoromethylphenylsulfonyloxy)diphenyl maleimide, N-(4-fluorophenylsulfonyloxy)diphenyl Maleimide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-methylphenylsulfonyl) (Oxyoxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyamido, N-(trifluoromethanesulfonoxy)bicyclo[2.2.1]hept-5-ene-2 ,3-Dicarboxyimide, N-(nonafluorobutanesulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(camphorsulfonyloxy) )Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2 , 3-Dicarboxy imine, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxy imine, N- (4-Methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-methylphenylsulfonyloxy)-7 -Oxadiene Cyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxyimide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate Imine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimine, N-(4-fluorophenylsulfonyloxy) )-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5 ,6-Oxy-2,3-dicarboxyimines, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyimines , N-(4-Methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyimid, N-(2-trifluoromethyl Phenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyimidimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2. 1) Heptane-5,6-oxy-2,3-dicarboxylimidine, N-((trifluoromethylsulfonyl)oxy)naphthalene dicarboximide), N-(camphorsulfonyloxy) naphthalene dimethymide, N-(4-methylphenylsulfonyloxy) naphthalene dimethymide, N-(phenylsulfonyloxy) Naphthalenedimethimide, N-(2-trifluoromethylphenylsulfonyloxy) naphthalenedimethimide, N-(4-fluorophenylsulfonyloxy)naphthalenedimide, N-(Pentafluoroethylsulfonyloxy) naphthalene dimethymide, N-(heptafluoropropylsulfonyloxy) naphthalene dimethymide, N-(nonafluorobutylsulfonyloxy) Naphthalimide, N-(ethyl sulfonyloxy) naphthalene dimethyl methimide, N-(propyl sulfonyloxy) naphthalene dimethyl methimide, N-(butylsulfonyloxy) ) Naphthalimide, N-(pentylsulfonyloxy) naphthalene dimethymine, N-(hexylsulfonyloxy) naphthalene dimethymide, N-(heptylsulfonyloxy) ) Naphthalimide, N-(octylsulfonyloxy) naphthalimide, N-(nonyl Sulfooxy) naphthalenedimethimide and the like.

As the onium salt, halogen-containing compound, diazomethane compound, sulfonium compound, sulfonate compound, carboxylate compound, etc., compounds described in Japanese Patent Laid-Open No. 2011-232632 can be used. For example: benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate.

The photoacid generator (B) is preferably a compound represented by the formula (3-4) to (3-8) in the oxime sulfonate compound represented by the formula (3). In addition, preferably, the photoacid generator (B) also contains an N-sulfonyloxyimide compound.

Based on 100 parts by weight of the total usage of the resin (A), the content of the photoacid generator (B) is 0.2 to 5 parts by weight, preferably 0.3 to 4.5 parts by weight, more preferably 0.4 parts by weight to 4 parts by weight. If the compound containing the oxime sulfonate group of formula (3) in the chemically amplified positive photosensitive resin composition is used as the photoacid generator (B), the sensitivity can be further improved.

Solvent (C)

The type of solvent (C) in the present invention is not particularly limited. Specific examples of the solvent (C) are an alcoholic hydroxy-containing compound or a carbonyl group-containing cyclic compound.

Specific examples of compounds containing alcoholic hydroxyl groups are acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl 2-butanone (4-hydroxy-3-methyl-2-butanone), 5-hydroxy-2-pentanone (5-hydroxy-2-pentanone), 4-hydroxy-4-methyl-2-pentanone Ketone (4-hydroxy-4-methyl-2-pentanone) (also known as diacetone alcohol (diacetone alcohol, DAA for short)), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether (PGEE for short), propylene glycol monoethyl ether Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether Butyl ether (propylene glycol mono-t-butyl ether), diethylene glycol methyl ethyl ether (diethylene glycol methyl ethyl ether), diethylene glycol dimethyl ether, 3-methoxy-1-butanol (3-methoxy- 1-butanol), 3-methyl-3-methoxy-1-butanol (3-methyl-3-methoxy-1-butanol) or a combination thereof. It is worth noting that the compound containing alcoholic hydroxyl group is preferably diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or a combination thereof. The alcoholic hydroxyl group-containing compound can be used alone or in combination of multiple types.

