TWI795489B - 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 adhesiveness after a developing treatment 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-type photosensitive resin composition and its application

The present invention relates to a chemically amplified positive-type photosensitive resin composition, a protective film formed therefrom, and an element with the protective film. Among them, in particular, a positive-type photosensitive resin composition for a protective film formed after exposure and development is provided, which has the characteristics of good development adhesion, good chemical resistance, and the like. This protective film is suitable for flattening film for thin film transistor (Thin Film Transistor; TFT) substrate of liquid crystal display element, organic EL display element, etc., interlayer insulating film or core material or cladding material of optical waveguide.

A display element such as a thin film transistor liquid crystal display element or an organic electroluminescence device (organic electroluminescence device, organic EL element) generally includes an insulating film such as an interlayer insulating film or a planarizing film. Such an insulating film is usually formed using a radiation-sensitive composition. From the point of view of patterning performance, it is known that positive-type radiation-sensitive products using acid generators such as naphthoquinone diazide (naphthoquinone diazide) are often used. A resin composition (refer to Japanese Patent Application Laid-Open No. 2001-354822 ) is such a radiation-sensitive composition, but various radiation-sensitive compositions have been proposed in recent years.

For example, a positive-type chemically amplified material has been proposed for the purpose of forming a display element with a higher sensitivity than the aforementioned positive-type radiation-sensitive resin composition using an acid generator such as naphthoquinonediazide. Cured film for use (refer to Japanese Patent Laid-Open No. 2004-4669). The positive chemical amplification material contains a crosslinking agent, an acid generator and an acid dissociative resin. Acid dissociative resins have protective groups that can be dissociated by the action of acids. Although acid dissociative resins themselves are insoluble or hardly soluble in alkaline aqueous solutions, they are dissociated by the action of acids and become soluble in alkalis. in 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 (refer to Japanese Patent Laid-Open No. 2004-264623, 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 be achieved. Chemical resistance to swelling due to developer, etc. Furthermore, the pattern formed by the cured film can also achieve: after development, the pattern is fully adhered to the substrate and is difficult to peel off; the cured film has sufficient transparency; and, even if placed after exposure, the pattern is also consistent with The substrates are sufficiently adhered to be difficult to peel off.

However, the development adhesion and chemical resistance of the current photosensitive resin composition are still not acceptable to 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 a resin (A), a photoacid generator (B) and a solvent (C), which are described in detail below.

Resin (A)

The resin (A) is obtained by copolymerizing the mixture. The mixture at least includes unsaturated carboxylic acid monomer (a-1), silyl group-containing unsaturated compound (a-2) and acid dissociative group-containing monomer (a-3).

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 a carboxylic acid anhydride structure and an unsaturated bond for polymerization. Its structure is not particularly limited, and may include but not limited to unsaturated mono 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)acrylethoxysuccinate, 2 -(meth)acrylethoxyhexahydrophthalate, 2-(meth)acrylethoxyphthalate, omega-carboxypolycaprolactone polyol monoacrylate (trade name ARONIX M-5300, manufactured by Toagosei).

Specific examples of the aforementioned unsaturated dicarboxylic acid compounds: Malay acid, fumaric acid, methyl fumaric acid, itaconic acid, citraconic acid, etc. In a specific example of the present invention, the unsaturated dicarboxylic acid anhydride compound is an 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-carboxybicyclo[2.2.1]hept-2-ene, 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.

A specific example of the aforementioned polycyclic unsaturated dicarboxylic acid compound is: 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-methacrylethoxysuccinate, 2-methacrylylethyl Oxyhexahydrophthalic acid or combinations thereof.

The said unsaturated carboxylic acid monomer (a-1) can be used individually or in mixture of plural types. Based on 100 parts by weight of the mixture of synthetic resin (A), the usage of unsaturated carboxylic acid monomer (a-1) is 5 parts by weight to 50 parts by weight; preferably 10 parts by weight to 45 parts by weight; more preferably It is 15 parts by weight to 45 parts by weight.

Unsaturated compounds containing silyl groups (a-2)

The silyl group-containing unsaturated compound (a-2) of the present invention has the following structural formula (1-1):

In the structural formula (1-1), R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ represent independent alkyl groups with 1 to 12 carbons, phenyl, and alkoxy groups with 1 to 6 carbons The group shown in group or structural formula (1-2); When R ² and R ³ are plural, each R ² and R ³ are the same or different; a represents an integer from 1 to 6; b represents an integer from 1 to 150 ; R ⁴ represents an alkyl group with a carbon number of 1 to 6 or a group represented by structural formula (1-3).

In the structural formula (1-2), R ⁵ , R ⁶ and R ⁷ represent independent alkyl or phenyl groups with 1 to 12 carbons; when R ⁶ and R ⁷ are plural, each R ⁶ and R ⁷ are the same or different; c represents an integer from 1 to 13.

In the structural formula (1-3), R ⁸ , R ⁹ and R ¹⁰ represent independent alkyl groups or phenyl groups with 1 to 12 carbon atoms.

Specific examples of the alkyl group having a carbon number of 1 to 12 are methyl, ethyl, and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.

Specific examples of the alkoxy group having 1 to 6 carbon atoms are methoxy, ethoxy, propoxy or butoxy.

