TW202125106A - Chemically amplified positive photosensitive resin composition and uses thereof - Google Patents

Abstract

The present invention relates to a chemically amplified positive photosensitive resin compostion including a first resin (A1), a second resin (A2), a photoacid generator (B), a solvent (C), a compound (D) represented by Formula (6) or Formula (7), and a hindered amine compound (E) represented by Formula (e1). A protection film formed by the chemically amplified positive photosensitive resin composition has the advantages of favorable sensitivity and stability over time. The present invention further relates to the protection film and a component including the protection film.

Description

Chemically amplified positive photosensitive resin composition and its application

The present invention relates to a chemically amplified positive photosensitive resin composition and its application, and in particular to a chemically amplified positive photosensitive resin, which has the advantages of good sensitivity and stability over time, and its preparation The protective film and the components containing the protective film.

Display elements such as thin film transistor type liquid crystal display elements or organic electroluminescence devices (organic electroluminescence devices, organic EL elements) usually include insulating films such as interlayer insulating films or planarization films, and such insulating films are usually composed of radiation-sensitive components Things to form. In order to meet the requirements of patterning performance, a positive photosensitive resin composition containing acid generators such as naphthoquinone diazide (naphthoquinone diazide) can usually be used (refer to Japanese Patent Laid-Open No. 2001-354822), but in recent years Many other photosensitive compositions are still being proposed.

For example, Japanese Patent Laid-Open No. 2004-4669 relates to a positive type chemically amplified material that forms a hardened film for display elements. The positive type chemically amplified material uses a naphthoquinone diazide compound, etc. The positive photosensitive resin composition of the acid generator has higher sensitivity. The positive chemical amplification material contains a crosslinking agent, an acid generator, and an acid dissociable resin, wherein 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 alkaline In aqueous solution, but the protective group is dissociated by the action of acid and it is soluble in alkaline aqueous solution. In addition, for example, Japanese Patent Laid-Open No. 2004-264623, Japanese Patent Laid-Open No. 2011-215596, and Japanese Patent Laid-Open No. 2008-304902 also propose to contain an acetal structure and/or a ketal structure and an epoxy group. The positive photosensitive composition of the resin and acid generator.

In such photosensitive resin compositions, in addition to high photosensitivity, storage stability that does not easily change in viscosity during long-term storage is also required, so that the cured film formed by such photosensitive resin compositions can be free from developer The chemical resistance of swelling and so on. According to this, the pattern formed by the cured film may be sufficiently adhered to the substrate after development and not easily peeled off, and the cured film has sufficient transparency, even if it is left after exposure, the pattern is sufficiently adhered to the substrate and not easily peeled off.

However, the current photosensitive resin composition still has the problem of poor sensitivity and stability over time, and it is still unacceptable in the industry.

The present invention can make it have the advantages of good sensitivity and stability over time by the special composition and/or ratio of the chemically amplified positive photosensitive resin composition.

式(1) 式(1)中，R₁₁ 和R₁₂ 各自獨立為氫原子、烷基、脂環式烴基或芳基，其中所述烷基、脂環式烴基或芳基所具有的氫原子可部分或全部被取代，且R₁₁ 及R₁₂ 不同時為氫原子；R₁₃ 為烷基、脂環式烴基、芳烷基或芳基，其中所述烷基、脂環式烴基、芳烷基及芳基所具有的氫原子可部分或全部被取代；R₁₁ 與R₁₃ 可相互鍵結而與R₁₁ 所鍵結的碳原子以及R₁₃ 所鍵結的氧原子共同形成環狀醚結構； 一第二樹脂(A2)，由一第二混合物共聚合而得，該第二混合物包含不飽和羧酸單體(a2-1)以及含酚性羥基的不飽和單體(a2-2)； 一光酸產生劑(B)； 一溶劑(C)； 一式(6)或式(7)所示之化合物(D)：

式(6) 式(6)中，R¹ 及R² 各自獨立為碳數1至4的烷基；n₆ 為0至2的整數；L¹ 為單鍵或二價連結基；X¹ 為-S-或-NH-；R³ 為一價有機基；

式(7) 式(7)中，R⁵ 及R⁶ 各自獨立為碳數1至4的烷基；n₇ 為0至2的整數；L² 為單鍵或二價連結基；X² 為-S-或-NH-；A為包含碳原子及氮原子的雜環；以及 一式(e1)所示之受阻胺化合物(E)，

式(e1) 式(e1)中，n為4以上的整數；E₁ 為n價有機基；E₂ 至E₅ 各自獨立為碳數1至12的一價有機基；E₆ 為氫原子或碳數1至12的一價烷基。Therefore, the present invention provides a chemically amplified positive photosensitive resin composition, comprising: a first resin (A1) obtained by copolymerization of a first mixture, the first mixture containing an unsaturated carboxylic acid monomer (a1) -1), the monomer (a1-2) containing the acid dissociable group represented by the structural formula (1) and the unsaturated monomer (a1-3) containing the lactone structure;

Formula (1) In formula (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 atom of the alkyl group, alicyclic hydrocarbon group or aryl group It may be partially or fully 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 the alkyl group, alicyclic hydrocarbon group, aralkyl group The hydrogen atoms of the group and the aryl group can be partially or fully substituted; R ₁₁ and R ₁₃ can be bonded to each other to form a cyclic ether structure with the carbon atom bonded _{to R 11 and the oxygen atom bonded to R 13} ; A second resin (A2), obtained by copolymerization of a second mixture, the second mixture containing unsaturated carboxylic acid monomer (a2-1) and phenolic hydroxyl-containing unsaturated monomer (a2-2) ; One photoacid generator (B); One solvent (C); One compound (D) represented by formula (6) or formula (7):

Formula (6) In formula (6), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms; n ₆ is an integer from 0 to 2; L ¹ is a single bond or a divalent linking group; X ¹ is -S- or -NH-; R ³ is a monovalent organic group;

Formula (7) In formula (7), R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbons; n ₇ is an integer from 0 to 2; L ² is a single bond or a divalent linking group; X ² is -S- or -NH-; A is a heterocyclic ring containing carbon atoms and nitrogen atoms; and a hindered amine compound (E) represented by formula (e1),

Formula (e1) In formula (e1), n is an integer of 4 or more; E ₁ is an n-valent organic group; E ₂ to E ₅ are each independently a monovalent organic group with 1 to 12 carbon _{atoms; E 6} is a hydrogen atom or A monovalent alkyl group having 1 to 12 carbons.