Specific examples of carbonyl-containing cyclic compounds are γ-butyrolactone, γ-valerolactone, δ-valerolactone, and propylene carbonate , N-methyl pyrrolidone (N-methyl pyrrolidone), cyclohexanone (cyclohexanone) or cycloheptanone (cycloheptanone), etc. It is worth noting that the carbonyl-containing cyclic compound is preferably γ-butyrolactone, nitrogen-methylpyrrolidone, cyclohexanone or a combination thereof. The carbonyl group-containing cyclic compound can be used alone or in combination of multiple types.

The alcoholic hydroxyl group-containing compound can be used in combination with the carbonyl group-containing cyclic compound, and the weight ratio is not particularly limited. The weight ratio of the alcoholic hydroxyl-containing compound to the carbonyl-containing cyclic compound is preferably 99/1 to 50/50; more preferably 95/5 to 60/40.

Other solvents may be contained within a range that does not impair the effects of the present invention. Specific examples of the 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 or diisobutyl ketone, etc.; or (3) Ethers: diethyl ether, diisopropyl ether, di-n-butyl ether or diphenyl ether, etc.

The content of the solvent (C) is from 100 parts by weight to 1500 parts by weight, preferably from 120 parts by weight to 1400 parts by weight, more preferably from 150 parts by weight to 100 parts by weight based on the total use amount of the resin (A) 1300 parts by weight.

Other additives (D)

Optionally, the chemically amplified positive photosensitive resin composition of the present invention may contain other additives (D). Specifically, specific examples of other additives (D) are sensitizers, adhesion auxiliary agents, surfactants, solubility promoters, and defoamers. ) Or a combination thereof.

The type of sensitizer is not particularly limited. The sensitizer is preferably a compound containing phenolic hydroxy. Specific examples are: (1) trisphenol type compound: such as Tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)- 2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3- Hydroxyphenylmethane, bis(4-hydroxy-3,5-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenyl Methane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, Bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxy Phenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxybenzene Methane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3- Hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane or bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)- 3,4-dihydroxyphenylmethane, etc.; (2) bisphenol type compound: such as bis(2,3,4-trihydroxyphenyl) methane, bis(2,4-dihydroxyphenyl) ) Methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-tri Hydroxyphenyl)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-dihydroxybenzene) Yl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane or 2-(2,3,4 -Trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane, etc.; (3) Polynuclear branched compound: 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, etc.; (4) Condensation type phenol compound: such as 1,1-bis(4-hydroxyphenyl) cyclohexane, etc.; (5) polyhydroxy benzophenone: such as 2, 3,4-Trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'- Methyl benzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4,2',4'-tetrahydroxybenzophenone, 2,4,6,3',4 '-Pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4 ,6,3',4',5'-hexahydroxybenzophenone or 2,3,4,3',4',5'-hexahydroxybenzophenone, etc.; or (6) the above-mentioned various types contain A combination of phenolic hydroxyl compounds.

Based on 100 parts by weight of resin (A), the amount of sensitizer used is 5 to 50 parts by weight; preferably 8 to 40 parts by weight; and more preferably 10 to 35 parts by weight .

Specific examples of the adhesion aid are melamine compounds and silane-based compounds. The role of the adhesion assistant is to increase the adhesion between the film formed by the photocurable polysiloxane composition and the element or substrate.

Specific examples of commercially available products of melamine are Cymel-300 or Cymel-303 manufactured by Mitsui Chemicals; or the commercial names manufactured by Sanwa Chemicals are MW-30MH, MW-30, MS-11, MS- 001, MX-750 or MX-706 etc.

When a melamine compound is used as an adhesion aid, based on 100 parts by weight of the resin (A), the usage amount of the melamine compound is 0 parts by weight to 20 parts by weight; preferably 0.5 parts by weight to 18 parts by weight ; And more preferably 1.0 parts by weight to 15 parts by weight.