The silane group-containing unsaturated compound (a-2) represented by the structural formula (1-1) includes allylsilanes and methacrylic silanes, and its specific example is 3- Methacryloxypropyltrimethoxysilane (3-methacryloxypropyltrimethoxysilane), 3-methacryloxypropyltriethoxysilane (3-methacryloxypropyltriethoxysilane), 3-methacryloxypropyltrimethoxysilane 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane (3-methacryloxypropylmethyldiethoxysilane), from the following formula (1-1-1) to (1- The compound shown in 1-6), (3-methacryloyloxy) propyl tris (trimethylsilyloxy) silane ((3-methacryloyloxy) propyltris shown in formula (1-1-7) (trimethylsiloxy)silane; 3MPTS) or FM-0711, FM-0721, FM-0725 (manufactured by Chisso Corporation).

Preferred specific examples of the silyl group-containing unsaturated compound (a-2) represented by the above structural formula (1-1) are 3-methacryloxypropyl trimethoxysilane, 3-methacryl Oxypropyltriethoxysilane, (3-methacryloxy)propyltris(trimethylsiloxy)silane represented by formula (1-1-7), FM-0711 (Chisso Corporation) or a combination thereof.

The silyl group-containing unsaturated compound (a-2) represented by the above structural formula (1-1) can be used alone or in combination. Based on 100 parts by weight of the synthetic resin (A) mixture, the amount of the silyl group-containing unsaturated compound (a-2) represented by the structural formula (1-1) is 5 parts by weight to 50 parts by weight; preferably 10 parts by weight to 45 parts by weight; more preferably 15 parts by weight to 45 parts by weight. If the mixture of the synthetic resin (A) does not contain the silyl group-containing unsaturated compound (a-2) represented by the structural formula (1-1), the protection formed by the chemically amplified positive photosensitive resin composition The film has problems of development adhesion and poor chemical resistance.

Acid dissociative group-containing monomer (a-3)

The acid-dissociating group-containing monomer (a-3) of the present invention has an acid-dissociating group represented by the following structural formula (2-1).

The acid-dissociable group of the acid-dissociable group-containing monomer (a-3) is dissociated by the action of the acid generated from the photoacid generator (B) described later at the time of exposure to generate a polar group, so it is originally insoluble Or the resin (A) which is poorly soluble in aqueous alkali solution becomes soluble in aqueous alkali solution.

The acid dissociative group-containing monomer (a-3) is not particularly limited as long as it has the structure of the structural formula (2-1). The monomer (a-3) containing the acid dissociative group of the structural formula (2-1) can be easily dissociated by acid. In the above structural formula (2-1), R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, wherein the hydrogen contained in the alkyl group, alicyclic hydrocarbon group or aryl group is Part or all of the atoms can be substituted; and, R ¹¹ and R ¹² are not hydrogen atoms at the same time; R ¹³ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group or an aryl group; wherein R ¹³ is an alkyl group, an alicyclic group Part or all of the hydrogen atoms of the hydrocarbon group, aralkyl group, and aryl group may be substituted; R ¹¹ and R ¹³ may be linked to form a cyclic ether structure. For example: R ¹¹ and R ¹³ may be bonded to each other to form a cyclic ether structure together with the carbon atom to which R ¹¹ is bonded and the oxygen atom to which R ¹³ is bonded.

Examples of the alicyclic hydrocarbon groups represented by R ¹¹ and R ¹² above include alicyclic hydrocarbon groups having 3 to 20 carbon atoms. In addition, this alicyclic hydrocarbon group having a carbon number of 3 to 20 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.

The aryl group represented by the above-mentioned R ¹¹ and R ¹² includes, for example, an aryl group having 6 to 14 carbon atoms. The above-mentioned aryl group having 6 to 14 carbon atoms may be a single ring, may be a structure in which single rings are connected, or may be a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include phenyl, naphthyl and the like.

The substituents of the optionally substituted alkyl, alicyclic hydrocarbon group, and aryl group represented by the above-mentioned R ¹¹ and R ¹² include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, and an alicyclic hydrocarbon group ( Such as 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 a carbon number of 1 to 20, etc.), acyl groups (such as Acyl, propionyl, butyryl, isobutyryl and other acyl groups with 2 to 20 carbon atoms, etc.), acyloxy (such as acetyloxy, propionyloxy, butyryloxy, tertiary butyryloxy acyloxy group with a carbon number of 2 to 10, such as the third pentyloxy group, etc.), an alkoxycarbonyl group (such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, etc., with a carbon number of 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 Straight-chain alkyl such as alkyl, branched alkyl such as isopropyl, isobutyl, tertiary butyl, neopentyl, 2-hexyl, 3-hexyl, etc.; cyclopropyl, cyclobutyl, Cyclopentyl, norbornyl, adamantyl and other alicyclic hydrocarbon groups, groups obtained by substituting some or all of the hydrogen atoms of the above groups with halogen atoms), hydroxyalkyl groups (such as hydroxymethyl, etc.), etc. .

The alkyl group, alicyclic hydrocarbon group, and aryl group represented by the above-mentioned R ¹³ can apply the description of each group represented by the above-mentioned R ¹¹ and R ¹² . In addition, the above-mentioned alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl group, ethyl group and n-propyl group. The aralkyl group represented by ^R13 above includes benzyl, phenethyl, naphthylmethyl, naphthylethyl and the like.

The cyclic ether structure formed by the above-mentioned R ¹¹ and R ¹³ being bonded to each other is preferably a cyclic ether structure with 3 to 20 ring members, more preferably a cyclic ether structure with 5 to 8 ring members, and even more Preferable are tetrahydrofuran and tetrahydropyran.