The present invention also provides a protective film, which is formed by coating the aforementioned chemically amplified positive photosensitive resin composition on a substrate, and then undergoing pre-baking, exposure, development and post-baking treatments.

The present invention also provides a device with a protective film, comprising a substrate and the aforementioned protective film, and the protective film is attached to the substrate.

式(1) 式(1)中，R₁₁ 和R₁₂ 各自獨立為氫原子、烷基、脂環式烴基或芳基，其中所述烷基、脂環式烴基或芳基所具有的氫原子可部分或全部被取代，且R₁₁ 及R₁₂ 不同時為氫原子；R₁₃ 為烷基、脂環式烴基、芳烷基或芳基，其中所述烷基、脂環式烴基、芳烷基及芳基所具有的氫原子可部分或全部被取代；R₁₁ 與R₁₃ 可相互鍵結而與R₁₁ 所鍵結的碳原子以及R₁₃ 所鍵結的氧原子共同形成環狀醚結構； 一第二樹脂(A2)，由一第二混合物共聚合而得，該第二混合物包含不飽和羧酸單體(a2-1)以及含酚性羥基的不飽和單體(a2-2)； 一光酸產生劑(B)； 一溶劑(C)； 一式(6)或式(7)所示之化合物(D)：

式(6) 式(6)中，R¹ 及R² 各自獨立為碳數1至4的烷基；n₆ 為0至2的整數；L¹ 為單鍵或二價連結基；X¹ 為-S-或-NH-；R³ 為一價有機基；

式(7) 式(7)中，R⁵ 及R⁶ 各自獨立為碳數1至4的烷基；n₇ 為0至2的整數；L² 為單鍵或二價連結基；X² 為-S-或-NH-；A為包含碳原子及氮原子的雜環；以及 一式(e1)所示之受阻胺化合物(E)，

式(e1) 式(e1)中，n為4以上的整數；E₁ 為n價有機基；E₂ 至E₅ 各自獨立為碳數1至12的一價有機基；E₆ 為氫原子或碳數1至12的一價烷基。The present invention provides a chemically amplified positive photosensitive resin composition, comprising: a first resin (A1) obtained by copolymerization of a first mixture, the first mixture containing an unsaturated carboxylic acid monomer (a1-1) ), a monomer (a1-2) containing an acid dissociable group represented by the structural formula (1) and an unsaturated monomer (a1-3) containing a lactone structure;

Formula (1) In formula (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 atom of the alkyl group, alicyclic hydrocarbon group or aryl group It may be partially or fully 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 the alkyl group, alicyclic hydrocarbon group, aralkyl group The hydrogen atoms of the group and the aryl group can be partially or fully substituted; R ₁₁ and R ₁₃ can be bonded to each other to form a cyclic ether structure with the carbon atom bonded _{to R 11 and the oxygen atom bonded to R 13} ; A second resin (A2), obtained by copolymerization of a second mixture, the second mixture containing unsaturated carboxylic acid monomer (a2-1) and phenolic hydroxyl-containing unsaturated monomer (a2-2) ; One photoacid generator (B); One solvent (C); One compound (D) represented by formula (6) or formula (7):

Formula (6) In formula (6), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms; n ₆ is an integer from 0 to 2; L ¹ is a single bond or a divalent linking group; X ¹ is -S- or -NH-; R ³ is a monovalent organic group;

Formula (7) In formula (7), R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbons; n ₇ is an integer from 0 to 2; L ² is a single bond or a divalent linking group; X ² is -S- or -NH-; A is a heterocyclic ring containing carbon atoms and nitrogen atoms; and a hindered amine compound (E) represented by formula (e1),

Formula (e1) In formula (e1), n is an integer of 4 or more; E ₁ is an n-valent organic group; E ₂ to E ₅ are each independently a monovalent organic group with 1 to 12 carbon _{atoms; E 6} is a hydrogen atom or A monovalent alkyl group having 1 to 12 carbons.

Hereinafter, each component of the chemically amplified positive photosensitive resin composition used in the present invention will be described in detail.

The first resin (A1) of the present invention can be obtained by copolymerization of a first mixture. The first mixture can contain unsaturated carboxylic acid monomer (a1-1) and contains the acid dissociation shown by structural formula (1). Monomers (a1-2) and lactone-containing unsaturated monomers (a1-3).

The unsaturated carboxylic acid monomer (a1-1) of the present invention refers to a compound containing a carboxylic acid group or carboxylic acid anhydride structure and an unsaturated bond for polymerization. The structure is not particularly limited and may include, but is not limited to, an unsaturated monomer A carboxylic acid compound, an unsaturated dicarboxylic acid compound, an unsaturated dicarboxylic anhydride compound, a polycyclic unsaturated carboxylic acid compound, a polycyclic unsaturated dicarboxylic acid compound, and a polycyclic unsaturated dicarboxylic 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 It is 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.

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 (a1-1) are acrylic acid, methacrylic acid, maleic anhydride, 2-methacrylic acid ethoxy succinate, and 2-methacrylic acid ethyl ester. Oxyhexahydrophthalic acid or a combination thereof.

The above-mentioned unsaturated carboxylic acid monomer (a1-1) can be used singly or as a mixture of plural kinds. Based on 100 parts by weight of the total usage of the first mixture of the first resin (A1), the usage amount of the unsaturated carboxylic acid monomer (a1-1) is 3 parts by weight to 30 parts by weight; preferably 4 parts by weight To 28 parts by weight; more preferably 5 parts by weight to 25 parts by weight.