Specific examples of silane-based compounds are vinyltrimethoxysilane, vinyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, Nitrogen-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-amine Propyl triethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl dimethyl methoxy silane, 2-(3,4-epoxycyclohexyl) ) Ethyl trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropane Trimethoxysilane or a commercially available product manufactured by Shin-Etsu Chemical Co., Ltd. (trade name such as KBM403).

When using a silane-based compound as an adhesion aid, based on 100 parts by weight of the resin (A), the amount of the silane-based compound is 0 to 2 parts by weight; 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 anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, silicone surfactants, fluorine surfactants, or combinations thereof.

Examples of surfactants include (1) polyethylene oxide alkyl ethers (polyoxyethylene alkyl ethers): polyethylene oxide dodecyl (2) Polyoxyethylene phenyl ethers: polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, etc.; (3) polyoxyethylene phenyl ethers Polyethylene glycol diesters: polyethylene glycol dilaurate, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; and ( 5) Fatty acid modified poly esters modified with fatty acid; and (6) tertiary amine modified polyurethane modified with tertiary amines. Specific examples of commercially available products of surfactants are KP (manufactured by Shin-Etsu Chemical Industry), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Dow Corning Toray Silicone Co., Ltd.) Manufactured by Kyoeisha Oleochemical Industry), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by Dainippon Ink Chemical Industry (DIC)), Fluorade (Manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Chunichi Synthetic Chemical), F-475 (manufactured by Dai Nippon Ink Chemical Industry), or a combination thereof .

Based on 100 parts by weight of resin (A), the amount of surfactant used is 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 defoamers 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, Surfynol DF210 (manufactured by Air products), etc.

Based on 100 parts by weight of resin (A), the amount of defoamer used is 1 to 10 parts by weight; preferably 2 to 9 parts by weight; and more preferably 3 to 8 parts by weight .

Examples of the dissolution promoter include N-hydroxydicarboxylic imide compounds and compounds containing phenolic hydroxyl groups. A specific example of the dissolution accelerator is a phenolic hydroxyl group-containing compound used in o-naphthoquinone diazide sulfonate (B).

Based on 100 parts by weight of resin (A), the use amount of dissolution promoter is 1 part by weight to 20 parts by weight; preferably 2 parts by weight to 15 parts by weight; and more preferably 3 parts by weight to 10 parts by weight .

A specific example of the chemically amplified positive photosensitive resin composition is prepared in the following manner: the resin (A), the photoacid generator (B) and the solvent (C) are placed in a stirrer and stirred to make them uniformly mixed into In solution state, other additives (D) can be added if necessary.

The present invention also provides a protective film, which comprises coating the above chemically amplified positive photosensitive resin composition on a substrate, and then pre-baking, exposing, developing, and post-baking.

The present invention further provides a device with a protective film, which includes a substrate and the protective film.

Method of 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 element. another In addition, the present invention also includes a protective film suitable for display elements formed of a chemically amplified positive photosensitive resin composition.

The method of forming the protective film includes 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) ) The step of irradiating at least a part of the coating film with radiation (hereinafter also referred to as "step (2)"); (3) the step of developing the coating film after radiation exposure (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 this formation method, it is possible to form a protective film for a display element having excellent surface hardness, solvent resistance, heat resistance, and voltage retention. In addition, by using a chemically amplified positive photosensitive resin composition with good sensitivity, a protective film for a display element having a fine and delicate pattern can be easily formed. Therefore, the formed protective film for display elements is suitable for display elements such as liquid crystal display elements and organic EL display elements.

[step 1)]

In this step, the chemically amplified positive photosensitive resin composition is applied on the substrate to form a coating film. Preferably, the solvent is removed by pre-baking the coated surface.

Examples of the substrate include glass, quartz, silicon substrate, and resin. Examples of the resin include ring-opening polymers of polyethylene terephthalate, polybutylene terephthalate, polyether ether, polycarbonate, polyimide, and cyclic olefin, and hydrogenated products thereof. The pre-baking conditions also depend on the types of ingredients, The mixing ratio is different, and it can be set at 70°C to 120°C for 1 minute to 10 minutes.