As for the group represented by the said structural formula (2-1), the group etc. which are represented by the following formula are mentioned, for example.

Examples of the monomer (a-3) containing an acid dissociative group 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 -Ethylhexyloxy)ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1-(2-cyclohexylethoxy)ethyl methacrylate , 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 2-tetrahydrofuranyl methacrylate (2-Tetrahydrofuranyl methacrylate), 1-ethoxyethyl acrylate, 1- Methoxyethyl ester, 1-n-butoxyethyl acrylate, propylene 1-isobutoxyethyl acrylate, 1-tert-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-tetrahydropyridine acrylate Nyl ester, 5,6-bis(1-methoxyethoxycarbonyl)-2-norbornene, 5,6-bis(1-(cyclohexyloxy)ethoxycarbonyl)-2-norbornene Bornene, 5,6-bis(1-(benzyloxy)ethoxycarbonyl)-2-norbornene, p-1-ethoxyethoxystyrene or m-1-ethoxyethoxy p-1-methoxyethoxystyrene or m-1-methoxyethoxystyrene, p-1-n-butoxyethoxystyrene or m-1-n-butyl Oxyethoxystyrene, p-1-isobutoxyethoxystyrene or m-1-isobutoxyethoxystyrene, p-1-(1,1-dimethylethoxy base) 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)ethoxy Styrene, 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, etc.

The acid dissociative group-containing monomer (a-3) is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate , 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 2-tetrahydrofuran methacrylate, more preferably 2-tetrahydropyranyl methacrylate and 2-tetrahydrofuran Methacrylate.

Based on 100 parts by weight of the mixture, the monomer (a-3) is used in an amount of 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-3) is not used, there are problems of poor image development adhesion and poor chemical resistance.

Unsaturated monomer containing epoxy group (a-4)

In some embodiments, the mixture may further include an epoxy group-containing unsaturated monomer (a-4).

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

In the structural formula (3-1), R ¹⁴ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; R ¹⁵ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent 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 compounds: glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-(meth)acrylate Epoxybutyl, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxy(meth)acrylate Cyclohexyl methyl ester.

Specific examples of the aforementioned α-alkyl acrylate compounds containing epoxy groups: α-glycidyl ethacrylate, α-glycidyl propyl acrylate, α-glycidyl butyl acrylate, α - 6,7-epoxyheptyl ethacrylate.

Specific examples of the aforementioned glycidyl ether compounds: o-vinylbenzylglycidylether (o-vinylbenzylglycidylether), m-vinylbenzylglycidylether (m-vinylbenzylglycidylether), p-vinylbenzylglycidylether Glycidyl ether (p-vinylbenzylglycidylether).

Specific examples of the above-mentioned ethylenically unsaturated monomers having an oxetane group as shown in structural formula (3-1) may include but not limited to methacrylate compounds, acrylate compounds or have the following formula ( 3-2) Unsaturated monomers having structures represented by formula (3-5).

The aforementioned methacrylate compounds may include, but are not limited to, 3-(methacryloxymethyl)oxetane [3-(methacryloyloxymethyl)oxetane; OXMA], 3-(methacryloxymethyl) 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-(methacryloxymethyl)-2,2-difluorooxetane, 3-(methacryloxymethyl)-2,2 ,4- Trifluorooxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloxyethyl)oxy Hetetane, 3-(methacryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloxyethyl)oxetane , 3-(methacryloxyethyl)-2-trifluoromethyloxetane, 3-(methacryloxyethyl)-2-pentafluoroethyloxetane , 3-(methacryloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(methacryloxyethyl)oxetane, 3 -(methacryloxyethyl)-2,2,4-trifluorooxetane or 3-(methacryloxyethyl)-2,2,4,4-tetrafluorooxetane Compounds such as heterocyclobutane.

The above-mentioned acrylate compounds may include but 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 3-(acryloxymethyl)-2,2-difluorooxetane, 3-(acryloxymethyl)-2,2,4-trifluorooxetane Heteretane, 3-(acryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(acryloxyethyl)oxetane, 3- (Acryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(acryloxyethyl)oxetane, 3-(acryloxyethyl) -2-trifluoromethyloxetane, 3-(acryloxyethyl)-2-pentafluoroethyloxetane, 3-(acryloxyethyl)-2-benzene oxetane, 2,2-difluoro-3-(acryloxyethyl)oxetane, 3-(acryloxyethyl)-2,2,4-trifluorooxy heterocyclobutane or 3-(acryloxyethyl base)-2,2,4,4-tetrafluorooxetane and other compounds.

The aforementioned unsaturated monomers having structures represented by formula (3-2) to formula (3-5) are shown below.

In some embodiments, the epoxy-containing unsaturated monomer (a-4) may further include other ethylenically unsaturated monomers having an oxetanyl group, such as: 3-methyl-3- (Ethyleneoxymethyl)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)oxetane, 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-vinyloxybutyl) oxetane, 3-propyl- 3-(3-vinyloxybutyl) oxetane, ethylene glycol [(3-ethyl-3-oxetanyl) methyl] vinyl ether, propylene glycol [(3-ethyl- Vinyl ether compounds having an oxetanyl group such as 3-oxetanyl)methyl]vinyl ether or 3,3-bis[(vinyloxy)methyl]oxetane.