式(1) 式(1)中，R₁₁ 和R₁₂ 各自獨立為氫原子、烷基、脂環式烴基或芳基，其中所述烷基、脂環式烴基或芳基所具有的氫原子可部分或全部被取代，且R₁₁ 及R₁₂ 不同時為氫原子；R₁₃ 為烷基、脂環式烴基、芳烷基或芳基，其中所述烷基、脂環式烴基、芳烷基及芳基所具有的氫原子可部分或全部被取代；R₁₁ 與R₁₃ 可相互鍵結而與R₁₁ 所鍵結的碳原子以及R₁₃ 所鍵結的氧原子共同形成環狀醚結構。The acid-dissociable group-containing monomer (a1-2) of the present invention has an acid-dissociable group represented by the following formula (1):

Formula (1) In formula (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 atom of the alkyl group, alicyclic hydrocarbon group or aryl group It may be partially or fully 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 the alkyl group, alicyclic hydrocarbon group, aralkyl group The hydrogen atoms of the group and the aryl group can be partially or fully substituted; R ₁₁ and R ₁₃ can be bonded to each other to form a cyclic ether structure with the carbon atom bonded _{to R 11 and the oxygen atom bonded to R 13} .

The acid dissociable group of the acid dissociable group-containing monomer (a1-2) 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 (a1-2) is not particularly limited as long as it contains a structure as in formula (1). This acid-dissociable group-containing monomer (a1-2) can be easily dissociated by acid.

Examples of the alicyclic hydrocarbon group represented by R ₁₁ and R ₁₂ include alicyclic hydrocarbon groups having 3 to 20 carbon atoms. In addition, the alicyclic hydrocarbon group having 3 to 20 carbon atoms may be polycyclic. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bornyl, norbornyl, adamantyl, and the like.

Examples of the aryl group represented by R ₁₁ and R ₁₂ include an aryl group having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms may be a monocyclic ring, a structure formed by linking monocyclic rings, or a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the substituents of the substituted alkyl group, alicyclic hydrocarbon group, and aryl group represented by R ₁₁ and R ₁₂ 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 (e.g., phenyl, naphthyl, etc.), alkoxy (e.g. Methoxy, ethoxy, propoxy, n-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and other alkoxy groups having 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 and other carbon 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, a group obtained by substituting a part or all of the hydrogen atoms of the above groups with halogen atoms), hydroxyalkyl groups (for example, hydroxymethyl, etc.), etc. .

As for the alkyl group, alicyclic hydrocarbon group, and aryl group represented by R ₁₃ above, the description of each group represented by _{R 11} and R _{12 can be applied.} 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 ₁₃ include benzyl, phenethyl, naphthylmethyl, and naphthylethyl.

The above-mentioned _{cyclic ether structure formed by bonding R 11} and R ₁₃ to each other is preferably a cyclic ether structure with a ring member number of 3 to 20, more preferably a cyclic ether structure with a ring member number of 5 to 8, 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 (a1-2) 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, 1-ethoxyethyl acrylate, 1-methoxy acrylate Ethyl acrylate, 1-n-butoxy ethyl acrylate, 1-isobutoxy ethyl acrylate, 1-tert-butoxy ethyl acrylate, 1-(2-chloroethoxy) ethyl acrylate, acrylic acid 1-(2-Ethylhexyloxy) ethyl, 1-n-propoxy ethyl acrylate, 1-cyclohexyloxy ethyl acrylate, 1-(2-cyclohexylethoxy) ethyl acrylate, acrylic acid 1-Benzyloxyethyl, 2-tetrahydropyranyl acrylate, 5,6-bis(1-methoxyethoxycarbonyl)-2-norbornene, 5,6-bis(1-( Cyclohexyloxy)ethoxycarbonyl)-2-norbornene, 5,6-bis(1-(benzyloxy)ethoxycarbonyl)-2-norbornene, p-1-ethoxyethyl Oxystyrene or m-1-ethoxyethoxystyrene, p-1-methoxyethoxystyrene or m-1-methoxyethoxystyrene, p-1-n-butyl Oxyethoxystyrene or m-1-n-butoxyethoxystyrene, p-1-isobutoxyethoxystyrene or m-1-isobutoxyethoxystyrene, P-1-(1,1-dimethylethoxy)ethoxystyrene or m-1-(1,1-dimethylethoxy)ethoxystyrene, p-1-(2 -Chloroethoxy)ethoxystyrene or meta-1-(2-chloroethoxy)ethoxystyrene, p-1-(2-ethylhexyloxy)ethoxystyrene or meta -1-(2-ethylhexyloxy)ethoxystyrene, 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 dissociable group-containing monomer (a1-2) is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate , 1-benzyloxyethyl methacrylate, 1-cyclohexoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, more preferably 2-tetrahydropyranyl methacrylate and methacrylic acid Tetrahydrofurfuryl ester.

The total usage amount of the first mixture based on the first resin (A1) is 100 parts by weight, and the usage amount of the acid dissociable group-containing monomer (a1-2) is 15 parts by weight to 70 parts by weight, preferably 17 parts by weight. Parts by weight to 68 parts by weight, more preferably 20 parts by weight to 65 parts by weight.

If the chemically amplified positive photosensitive resin composition of the present invention does not use the acid dissociable group-containing monomer (a1-2) in the first mixture of the first resin (A1) used, it is likely to have The problem of poor sensitivity.

式(3) 式(3)中，R^X1 為氫原子或烷基；R^A2 為碳數1至8的烷基、碳數3至7的環烷基、碳數1至8的烷氧基、碳數2至8的烷氧基羰基、羧基、鹵素原子、羥基、氰基或酸分解性基，當n₂ 大於1時，複數個R^A2 可相同或不同；A¹ 為單鍵或二價連結基；Z² 為含有-O-C(=O)-的單環或多環結構；n₂ 為0以上的整數。The unsaturated monomer (a1-3) containing a lactone structure of the present invention is preferably a compound represented by formula (3):

Formula (3) In formula (3), R ^X1 is a hydrogen atom or an alkyl group; R ^A2 is an alkyl group having 1 to 8 carbons, a cycloalkyl group having 3 to 7 carbons, or an alkoxy group having 1 to 8 carbons , Alkoxycarbonyl group, carboxyl group, halogen atom, hydroxyl group, cyano group or acid-decomposable group with 2 to 8 carbon atoms, when n _{2 is} greater than 1, plural R ^A2 may be the same or different; A ¹ is a single bond or two Valence linking group; Z ² is a monocyclic or polycyclic structure containing -OC(=O)-; n ₂ is an integer of 0 or more.