[Step (2)]

In this step, at least a part of the formed coating film is irradiated with radiation for exposure. At the time of exposure, exposure is usually performed through a mask having a predetermined pattern. The radiation used for exposure is preferably radiation having a wavelength in the range of 190 nm to 450 nm, and more preferably radiation including ultraviolet rays of 365 nm. The exposure level is a value obtained by measuring the intensity of the radiation at a wavelength of 365 nm using an illuminance meter (OAI model 356, manufactured by OAI Optical Associates), and is preferably 500 J/m ² to 6,000 J/m ² , and more Preferably, it is 1,500 J/m ² to 1,800 J/m ² .

[Step (3)]

In this step, the coating film irradiated with radiation is developed. By developing the exposed coating film, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern. The developer used in the development 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 amine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

To the aqueous alkali solution, a suitable amount of water-soluble organic solvents such as methanol and ethanol or surfactants can also be added and used. From the viewpoint of obtaining appropriate developability, the concentration of the alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less. Examples of the development method include a puddle method, a dipping method, a shaking dipping method, and a spray method. The development time varies according to the composition of the chemically amplified positive photosensitive resin composition. About 10 seconds to 180 seconds. After the development process, by performing, for example, running water washing for 30 to 90 seconds, and then using compressed air or compressed nitrogen, the coating film is air-dried to form a desired pattern.

[Step (4)]

In this step, the developed coating film is heated. During heating, the patterned film is heated by using a heating device such as a hot plate and an oven to promote the curing reaction of the resin (A) and obtain a cured product. The heating temperature is, for example, about 120°C to 250°C. The heating time varies depending on the type of heating equipment, for example, it is about 5 minutes to 30 minutes on a hot plate, and about 30 minutes to 90 minutes in an oven. In addition, a staged baking method in which heating steps are performed twice or more may also be used. In this way, a patterned thin film corresponding to the target protective film for display elements can be formed on the surface of the substrate. In addition, the use of the above-mentioned cured film is not limited to the protective film for display elements, and it can be used as a spacer or an interlayer insulating film.

The thickness of the formed protective film for display elements is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and still more preferably 0.1 μm to 4 μm.

Hereinafter, a number of preparation examples, examples, and comparative examples are used to illustrate the manufacturing method and application of the chemically amplified positive photosensitive resin composition of the present invention.

Prepare resin (A) Preparation Example A-1

A four-necked conical flask with a volume of 1000 ml is equipped with a nitrogen inlet, a stirrer, a heater, a condenser and a thermometer. After the nitrogen is introduced, 3 parts by weight of methacrylic acid (hereinafter referred to as MAA) and 20 parts by weight of methyl are added. Tetrahydrofurfuryl acrylate, 22 parts by weight of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 25 parts by weight of dicyclopentyl methacrylate (hereinafter referred to as FA-513M), 30 parts by weight of benzene methacrylate Methyl ester (hereinafter referred to as BzMA), 1 part by weight of 2-ethylhexyl 3-mercaptopropionate (hereinafter referred to as EHMP), 10 parts by weight of 2,2'-azobis(2,4-dimethylpentene) Nitrile) (hereinafter referred to as ADVN) and 240 parts by weight of diethylene glycol dimethyl ether (hereinafter referred to as Diglyme) solvent. Next, slowly stir the above components to raise the temperature of the solution to 70°C, and polycondense at this temperature for 6 hours. Then, after the solvent is devolatilized, resin (A-1) with a weight average molecular weight of 12,000 can be obtained.

Preparation Examples A-2 to A-10 and Preparation Comparative Examples A'-1 to A'-4

The preparation of the resins (A-2) to (A-10) and the preparation comparative examples (A'-1) to (A'-4) are similar to the preparation examples of the aforementioned resin (A-1), in which the type of monomer And the usage amount is shown in Table 1. However, the usage amount of solvent and catalyst, reaction temperature and reaction time of polycondensation are different from the aforementioned resin (A-1), which is also shown in Table 1.