Based on the usage amount of the mixture being 100 parts by weight, the usage amount of the epoxy group-containing unsaturated monomer (a-4) is 5 parts by weight to 80 parts by weight, preferably 10 parts by weight to 70 parts by weight , More preferably 15 parts by weight to 65 parts by weight. If the epoxy-group-containing unsaturated monomer (a-4) is used, it will have the advantage of good developing adhesiveness.

In some embodiments, preferably, based on 100 parts by weight of the mixture, the usage amount of the ethylenically unsaturated monomer having an oxetanyl group shown in structural formula (3-1) It is 5 parts by weight to 80 parts by weight, preferably 10 parts by weight to 70 parts by weight, more preferably 15 parts by weight to 65 parts by weight, which can further improve the developing adhesiveness.

Other unsaturated monomers (a-5)

The mixture for forming the resin (A) may further include other unsaturated monomers (a-5). In some embodiments, other unsaturated monomers (a-5) may include, but are not limited to, alkyl (meth)acrylates, cycloaliphatic (meth)acrylates, aryl (meth)acrylates, Saturated dicarboxylic acid diesters, hydroxyalkyl (meth)acrylates, polyethers of (meth)acrylates, aromatic vinyl compounds, and other unsaturated compounds other than those mentioned above.

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

Specific examples of the aforementioned cycloaliphatic (meth)acrylates: cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8 -yl (meth)acrylate (or dicyclopentyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofuran (meth)acrylate ester.

Specific examples of the aforementioned aryl (meth)acrylate: phenyl (meth)acrylate, 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)acrylates include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

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

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

Specific examples of other unsaturated compounds other than the above: acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, ethylene ethyl ester, 1,3-butadiene, iso Pentadiene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N -Succimidyl-3-maleimide benzoate, N-succimidyl-4-maleimide butyrate, N-succimidyl-6 -maleimide caproate, N-succimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide.

Based on the usage amount of the mixture being 100 parts by weight, the usage amount of the other unsaturated monomer (a-5) is 0 parts by weight to 90 parts by weight, preferably 5 parts by weight to 85 parts by weight, more preferably 5 parts by weight to 80 parts by weight.

Preparation of Resin (A)

The solvent used in the manufacture of resin (A) of the present invention may include but not limited to alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, Propylene Glycol Alkyl Ether Acetate, Propylene Glycol Alkyl Ether Propionate, Aromatic Hydrocarbon, Ketone, Ester.

Specific examples of the aforementioned alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol. A specific example of the aforementioned ether is 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 aforementioned ethylene glycol alkyl ether acetates include ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, and ethylene glycol methyl ether acetate. aforementioned Specific examples of diethylene glycol: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl 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, and 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 aforementioned propylene glycol alkyl ether acetates 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: 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 and xylene. Specific examples of the aforementioned ketones include methyl ethyl ketone, cyclohexanone, and diacetone alcohol. Specific examples of the aforementioned esters: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl glycolate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3 - Propyl hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl Methyl oxyacetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, propoxy Butyl acetate, butoxy methyl acetate, butoxy ethyl acetate, butoxy propyl acetate, butoxy butyl acetate, 3-methoxybutyl acetate, 2-methoxypropane Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate ethyl acetate, 2-ethoxypropane Propyl 2-ethoxypropionate, butyl 2-butoxypropionate, methyl 2-butoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionate Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Butyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxypropionate Methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionate Ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate.

Preferred specific examples of the solvent used in the manufacture of the resin (A) of the present invention are diethylene glycol dimethyl ether and propylene glycol methyl ether acetate. The above-mentioned solvents can be used alone or in combination.

The specific example of the polymerization initiator used in the production of the resin (A) of the present invention is an azo compound or a peroxide. Specific examples of the aforementioned azo compounds: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4 -methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-Azobis(dimethyl-2-methylpropionate). Specific examples of the aforementioned peroxides: dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxypivalate, 1,1-bis(tert butylperoxy)cyclohexane (1,1-di(tert-butylperoxy)cyclohexane), hydrogen peroxide. The above-mentioned polymerization initiators can be used alone or in combination.

The weight average molecular weight of the resin (A) of the present invention is generally 3,000 to 100,000, preferably 4,000 to 80,000, more preferably 5,000 to 60,000. The molecular weight adjustment of the resin (A) of the present invention can be achieved by using a single resin, or by using two or more resins with different molecular weights in combination.

Photoacid Generator (B)

The photoacid generator (B) is a compound that generates an acid by irradiation with radiation, and a compound selected from oxime sulfonate groups represented by the following structural formula (4-1), and N-sulfonyloxyacyl at least one of imine compounds. As the radiation, for example, visible rays, ultraviolet rays, deep ultraviolet rays, electron beams, X-rays and the like can be used. Since the chemically amplified positive-type photosensitive resin composition of the present invention contains a photoacid generator (B), the chemically amplified positive-type photosensitive resin composition can exhibit radiation-sensitive (or light-sensitive) 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, or may be formed as a part of the polymer constituting the resin (A). The form incorporated into the resin (A) may also be a combination of these two forms. These photoacid generators (B) may be used individually, and may use 2 or more types together.

The photoacid generator (B) may contain, in addition to an oxime sulfonate compound containing an oxime sulfonate group, an N-sulfonyloxyimide compound, an onium salt, a halogen-containing compound, a diazomethane compound , Sulfonate compounds, sulfonate compounds, carboxylate compounds, etc.