The alkyl group of R ^X1 is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. The alkyl group may have a substituent, and the substituent is preferably a hydroxyl group or a halogen atom (especially a fluorine atom).

The aforementioned R ^{A2 is} preferably an alkyl group having 1 to 4 carbon atoms or a cyano group.

Examples of the aforementioned ^{divalent linking group of A 1} include linear, branched or cyclic alkylene, aryl alkylene, -O-, -COO-, -S-, -NR"-, -CO- , -NR"CO-, -SO ₂ -and other divalent groups, or groups containing a combination of these groups, R" is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, preferably a hydrogen atom. Among them, The ^{divalent linking group of A 1} preferably contains at least one of -O-, -COO-, -S-, -NH- and -CO-, or a combination of _{these groups and -(CH 2} ) _m- As a group, m is an integer from 1 to 10, preferably an integer from 1 to 6, and more preferably an integer from 1 to 4.

The aforementioned Z ^{2 is} preferably a monocyclic structure. When Z ² represents a monocyclic structure, it is preferable to form a 5-membered to 7-membered lactone structure, and it is more preferable to form a 5-membered or 6-membered lactone structure. When Z ¹ represents a polycyclic structure, it is preferable that other ring structures are condensed to the lactone structure in the form of a bicyclic structure or a spiro structure. Examples of other ring structures include cyclic hydrocarbon groups having 3 to 20 carbon atoms, heterocyclic groups having 3 to 20 carbon atoms, and the like. The heterocyclic group is not particularly limited, and one or more of the atoms constituting the ring are heteroatoms, or an aromatic heterocyclic group. In addition, the heterocyclic group is preferably a 5-membered ring or a 6-membered ring, and particularly preferably a 5-membered ring. Specifically, the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.

The aforementioned n _{2 is} preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. When n ₂ represents an integer of 2 or more, a plurality of R ^A2 may be the same or different. In addition, a plurality of ^RA2 may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.

式(3-1) 式(3-1)中，R^X2 為氫原子或烷基；R^A3 為碳數1至8的烷基、碳數3至7的環烷基、碳數1至8的烷氧基、碳數2至8的烷氧基羰基、羧基、鹵素原子、羥基、氰基或酸分解性基，當n₃ 大於1時，複數個R^A3 可相同或不同；A² 為單鍵或二價連結基；Z³ 為含有-O-C(=O)-的單環或多環結構；n₃ 為0以上的整數；X¹ 為氧原子或-NR"-，且R"為氫原子或烷基。In addition, the unsaturated monomer (a1-3) containing a lactone structure is preferably represented by the following general formula (3-1):

Formula (3-1) In the formula (3-1), R ^X2 is a hydrogen atom or an alkyl group; R ^A3 is an alkyl group having 1 to 8 carbons, a cycloalkyl group having 3 to 7 carbons, and a carbon number of 1 to 8 When n _{3 is} greater than 1, plural R ^A3 may be the same or different; A ² is Single bond or divalent linking group; Z ³ is a monocyclic or polycyclic structure containing -OC(=O)-; n ₃ is an integer greater than 0; X ¹ is an oxygen atom or -NR"-, and R" is Hydrogen atom or alkyl group.

The alkyl group of R ^X2 is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. The alkyl group may have a substituent, and the substituent is preferably a hydroxyl group or a halogen atom (especially a fluorine atom).

The aforementioned R ^{A3 is} preferably an alkyl group having 1 to 4 carbon atoms or a cyano group.

The above-mentioned ^{divalent linking group of A 2 can} be exemplified by linear, branched or cyclic alkylene, aryl alkylene, -O-, -COO-, -S-, -NR"-, -CO- , -NR"CO-, -SO ₂ -and other divalent groups, or groups containing a combination of these groups, R" is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, preferably a hydrogen atom. Among them, The ^{divalent linking group of A 2} is preferably a group containing at least one of -COO-, -CO-, or _{a combination of these groups and -(CH 2} ) _m -, and m is an integer from 1 to 10, more It is preferably an integer of 1 to 6, and more preferably an integer of 1 to 4. A ^{2 is} particularly preferably a single bond.

The aforementioned Z ^{3 is} preferably a monocyclic structure. When Z ³ represents a monocyclic structure, it is preferable to form a 5-membered to 7-membered lactone structure, and it is more preferable to form a 5-membered or 6-membered lactone structure. When Z ¹ represents a polycyclic structure, it is preferable that other ring structures are condensed to the lactone structure in the form of a bicyclic structure or a spiro structure. Examples of other ring structures include cyclic hydrocarbon groups having 3 to 20 carbon atoms, heterocyclic groups having 3 to 20 carbon atoms, and the like. The heterocyclic group is not particularly limited, and one or more of the atoms constituting the ring are heteroatoms, or an aromatic heterocyclic group. In addition, the heterocyclic group is preferably a 5-membered ring or a 6-membered ring, and particularly preferably a 5-membered ring. Specifically, the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.

The aforementioned n _{3 is} preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. When n ₃ represents an integer of 2 or more, a plurality of R ^A3 may be the same or different. In addition, a plurality of ^RA3 may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.

The aforementioned X ^{1 is} preferably an oxygen atom. If X ¹ is -NR"-, R" may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom.

式(LC1-1)至式(LC1-21)中，Rb₂ 為碳數1至8的烷基、碳數3至7的環烷基、碳數1至8的烷氧基、碳數2至8的烷氧基羰基、羧基、鹵素原子、羥基、氰基或酸分解性基，當n4大於1時，複數個Rb₂ 可相同或不同。The structure represented by formula (3) preferably contains a structure represented by any one of the following formulas (LC1-1) to (LC1-21):

In formulas (LC1-1) to (LC1-21), Rb ₂ is an alkyl group having 1 to 8 carbons, a cycloalkyl group having 3 to 7 carbons, an alkoxy group having 1 to 8 carbons, and a carbon number of 2 Up to 8 alkoxycarbonyl groups, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups or acid-decomposable groups, when n4 is greater than 1, plural Rb ₂ may be the same or different.