Example 1 Preparation of chemically amplified positive photosensitive resin composition

Add 100 parts by weight of resin (A-1) and 0.2 parts by weight of benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate (B-1) to 100 parts by weight After mixing the propylene glycol methyl ether acetate (C-1) uniformly with a shaking type stirrer, the chemically amplified positive photosensitive resin composition of Example 1 can be obtained.

Form a protective film

Spin coating on a plain glass substrate (100×100×0.7mm) to obtain a coating film of approximately 3μm. After pre-baking at 110°C for 2 minutes, a positive photoresist mask is placed between the exposure machine and the coating film. And irradiate the coating film with the ultraviolet light of the exposure machine, the energy of which is 80mJ/cm ² . The exposed coating film was immersed in a 2.38% TMAH aqueous solution at 23°C for 70 seconds to remove the exposed part. After washing with clean water, directly irradiate the developed coating film with an exposure machine, and its energy is 300mJ/cm ² . Finally, after baking at 220°C for 45 minutes, the protective film on the plain glass substrate can be obtained.

The specific conditions and evaluation results of Example 1 are shown in Table 2.

Examples 2 to 12 and Comparative Examples 1 to 4

The chemically amplified positive photosensitive resin composition and protective film of Examples 2 to 12 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1. The difference is that Examples 2 to 12 and Comparative Examples 1 to 4 changed conditions such as composition or usage amount. The specific conditions and evaluation results of Examples 2 to 12 and Comparative Examples 1 to 4 are shown in Table 2.

Evaluation method

(1) Sensitivity:

After coating the chemically amplified positive photosensitive resin composition of the Examples and Comparative Examples on an ITO substrate (100mm×100mm), the temperature was heated at 110°C and 120°C. In the heating condition of one second, preheating is performed by approaching heating with a gap of about 1 mm to form a photoresist film with a thickness of 3 μm. Next, an i-line exposure device (device name: FX-702J, manufactured by Nikon, NA=0.14) was used to draw a photoresist pattern of 2.0μm L&S (line and space) and a photoresist pattern of 3.0μm L&S at the same time. Chart mask (scale line) for selective exposure. Next, using 23° C., 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution, after performing a development process for 70 seconds, rinsed with pure water for 15 seconds, and spin dried. The exposure level (Eop, unit: mJ) that can faithfully reproduce the 2.0μm L&S photoresist pattern is used as the index for sensitivity evaluation. The evaluation criteria are as follows:

◎: Exposure amount <60mJ

○: 60mJ≦Exposure amount<150mJ

△: 150mJ≦Exposure amount<300mJ

×: Exposure ≧300mJ.

(2) Chemical resistance:

After the coating film of the chemically amplified positive photosensitive resin composition is formed by the above-mentioned protective film formation method, the coating film is fired for 30 minutes in an oven heated to 230° C. to form a cured film. The cured film was immersed in an N-methylpyrrolidone solvent heated to 40°C for 6 minutes, and the film thickness change rate (%) before and after immersion was determined as an index of chemical resistance.

◎: Film thickness change rate <5%

○: 5%≦film thickness change rate<10%

△: 10%≦film thickness change rate<15%

×: 15%≦film thickness change rate.

According to the examples in Table 2, when the mixture of resin (A) of the synthetic chemically amplified positive photosensitive resin composition contains the aforementioned monomer (a-2) and a specific thiol compound, the chemically amplified positive The type photosensitive resin composition can have both good sensitivity and chemical resistance. In addition, when the mixture further contains the aforementioned monomer (a-3-1), the chemical resistance of the chemically amplified positive photosensitive resin composition can be further improved. When the chemically amplified positive photosensitive resin composition contains an oxime sulfonate group compound, the sensitivity can be further improved.