The oxime sulfonate compound is a compound containing an oxime sulfonate group of the following structural formula (4-1).

In the structural formula (4-1), ^R20 is an alkyl group with 1 to 20 carbons, a monovalent alicyclic hydrocarbon group, an aryl group, or the above-mentioned groups (alkyl, monovalent alicyclic hydrocarbon group , aryl) is a group in which hydrogen atoms are partially or fully substituted; and, * is a bond.

The alkyl group represented by R ²⁰ is preferably a linear or branched alkyl group with 1 to 12 carbon atoms.

The monovalent alicyclic hydrocarbon group represented by R ²⁰ is preferably an alicyclic hydrocarbon group with 4 to 12 carbon atoms.

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

The substituent includes, for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a pendant oxy group, a halogen atom, and the like.

As a compound containing the oxime sulfonate group represented by structural formula (4-1), the oxime sulfonate compound etc. which are represented by following formula (4-2) - a formula (4-4) are mentioned, for example.

In the formulas (4-2) to (4-4), R ²¹ has the same meaning as R ²⁰ in the structural formula (4-1). In the formulas (4-2) and (4-3), R ²² is an alkyl group with 1 to 12 carbons, or a fluoroalkyl group with 1 to 12 carbons. In formula (4-4), X is an alkyl group, an alkoxy group, or a halogen atom. i is an integer of 0 to 3. However, when i is 2 or 3, a plurality of X may be the same or different.

The alkyl group represented by X is preferably a linear or branched alkyl group with 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.

Examples of the oxime sulfonate compound represented by the formula (4-4) include compounds represented by the following formula (4-5) to formula (4-9).

The compounds represented by the formula (4-5) to the formula (4-9) are respectively: (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methyl Phenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-camphorsulfonyloxyimino- 5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl ) acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, 4-methylphenylsulfonyloxyimino-α-(4-methyl (oxyphenyl)acetonitrile, commercially available above-mentioned compounds can be used.

The aforementioned N-sulfonyloxyimide compounds include, for example, N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)butyl Diimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-( 4-Fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide imine, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N- (Trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyl Oxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyl Acyloxy)diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-( 4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(trifluoromethanesulfonyloxy)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-dicarboxyimide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-methylphenyl Sulfonyloxy)-7-oxabicyclo[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-dicarboxyimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N- (4-Fluorophenylsulfonyloxy)-7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxyl-2 ,3-Dicarboxyimide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxyl-2,3-dicarboxyimide, N-(4-methyl phenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyimide, N-(2-trifluoromethylphenylsulfonyloxy) Bicyclo[2.2.1]heptane-5,6-oxyl-2,3-dicarboxyimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5, 6-Oxy-2,3-dicarboxyimide, N-(trifluoromethylsulfonyloxy)naphthalene dicarboximide (N-((trifluoromethylsulfonyl)oxy)naphthalene dicarboximide), N-(camphor Sulfonyloxy)naphthalimide, N-(4-methylphenylsulfonyloxy)naphthalimide, N-(phenylsulfonyloxy)naphthalimide, N-(2-trifluoromethylphenylsulfonyloxy)naphthalimide, N-(4-fluorophenylsulfonyloxy)naphthalimide, N-(pentafluoroethyl Sulfonyloxy)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, etc.

As the onium salt, halogen-containing compound, diazomethane compound, sulfonate compound, sulfonate compound, carboxylate compound, etc., compounds described in JP-A-2011-232632 can be used. For example: benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate.

Based on 100 parts by weight of the resin (A), 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 0.5 parts by weight to 6 parts by weight. If the compound containing the oxime sulfonate group of structural formula (4-1) is used as the photoacid generator (B) in the chemically amplified positive photosensitive resin composition, the prepared protective film has chemical resistance Good advantage.

solvent (C)

The type of solvent (C) in the present invention is not particularly limited. Specific examples of the solvent (C) include alcoholic hydroxyl-containing compounds, carbonyl group-containing cyclic compounds, and the like.

Specific examples of compounds containing alcoholic hydroxyl groups are acetol (acetol), 3-hydroxy-3-methyl-2-butanone (3-hydroxy-3-methyl-2-butanone), 4-hydroxy-3-methyl Base-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 (DAA)), ethyl lactate (ethyl lactate), butyl lactate (butyl lactate), propylene glycol monomethyl ether Propylene glycol monomethyl ether), propylene glycol monoethyl ether (PGEE for short), propylene glycol monomethyl ether acetate (PGMEA for short), 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), 3-methoxy-1-butanol (3-methoxy-1-butanol), 3-methyl Base-3-methoxy-1-butanol (3-methyl-3-methoxy-1-butanol) or a combination thereof. It should be noted that the compound containing alcoholic hydroxyl group is preferably diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate or a combination thereof. The alcoholic hydroxyl group-containing compound can be used alone or in combination.

Specific examples of carbonyl-containing cyclic compounds are γ-butyrolactone (γ-butyrolactone), γ-valerolactone (γ-valerolactone), δ-valerolactone (δ-valerolactone), propylene carbonate (propylene carbonate) , N-methyl pyrrolidone (N-methyl pyrrolidone), cyclohexanone (cyclohexanone) or cycloheptanone (cycloheptanone), etc. It should be noted 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.