The formulas (LCl-1) to formula (LC1-21) may have a structure represented by Rb ₂ may not have Rb _2; preferably having no Rb _2, i.e., n4 is 0. The aforementioned Rb _{2 is} preferably an alkyl group having 1 to 4 carbons or a cyano group.

The aforementioned n4 is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0. When n4 represents an integer of 2 or more, a plurality of Rb ₂ may be the same or different. In addition, a plurality of Rb ₂ may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.

Among them, the structure represented by formula (3) preferably contains formula (LC1-1), formula (LC1-4), formula (LC1-5), formula (LC1-6), formula (LC1-13), The structure represented by (LC1-14) and formula (LC1-17) more preferably contains the structure represented by formula (LC1-1), formula (LC1-4), and formula (LC1-17).

式(3-3) 式(3-4) 式(3-5) 式(3-6)

式(3-7) 式(3-8) 式(3-9) 式(3-10)

式(3-11) 式(3-12) 式(3-13) 式(3-14)

式(3-15) 式(3-16) 式(3-17) 式(3-18)

式(3-19) 式(3-20) 式(3-21) 式(3-22)

         式(3-23)          式(3-23)至式(3-23)中R^8e 之定義與前述R^X2 之定義相同。The following formulas (3-3) to (3-23) are specific examples of the lactone structure-containing unsaturated monomer (a1-3) of the present invention, but the present invention is not limited to this:

Formula (3-3) Formula (3-4) Formula (3-5) Formula (3-6)

Formula (3-7) Formula (3-8) Formula (3-9) Formula (3-10)

Formula (3-11) Formula (3-12) Formula (3-13) Formula (3-14)

Formula (3-15) Formula (3-16) Formula (3-17) Formula (3-18)

Formula (3-19) Formula (3-20) Formula (3-21) Formula (3-22)

Formula (3-23) The definition ^{of R 8e in} formula (3-23) to formula (3-23) is the same as the definition of ^{R X2 mentioned above.}

式(3-24) 式(3-25) 式(3-26) 式(3-27)

式(3-28) 式(3-29) 式(3-30) 式(3-31)

   式(3-32) 式(3-33) 式(3-34)    Preferably, the unsaturated monomer (a1-3) containing a lactone structure is a structure represented by the following formula (3-24) to formula (3-34), preferably formula (3-24) to The structure represented by formula (3-29).

Formula (3-24) Formula (3-25) Formula (3-26) Formula (3-27)

Formula (3-28) Formula (3-29) Formula (3-30) Formula (3-31)

Formula (3-32) Formula (3-33) Formula (3-34)

The total usage amount of the first mixture based on the first resin (A1) is 100 parts by weight, and the usage amount of the lactone structure-containing unsaturated monomer (a1-3) is 1 part by weight to 15 parts by weight, It is preferably 1 part by weight to 14 parts by weight, more preferably 2 parts by weight to 13 parts by weight. If the chemically amplified positive photosensitive resin composition of the present invention does not use the lactone structure-containing unsaturated monomer (a1-3) in the first mixture of the first resin (A1) used, it is easy to There is a problem of poor sensitivity.

The first mixture of the first resin (A1) may further include other unsaturated monomers (a1-4). The other unsaturated monomers (a1-4) of the present invention are the aforementioned unsaturated carboxylic acid monomers (a1-1), acid-dissociable group-containing monomers (a1-2), and lactone-containing unsaturated monomers Unsaturated monomers other than (a1-3). In some embodiments, the other unsaturated monomers (a1-4) include epoxy-containing unsaturated monomers, alkyl (meth)acrylates, cycloaliphatic (meth)acrylates, (methyl) ) Aryl acrylate, unsaturated dicarboxylic acid diester, hydroxyalkyl (meth)acrylate, polyether of (meth)acrylate, aromatic vinyl compound, and other unsaturated compounds other than the foregoing.

式(9) 式(9)中，R⁸ 為氫原子或碳數為1至4之烷基；R⁹ 為氫原子或碳數為1至4之烷基；R¹⁰ 、R¹¹ 、R¹² 及R¹³ 各自獨立為氫原子、氟原子、苯基、碳數為1至4之烷基或碳數為1至4之全氟烷基；且a為1至6之整數。The epoxy-containing unsaturated monomers may include, but are not limited to, epoxy-containing (meth)acrylate compounds, epoxy-containing α-alkyl acrylate compounds, glycidyl ether compounds, such as (9) The ethylenically unsaturated monomer with oxetanyl group shown in (9), and any combination of the above:

Formula (9) In formula (9), R ⁸ is a hydrogen atom or an alkyl group with a carbon number of 1 to 4; R ⁹ is a hydrogen atom or an alkyl group with a carbon number of 1 to 4; R ¹⁰ , R ¹¹ , R ¹² And R ¹³ are each independently a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having a carbon number of 1 to 4, or a perfluoroalkyl group having a carbon number of 1 to 4; and a is 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 compounds: o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p-vinylbenzylglycidylether P-vinylbenzylglycidylether (p-vinylbenzylglycidylether).

式(9-1) 式(9-2)

式(9-3) 式(9-4) Specific examples of the aforementioned ethylenically unsaturated monomer having an oxetanyl group as shown in formula (9) may include, but are not limited to, methacrylate compounds, acrylate compounds or have the following formula (9-1 ) To the unsaturated monomer of the structure shown in formula (9-4):

Formula (9-1) Formula (9-2)

Formula (9-3) Formula (9-4)

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-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-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) Group) oxetane, 3-(methacryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloyloxyethyl)oxa Cyclobutane, 3-(methacryloxyethyl)-2-trifluoromethyloxetane, 3-(methacryloxyethyl)-2-pentafluoroethyloxa Cyclobutane, 3-(methacryloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(methacryloxyethyl)oxetane Alkyl, 3-(methacryloxyethyl)-2,2,4-trifluorooxetane or 3-(methacryloxyethyl)-2,2,4,4- Tetrafluorooxetane and other compounds.