On the other hand, if the acid-dissociable group-containing monomer (a-2) is not used in the mixture, the sensitivity and chemical resistance of the chemically amplified positive photosensitive resin composition are poor. On the other hand, if a specific thiol compound is not used in the mixture, the chemically amplified positive photosensitive resin composition has poor sensitivity. In addition, if the thiol compound synthetic resin (A) not claimed in the present invention is used, the sensitivity of the chemically amplified positive photosensitive resin composition cannot be improved.

The present invention provides a chemically amplified positive photosensitive resin composition with good sensitivity and chemical resistance, which can be used as a protective film. This protective film also has good chemical resistance and can be applied to various types of components.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field of the present invention can make various changes and modifications without departing from the spirit and scope of the present invention. Retouching, therefore, the scope of protection of the present invention shall be subject to the scope of the attached patent application.

Claims (8)

A chemically amplified positive photosensitive resin composition comprising: resin (A); photoacid generator (B); and solvent (C), wherein the resin (A) is obtained by copolymerizing a mixture, The mixture includes a polymerizable monomer and a thiol compound having the structure of the following formula (2), and the polymerizable monomer includes an unsaturated carboxylic acid monomer (a-1) and an acid dissociable group containing the formula (1) Monomer (a-2) and other unsaturated monomers (a-3) other than monomer (a-1) and monomer (a-2):

In the formula (1), the R ¹ and the R ² are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, wherein the hydrogen of the alkyl group, the alicyclic hydrocarbon group or the aryl group Part or all of the atoms may be substituted; moreover, the R ¹ and the R ² cannot be hydrogen atoms at the same time; the R ³ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group or an aryl group; wherein the alkane of the R ³ Part or all of the hydrogen atoms of the aryl group, the alicyclic hydrocarbon group, the aralkyl group, and the aryl group may be substituted; the R ¹ and the R ³ may be bonded to each other and the carbon to which the R ¹ is bonded Atom and the oxygen atom bonded by the R ³ together form a cyclic ether structure; XR ⁴ -SH Formula (2) In the formula (2), X represents an ester group, a hydroxyl group, an amino group or an alkoxysilyl group, And the R ⁴ represents a substituted or unsubstituted alkylene group or arylene group. The chemically amplified positive photosensitive resin composition described in item 1 of the scope of patent application, wherein the other unsaturated monomer (a-3) includes an epoxy group-containing unsaturated monomer (a-3-1) . The chemically amplified positive photosensitive resin composition described in item 1 of the scope of patent application, wherein the photoacid generator (B) is a compound having an oxime sulfonate group containing the following formula (3):

In the formula (3), the R ⁵ is an alkyl group having a carbon number of 1 to 20, an alicyclic hydrocarbon group, an aryl group, or a group in which the hydrogen atoms of the above groups are partially or fully substituted, and The * is the bond point. The chemically amplified positive photosensitive resin composition as described in item 1 of the scope of patent application, wherein based on the total use amount of the resin (A) is 100 parts by weight, the content of the photoacid generator (B) is 0.2 Parts by weight to 5 parts by weight, and the content of the solvent (C) is from 100 parts by weight to 1500 parts by weight. The chemically amplified positive photosensitive resin composition described in item 1 of the scope of the patent application, wherein based on the total usage amount of the polymerizable monomer is 100 parts by weight, the unsaturated carboxylic acid monomer (a-1) The content is 1 part by weight to 50 parts by weight, the monomer (a-2) containing the acid dissociable group of formula (1) The content of the thiol compound is 5 to 90 parts by weight, the content of the other unsaturated monomer (a-3) is 5 to 94 parts by weight, and the content of the thiol compound having the structure of formula (2) is 1 weight Parts to 15 parts by weight. The chemically amplified positive photosensitive resin composition described in item 2 of the scope of patent application, wherein the total amount of the polymerizable monomer is 100 parts by weight, and the epoxy group-containing unsaturated monomer (a- The content of 3-1) is 5 parts by weight to 80 parts by weight. A protective film, which coats the chemically amplified positive photosensitive resin composition as described in any one of items 1 to 6 of the scope of patent application on a substrate, and then undergoes prebaking, exposure, development and It is formed after baking. A device with a protective film includes a substrate and a protective film as described in item 7 of the scope of patent application.