The alcoholic hydroxyl group-containing compound may be used in combination with the carbonyl group-containing cyclic compound, and the weight ratio thereof 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 also be contained within the range not impairing the effect 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, diisopropanone or diisobutyl Ketones, etc.; or (3) ethers: diethyl ether, diisopropyl ether, di-n-butyl ether or diphenyl ether, etc.

Based on 100 parts by weight of the resin (A), the solvent (C) is used in an amount of 200 parts by weight to 2000 parts by weight, preferably 300 parts by weight to 1800 parts by weight, more preferably 500 parts by weight to 1500 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) include sensitizers, adhesion auxiliary agents, surfactants, solubility promoters, and defoamers. ) or a combination thereof.

The kind of sensitizer is not particularly limited. The sensitizer is preferably a compound containing a phenolic hydroxyl. 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-hydroxyphenylmethane, bis(4-hydroxy-2,5-di Methylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethyl Phenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-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)-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'-trihydroxyphenyl)propane, 2-(2,4-bis Hydroxyphenyl)-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-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane or 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyl -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 (polyhydroxy benzophenone): such as 2,3,4-trihydroxy benzophenone, 2,4,4'-trihydroxy benzophenone, 2,4,6-trihydroxy dibenzophenone Benzophenone, 2,3,4-trihydroxy-2'-methanol 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 types contain phenol Combinations of compounds of the formula hydroxy.

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

Specific examples of the adhesion aid include melamine compounds, silane compounds, and the like. The role of the adhesion aid is to increase the adhesion between the film formed by the photocurable polysiloxane composition and the device or the substrate.

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

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

Specific examples of silane compounds are vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, Nitrogen-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, Nitrogen-(2-aminoethyl)-3-aminopropyl Trimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropyldimethylmethoxysilane, 2-( 3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane Oxysilane, 3-mercaptopropyltrimethoxysilane, or a commercial product manufactured by Shin-Etsu Chemical Co., Ltd. (trade name such as KBM403) and the like.

When using a silane compound as an adhesion aid, based on 100 parts by weight of the resin (A), the amount of the silane compound used 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 surfactants are anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane-based surfactants, fluorine-based surfactants, or combinations thereof.

Examples of surfactants include (1) polyethylene glycol alkyl ethers (polyoxyethylene alkyl ethers): polyethylene glycol lauryl ether, etc.; (2) polyethylene glycol alkyl phenyl ethers (polyoxyethylene phenyl ethers): polyethylene glycol octylphenyl ether, polyethylene glycol nonylphenyl ether, etc.; (3) polyethylene glycol diesters: polyethylene glycol dilaurate, polyethylene glycol diesters Ethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; and (5) fatty acid modified polyesters; and (6) Polyurethanes modified by tertiary amines (tertiary amine modified polyurethanes), etc. Specific examples of commercially available surfactants are KP (manufactured by Shin-Etsu Chemical Industry), SF-8427 (manufactured by Dow Corning Toray Polysiloxane Co., Ltd. Co., Ltd. (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Kyoeisha Oleochemical Industry), F-Top (manufactured by Tochem Products Co., Ltd.) Manufactured), Megaface (manufactured by Dainippon Ink Chemical Industry (DIC)), Fluorade (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Sino-Nippon Synthetic Chemicals Manufactured), F-475 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), or a combination thereof.

Based on 100 parts by weight of the resin (A), the used amount of the surfactant 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 antifoaming agents 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 Gas products (Air products) manufacturing), etc.

Based on the amount of resin (A) used as 100 parts by weight, the amount of antifoaming agent 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 accelerator include N-hydroxydicarboxylic imide compounds (N-hydroxydicarboxylic imide) and compounds containing phenolic hydroxyl groups. A specific example of the dissolution accelerator is a phenolic hydroxyl group-containing compound used for o-naphthoquinonediazidesulfonate (B).

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

A specific example of the chemically amplified positive-type 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 a In solution state, other additives (D) may be added if necessary.

The present invention also provides a protective film, which is formed by coating the above-mentioned chemically amplified positive-type photosensitive resin composition on a substrate, followed by pre-baking, exposure, development and post-baking.

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

Formation method of 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. Moreover, this invention also includes the protective film for display elements which are applicable to the chemical amplification type positive photosensitive resin composition.

The forming method of the protective film comprises the following steps: (1) using a chemically amplified positive-type photosensitive resin composition to form a coating film on a substrate (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 irradiation with radiation (hereinafter also referred to as "step (3) ");as well as (4) The process (henceforth "process (4)") of heating the said coating film after image development.

According to this formation method, a protective film for a display element excellent in surface hardness, solvent resistance, heat resistance, and voltage retention can be formed. Moreover, the protective film for display elements which have a fine and fine pattern can be formed easily by using the chemically amplified positive type photosensitive resin composition which has favorable sensitivity. 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 coated on the substrate to form a coating film. Preferably, the solvent is removed by pre-baking the coated side.

Examples of the substrate include glass, quartz, silicon substrates, resins, and the like. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, ring-opened polymers of cyclic olefins, hydrogenated products thereof, and the like. The prebaking conditions also vary depending on the type of each component, the blending ratio, etc., and can be set at 70° C. to 120° C. for about 1 minute to 10 minutes.

[step (2)]

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

[step (3)]

In this step, the above-mentioned coating film irradiated with radiation is developed. By developing the exposed coating film, unnecessary parts (radiation irradiation parts) 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.