The above-mentioned acrylate compounds may include, but are not limited to, 3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3- (Acryloxymethyl)-3-Methyloxetane, 3-(Acryloxymethyl)-2-Methyloxetane, 3-(Acryloxymethyl) -2-Trifluoromethyloxetane, 3-(acryloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloxymethyl)-2-benzene Oxetane, 3-(acryloxymethyl)-2,2-difluorooxetane, 3-(acryloxymethyl)-2,2,4-trifluorooxy Etidine, 3-(propenyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(propenyloxyethyl)oxetane, 3- (Acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-(acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl) -2-Trifluoromethyloxetane, 3-(acryloxyethyl)-2-pentafluoroethyloxetane, 3-(acryloxyethyl)-2-benzene Oxetane, 2,2-difluoro-3-(propenyloxyethyl)oxetane, 3-(propenyloxyethyl)-2,2,4-trifluorooxy Compounds such as cyclobutane or 3-(propenyloxyethyl)-2,2,4,4-tetrafluorooxetane.

In some embodiments, the epoxy-containing unsaturated monomer may further include other ethylenically unsaturated monomers with oxetanyl groups, such as 3-methyl-3-(vinyloxymethyl基)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-vinyloxypropane Yl)oxetane, 3-methyl-3-(3-vinyloxybutyl)oxetane, 3-ethyl-3-(3-vinyloxybutyl)oxetane Alkane, 3-propyl-3-(3-vinyloxybutyl)oxetane, ethylene glycol [(3-ethyl-3-oxetanyl)methyl] vinyl ether, propylene glycol [(3-Ethyl-3-oxetanyl)methyl]vinyl ether or 3,3-bis[(vinyloxy)methyl]oxetane, etc. have an oxetanyl group The vinyl ether compound.

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 include 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 compound include 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, methacrylamide, ethyl vinyl, 1,3-butadiene, iso Pentadiene, 2,3-Dimethyl 1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N -Succinimidyl-3-maleimidin benzoate, N-succinimidyl-4-maleimidin butyrate, N-succinimidyl-6 -Maleimide caproate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide.

The above-mentioned other unsaturated monomers (a1-4) can be used singly or as a mixture of plural kinds. The total usage amount of the first mixture based on the first resin (A1) is 100 parts by weight, and the usage amount of the other unsaturated monomers (a1-4) is 5 parts by weight to 95 parts by weight, preferably 10 parts by weight. Parts by weight to 90 parts by weight, more preferably 15 parts by weight to 80 parts by weight.

The second resin (A2) of the present invention can be obtained by copolymerizing a second mixture. The second mixture can contain unsaturated carboxylic acid monomer (a2-1) and phenolic hydroxyl-containing unsaturated monomer (a2-2 ).

The definition, specific examples, and preferred specific examples of the unsaturated carboxylic acid monomer (a2-1) of the present invention may be the same as the aforementioned unsaturated carboxylic acid monomer (a1-1), and therefore will not be repeated here. In addition, the unsaturated carboxylic acid monomer (a1-1) used in the first mixture of the first resin (A1) can be combined with the unsaturated carboxylic acid monomer (a1-1) used in the second mixture of the second resin (A2) a2-1) Same or different.

The above-mentioned unsaturated carboxylic acid monomer (a2-1) can be used singly or as a mixture of plural kinds. Based on 100 parts by weight of the total usage of the second mixture of the second resin (A2), the usage amount of the unsaturated carboxylic acid monomer (a2-1) is 1 part by weight to 20 parts by weight; preferably 1 part by weight To 18 parts by weight; more preferably 2 parts by weight to 15 parts by weight.

式(4) 式(4)中，R²²⁰ 為氫原子或甲基；R²²¹ 為單鍵或二價連結基；R²²² 為鹵素原子或碳數1至5的直鏈或支鏈狀烷基，當b大於1時，複數個R²²² 可相同或不同；b為0至4的整數，c為1至5的整數，且b+c為5以下。The phenolic hydroxyl-containing unsaturated monomer (a2-2) of the present invention is preferably a compound represented by formula (4):

Formula (4) In formula (4), R ²²⁰ is a hydrogen atom or a methyl group; R ²²¹ is a single bond or a divalent linking group; R ²²² is a halogen atom or a linear or branched alkyl group with 1 to 5 carbon atoms When b is greater than 1, a plurality of R ²²² may be the same or different; b is an integer from 0 to 4, c is an integer from 1 to 5, and b+c is 5 or less.

The aforementioned R ^{220 is} preferably a methyl group.

The divalent linking group of R ²²¹ may be, for example, an alkylene group. Specific examples of the alkylene group include: methylene, ethylidene, propylidene, isopropylidene, n-butylene, isobutylene, Tertiary butyl, pentylene, isopentyl, neopentyl, hexylene, etc. Among them, R ^{221 is} preferably a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

Regarding the hydroxyl group on the benzene ring, if ^{the carbon atom bonded to R 221} is used as a reference (1 position), the hydroxyl group is preferably bonded to the 4 position. In addition, considering the effects and manufacturing convenience of the present invention, a is preferably 1 or 2, more preferably 1.

Specific examples of R ²²² include: fluorine atom, chlorine atom, bromine atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, pentyl, isopentyl, new Pentyl etc. Among them, in consideration of manufacturing convenience, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable.

式(4-1) 式(4-2)

式(4-3) 式(4-4)

式(4-5) 式(4-6)

式(4-7) 式(4-8) Specific examples of the phenolic hydroxyl group-containing unsaturated monomer (a2-2) can be the following formula (4-1) to formula (4-8), of which formula (4-1) to formula (4-5) ), but the present invention is not limited to this.

Formula (4-1) Formula (4-2)

Formula (4-3) Formula (4-4)

Formula (4-5) Formula (4-6)

Formula (4-7) Formula (4-8)

The total usage amount of the second mixture based on the second resin (A2) is 100 parts by weight, and the usage amount of the phenolic hydroxyl-containing unsaturated monomer (a2-2) is 5 parts by weight to 50 parts by weight, It is preferably 7 parts by weight to 45 parts by weight, more preferably 10 parts by weight to 40 parts by weight. If the chemically amplified positive photosensitive resin composition of the present invention does not use the phenolic hydroxyl group-containing unsaturated monomer (a2-2) in the second mixture of the second resin (A2) used, it is easy to There is a problem of poor stability over time.

式(2) 式(2)中，R₂₁ 和R₂₂ 各自獨立為氫原子、烷基、脂環式烴基或芳基，其中所述烷基、脂環式烴基或芳基所具有的氫原子可部分或全部被取代，且R₂₁ 及R₂₂ 不同時為氫原子；R₂₃ 為烷基、脂環式烴基、芳烷基或芳基，其中所述烷基、脂環式烴基、芳烷基及芳基所具有的氫原子可部分或全部被取代；R₂₁ 與R₂₃ 可相互鍵結而與R₂₁ 所鍵結的碳原子以及R₂₃ 所鍵結的氧原子共同形成環狀醚結構。The second mixture used for copolymerization to obtain the second resin (A2) of the present invention may further include an acid dissociable group-containing monomer (a2-3). The acid dissociable group-containing monomer (a2-3) of the present invention has an acid dissociable group represented by the following formula (2):

Formula (2) In formula (2), R ₂₁ and R ₂₂ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, wherein the hydrogen atom of the alkyl group, alicyclic hydrocarbon group or aryl group It may be partially or fully substituted, and R ₂₁ and R _{22 are} not hydrogen atoms at the same time; R ₂₃ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group or an aryl group, wherein the alkyl group, alicyclic hydrocarbon group, aralkyl group The hydrogen atoms of the group and the aryl group can be partially or completely substituted; R ₂₁ and R ₂₃ can be bonded to each other to form a cyclic ether structure with the carbon atom bonded _{to R 21 and the oxygen atom bonded to R 23} .

The acid-dissociable group of the acid-dissociable group-containing monomer (a2-3) 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 (a2-3) is not particularly limited as long as it contains a structure as in formula (2). This acid-dissociable group-containing monomer (a2-3) can be easily dissociated by acid.

In the acid-dissociable group-containing monomer (a2-3) of the present invention, _{the definitions, specific examples and preferred specific examples of R 21} , R ₂₂ and R ₂₃ can be respectively compared with the aforementioned acid-dissociable group-containing monomer (a1 -2) R ₁₁ , R ₁₂ and R _{13 are the} same, so they will not be repeated here. In addition, the acid-dissociable group-containing monomer (a1-2) used in the first mixture of the first resin (A1) can be combined with the acid-dissociable group-containing monomer (a1-2) used in the second mixture of the second resin (A2) The monomers (a2-3) are the same or different.

The total usage amount of the second mixture based on the second resin (A2) is 100 parts by weight, and the usage amount of the acid-dissociable group-containing monomer (a2-3) is 0 parts by weight to 70 parts by weight, preferably 0 parts by weight. Parts by weight to 65 parts by weight, more preferably 5 parts by weight to 60 parts by weight.

If the chemically amplified positive photosensitive resin composition of the present invention includes the acid dissociable group-containing monomer (a2-3) in the second mixture of the second resin (A2) used, it can be further improved Sensitivity.

The second mixture used for copolymerization to obtain the second resin (A2) of the present invention may further include other unsaturated monomers (a2-4). The other unsaturated monomers (a2-4) of the present invention are the aforementioned unsaturated carboxylic acid monomers (a2-1), phenolic hydroxyl-containing unsaturated monomers (a2-2), and acid dissociable group-containing monomers Unsaturated monomers other than (a2-3).

The definition, specific examples and preferred specific examples of the other unsaturated monomers (a2-4) of the present invention can be the same as those of the other unsaturated monomers (a1-4) mentioned above, so they will not be repeated here. In addition, the other unsaturated monomers (a1-4) used in the first mixture of the first resin (A1) can be combined with the other unsaturated monomers (a2- used in the second mixture of the second resin (A2)). 4) Same or different.

The above-mentioned other unsaturated monomers (a2-4) can be used singly or in combination of plural kinds. The total usage amount of the second mixture based on the second resin (A2) is 100 parts by weight, and the usage amount of the other unsaturated monomers (a2-4) is 5 parts by weight to 95 parts by weight, preferably 10 parts by weight. Parts by weight to 85 parts by weight, more preferably 15 parts by weight to 80 parts by weight.

The first resin (A1) can be polymerized, for example, by using a radical polymerization initiator to polymerize the monomers in the first mixture in a suitable solvent to produce the first resin (A1). For example, it is preferable to synthesize by the following method: a solution containing monomers and a radical polymerization initiator is added dropwise to a solution containing a reaction solvent or a monomer to carry out the polymerization reaction; a solution containing a monomer, and a solution containing a monomer The solution of the radical polymerization initiator is added dropwise to the solution containing the reaction solvent or monomer to carry out the polymerization reaction; the multiple solutions containing each monomer and the solution containing the radical polymerization initiator are added dropwise respectively The polymerization reaction and the like are carried out in a solution containing a reaction solvent or monomer.

Examples of the solvent used in the polymerization reaction of the first resin (A1) 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 Organic peroxides such as esters, 1,1'-bis-(tert-butylperoxy)cyclohexane; hydrogen peroxide, etc.

In the polymerization reaction of the first resin (A1), in order to adjust the molecular weight, a molecular weight modifier can be used in an appropriate amount. Examples of the molecular weight modifier include: chloroform, carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, and n-decyl mercaptan. Dialkyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, 3-mercaptopropionic acid, etc.

The polystyrene-converted weight average molecular weight (Mw) of the first resin (A1) obtained by Gel Penetration Chromatography (GPC) is 4000 to 38000, preferably 5000 to 28000, more preferably 6000 to 18000.

Similarly, the polymerization of the second resin (A2) can be the same as the polymerization of the aforementioned first resin (A1), except that the second mixture is used instead for polymerization, so it will not be repeated here. The second resin (A2) has a polystyrene conversion weight average molecular weight (Mw) obtained by colloid permeation chromatography of 2000 to 32000, preferably 3000 to 22000, more preferably 4000 to 12000.