The alkaline aqueous solution may be used by adding a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant. 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. As an image development method, a puddle method, a dipping method, a shaking dipping method, a shower method, etc. are mentioned, for example. 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 developing process, the coating film is air-dried by running water for 30 seconds to 90 seconds, and then air-dried to form a desired pattern.

[step (4)]

In this step, the above-mentioned developed coating film is heated. When heating, the patterned film is heated by using a heating device such as a heating plate or an oven to accelerate 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 machine, for example, it is about 5 minutes to 30 minutes on a heating plate, and 30 minutes in an oven. minutes to about 90 minutes. In addition, a staged baking method in which a heating step is performed two or more times, etc. can also 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. In addition, the use of the said cured film is not limited to the protective film for display elements, It can also utilize it as a spacer or an interlayer insulating film.

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

The manufacturing method and application of the chemically amplified positive-type photosensitive resin composition of the present invention will be described below by means of several preparation examples, examples and comparative examples.

Preparation of Resin (A)

Preparation Example A-1

A nitrogen inlet, a stirrer, a heater, a condenser tube and a thermometer are arranged on a four-necked conical flask with a volume of 1000 milliliters. After introducing nitrogen, add 5 parts by weight of methacrylic acid (hereinafter referred to as MAA), 20 parts by weight of 3- Methacryloxypropyltrimethoxysilane (hereinafter referred to as MAPTMS), 20 parts by weight of 2-tetrahydrofuran methacrylate, 20 parts by weight of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 25 parts by weight Parts of dicyclopentyl methacrylate (hereinafter referred to as FA-513M), 10 parts by weight of benzyl methacrylate ester (hereinafter referred to as BzMA), 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter referred to as ADVN) and 240 parts by weight of diethylene glycol dimethyl ether (hereinafter referred to as Diglyme) solvent. Next, the above ingredients were stirred slowly to raise the temperature of the solution to 70° C., and polycondensed at this temperature for 6 hours. Then, after the solvent is devolatilized, resin (A-1) can be obtained.

Preparation Examples A-2 to A-16 and Preparation Comparative Examples A'-1 to A'-4

The preparation of resins (A-2) to (A-16) and preparation comparative examples (A'-1) to (A'-4) is similar to the preparation of the aforementioned resin (A-1), wherein the type of monomer and usage are shown in Table 1. However, the amount of solvent and catalyst used, the reaction temperature and the reaction time of polycondensation are different from the aforementioned resin (A-1), which are also shown in Table 1.

Example 1

Preparation of chemically amplified positive photosensitive resin composition

With 100 parts by weight of resin (A-1) and 0.1 parts by weight of benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate (B-1), add 200 parts by weight of propylene glycol methyl ether acetate (C-1), and after stirring evenly with a shaking type stirrer, the chemically amplified positive photosensitive resin composition of Example 1 can be obtained.

Form a protective film

On a plain glass substrate (100×100×0.7mm), a coating film of about 3 μm was obtained by spin coating, followed by pre-baking at 110°C for 2 minutes, and a positive photoresist was placed between the exposure machine and the coating film Make a photomask, and irradiate the coating film with the ultraviolet light of the exposure machine, and the energy is 80mJ/cm ² . Immerse the exposed coating film in 2.38% TMAH aqueous solution at 23°C for 70 seconds to remove the exposed part. After washing with clean water, the developed coating film is directly irradiated with an exposure machine with an energy of 300mJ/cm ² . Finally, after baking at 220°C for 45 minutes, the protective film on the plain glass substrate of Example 1 can be obtained.

About the concrete condition of embodiment 1 and evaluation result, note as shown in table 2.

Examples 2 to 16 and Comparative Examples 1 to 4

The chemically amplified positive photosensitive resin compositions and protective films of Examples 2 to 16 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1. The difference is that conditions such as composition or usage amount were changed in Examples 2 to 16 and Comparative Examples 1 to 4. The specific conditions and evaluation results of Examples 2 to 16 and Comparative Examples 1 to 4 are shown in Table 2 and Table 3.

Evaluation method

(1) Development adhesion:

With the formation method of the above-mentioned protective film, after forming the coating film of the chemically amplified positive-type photosensitive resin composition, through a pattern photoresist having a line and space pattern with a width of 1 μm to 10 μm , the said The coating film was irradiated with ultraviolet rays of 80 mJ/cm ² . Next, after developing at 25 degreeC for 70 second using the 2.38 mass % aqueous solution of tetramethylammonium hydroxide, it wash|cleaned with running water for 1 minute with ultrapure water. Use a microscope to observe the peeling of the line and space patterns with a width of 1 μm to 10 μm after cleaning, as an evaluation of the development adhesion.

◎: No pattern peeling

○: A small amount of pattern peeling off

Δ: Part of the pattern peeled off

×: The entire surface of the pattern is peeled off

(2) Chemical resistance:

After forming a coating film of the chemically amplified positive-type photosensitive resin composition by the above method of forming a protective film, the coating film was 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 obtained 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

As shown in Table 2, when the mixture of resin (A) for synthesizing the chemically amplified positive photosensitive resin composition includes unsaturated carboxylic acid monomer (a-1), silyl-containing unsaturated compound (a- 2) and the acid-dissociable group-containing monomer (a-3), the protective film formed from the chemically amplified positive photosensitive resin composition can have good development adhesion and chemical resistance. In some embodiments, when the mixture further includes an epoxy group-containing unsaturated monomer (a-4), and especially an unsaturated monomer with oxetane, the development of the protective film can be further improved Adhesion. In some other embodiments, when the chemically amplified positive photosensitive resin composition uses a photoacid generator (B) having an oxime sulfonate group, the chemical resistance of the protective film can be further improved.

On the other hand, as shown in Table 3, if no silane-containing When the unsaturated compound (a-2) and/or acid-dissociative group-containing monomer (a-3) is used, the chemical resistance and development adhesion of the protective film obtained are not good.

Using the chemically amplified positive photosensitive resin composition of the present invention, the resin (A) synthesized from a specific monomer can form a protective film with good development adhesion and chemical resistance. This protective film can be used, for example, for display elements.

Although the present invention has been disclosed above in terms of implementation, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field of the present invention can make various modifications and changes without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be defined by the scope of the appended patent application.

Claims (8)

A chemically amplified positive-type photosensitive resin composition, comprising: a resin (A); a photoacid generator (B); and a solvent (C), wherein the resin (A) is obtained by copolymerizing a mixture, and the The mixture includes unsaturated carboxylic acid monomer (a-1), silyl group-containing unsaturated compound (a-2) represented by structural formula (1-1), and acid containing compound represented by structural formula (2-1) Dissociative group monomer (a-3), based on the usage amount of the mixture is 100 parts by weight, the usage amount of the unsaturated carboxylic acid monomer (a-1) is 5 parts by weight to 50 parts by weight, the silane-containing The use amount of the unsaturated compound (a-2) of the group is 5 parts by weight to 50 parts by weight, and the use amount of the monomer (a-3) containing an acid dissociative group is 5 parts by weight to 90 parts by weight:

In the structural formula (1-1), the R ¹ represents a hydrogen atom or a methyl group; the R ² and the R ³ represent independently independent alkyl groups with 1 to 12 carbon atoms, phenyl groups, and 1 to 12 carbon atoms. 6 alkoxy group or a group shown in structural formula (1-2); when the R ² and the R ³ are plural, each of the R ² and the R ³ is the same or different; the a represents 1 to 6 Integer; the b represents an integer from 1 to 150; the ^R represents an alkyl group with a carbon number of 1 to 6 or a group shown in structural formula (1-3);

In the structural formula (1-2), the R ⁵ , the R ⁶ and the R ⁷ represent independent alkyl or phenyl groups with 1 to 12 carbons; when the R ⁶ and the R ⁷ are plural , each of the R ⁶ and the R ⁷ is the same or different; the c represents an integer from 1 to 13; and

In the structural formula (1-3), the R ⁸ , the R ⁹ and the R ¹⁰ represent independently alkyl or phenyl groups with 1 to 12 carbons;

In the structural formula (2-1), the R ¹¹ and the R ¹² are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, wherein the alkyl group, the alicyclic hydrocarbon group or the aryl group are represented by A part or all of the hydrogen atoms may be substituted; moreover, the R ¹¹ and the R ¹² are not hydrogen atoms at the same time; the R ¹³ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group or an aryl group; wherein the R ¹³ Part or all of the hydrogen atoms of the alkyl group, the alicyclic hydrocarbon group, the aralkyl group and the aryl group may be substituted; when the R ¹³ is an alkyl group, the R ¹¹ and the R ¹³ are mutually bonded Together with the carbon atom to which R ¹¹ is bonded and the oxygen atom to which R ¹³ is bonded, a cyclic ether structure is formed, and the number of ring members of the cyclic ether structure is 3-5. The chemically amplified positive-type photosensitive resin composition as described in claim 1, wherein the mixture includes an epoxy group-containing unsaturated monomer (a-4). The chemically amplified positive-type photosensitive resin composition as described in item 2 of the scope of the patent application, wherein the epoxy group-containing unsaturated monomer (a-4) has the structure shown in the following structural formula (3-1) Unsaturated monomers of:

In the structural formula (3-1), the R ¹⁴ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; the R ¹⁵ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; the R ¹⁶ , the R ¹⁷ , the R ¹⁸ and the R ¹⁹ independently represent a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group with 1 to 4 carbons, or a perfluoroalkyl group with 1 to 4 carbons; and the a represents 1 Integers up to 6. The chemically amplified positive-type photosensitive resin composition as described in Item 1 of the patent application, wherein the photoacid generator (B) is a compound containing an oxime sulfonate group of the following structural formula (4-1):

In the structural formula (4-1), the ^R20 is an alkyl group, an alicyclic hydrocarbon group, an aryl group with a carbon number of 1 to 20, or a group in which the hydrogen atoms in the above groups are partially or fully substituted group; and, the * is a bond. The chemically amplified positive-type photosensitive resin composition as described in item 1 of the scope of the patent application, wherein the usage amount of the resin (A) is 100 parts by weight, and the usage amount of the photoacid generator (B) is 0.1 weight parts parts to 10 parts by weight, the solvent (C) is used in an amount of 200 parts by weight to 2000 parts by weight. The chemically amplified positive-type photosensitive resin composition as described in item 2 of the scope of the patent application, wherein the usage amount based on the mixture is 100 parts by weight, and the usage of the epoxy group-containing unsaturated monomer (a-4) The amount is 5 to 80 parts by weight. A protective film is coated on a substrate with a chemically amplified positive-type photosensitive resin composition as described in any one of items 1 to 6 of the scope of the patent application, and then prebaked, exposed, developed and Formed after post-baking. A component with a protective film, comprising a substrate and A protective film as described in item 7 of the scope of the patent application.