Based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the first resin (A1) is 40 parts by weight to 90 parts by weight, preferably 45 parts by weight To 85 parts by weight, more preferably 50 parts by weight to 80 parts by weight; the usage amount of the second resin (A2) is 10 parts by weight to 60 parts by weight, preferably 15 parts by weight to 55 parts by weight, more preferably 20 parts by weight to 50 parts by weight.

If the first resin (A1) is not used in the chemically amplified positive photosensitive resin composition of the present invention, the sensitivity is likely to be poor; and if the chemically amplified positive photosensitive resin composition of the present invention is not When the second resin (A2) is used, there is a problem of poor stability over time.

The photoacid generator (B) of the present invention is a compound that generates an acid by irradiation with radiation, and may be, for example, a compound containing an oxime sulfonate group of the following formula (8), and N-sulfonyloxyimide At least one of the compounds. 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, it may be in the form of a compound as described later, or it may be used to constitute the first resin (A1) or the second resin A form in which a part of the polymer of (A2) is incorporated into the first resin (A1) or the second resin (A2) may 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 oxime sulfonate compound containing oxime sulfonate group and N-sulfonyloxyimide compound, as well as: onium salt, halogen-containing compound, diazomethane compound , Chalcogen compound, sulfonate compound, carboxylate compound, etc.

式(8) 式(8)中，R¹⁶ 為碳數為1至20的烷基、脂環式烴基或芳基，其中所述烷基、脂環式烴基或芳基所具有的氫原子可部分或全部被取代；＊為鍵結處。The oxime sulfonate compound is a compound containing an oxime sulfonate group of the following formula (8):

Formula (8) In formula (8), R ¹⁶ is an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group or an aryl group, wherein the hydrogen atom of the alkyl group, alicyclic hydrocarbon group or aryl group may be Part or all of it is replaced; * is the junction.

The alkyl group represented by R ¹⁶ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.

The ^{monovalent alicyclic hydrocarbon group represented by R 16} is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms.

The aryl group represented by R ¹⁶ is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, a naphthyl group, a tolyl group, and a xylyl group.

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.

式(8-1)

式(8-2)

式(8-3)Examples of the compound containing the oxime sulfonate group represented by the formula (8) include oxime sulfonate compounds represented by the following formulas (8-1) to (8-3):

Formula (8-1)

Formula (8-2)

Formula (8-3)

In the formulas (8-1) to (8-3), R ²⁶ has the same meaning ^{as R 16 in the} structural formula (3). In the formulas (8-1) and (8-2), R ²⁷ is an alkyl group having 1 to 12 carbons or a fluoroalkyl group having 1 to 12 carbons. In the formula (8-3), X is an alkyl group, an alkoxy group or a halogen atom. i is an integer from 0 to 3, and when i is 2 or 3, a plurality of Xs may be the same or different from each other.

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbons; the alkoxy group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbons. Or a branched alkoxy group; the halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

式(8-4)

式(8-5)

式(8-6)

式(8-7)

式(8-8)Examples of the oxime sulfonate compound represented by the formula (8-3) include compounds represented by the following formulas (8-4) to (8-8):

Formula (8-4)

Formula (8-5)

Formula (8-6)

Formula (8-7)

Formula (8-8)

The compounds represented by the formulas (8-4) to (8-8) 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-thiophen-2-ylidene)-(2-methylphenyl) ) Acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, 4-methylphenylsulfonyloxyimino-α-(4-methyl For oxyphenyl)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 Butenediodiimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenyl Maleimide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-methylphenylsulfon) (Oxyoxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyamido, 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-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 -Oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5 -En-2,3-dicarboxyimines, 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-fluorophenylsulfonyl (Oxyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyamido, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept Alkyl-5,6-oxy-2,3-dicarboxyimide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxy Amide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyimid, N-(2-tri Fluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6 -Oxy-2,3-dicarboxyimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylate Imine, N-((trifluoromethylsulfonyl)oxy)naphthalene dicarboximide, N-((trifluoromethylsulfonyl)oxy)naphthalene dicarboximide, N-(camphorsulfonyloxy)naphthalene dicarboximide, N-(4-Methylphenylsulfonyloxy) naphthalenedimethimide, N-(phenylsulfonyloxy)naphthalenedimethimide, N-(2-trifluoromethylphenylsulfon) (Oxyoxy) naphthalenedimethimide, N-(4-fluorophenylsulfonyloxy) naphthalenedimethimide, N-(pentafluoroethylsulfonyloxy) naphthalenedimethimide, N-(heptafluoropropyl sulfonyloxy) naphthalene dimethionine, N-(nonafluorobutyl sulfonyloxy) naphthalene dimethionine, N-(ethylsulfonyloxy) naphthalene Formimines, N-(propylsulfonyloxy) naphthalene dimethylimines, N-(butylsulfonyloxy) naphthalene dimethylimines, N-(pentylsulfonyloxy) naphthalene Dimethimide, N-(hexylsulfonyloxy) naphthalene dimethymide, N-(heptylsulfonyloxy) naphthalene dimethymide, N-(octylsulfonyloxy)naphthalene Dimethimide, N-(nonylsulfonyloxy)naphthalimide, etc.

As the onium salt, halogen-containing compound, diazomethane compound, sulfonate 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 (8-4) to (8-8) in the compound containing the oxime sulfonate of the formula (8). In addition, preferably, the photoacid generator (B) also contains an N-sulfonyloxyimide compound.

Based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the photoacid generator (B) is 0.3 to 5 parts by weight, preferably 0.4 parts by weight Parts by weight to 4.5 parts by weight, more preferably 0.5 parts by weight to 4 parts by weight.

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 4-hydroxy-3-methyl-2-butanone, 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, butyl lactate, propylene glycol monomethyl ether propylene glycol monomethyl ether), propylene glycol monoethyl ether (PGEE), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol mono-n-propyl ether (propylene glycol mono-n-propyl ether) , Propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl 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 an 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.

Based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the solvent (C) is 150 parts by weight to 1200 parts by weight, preferably 170 parts by weight to 1100 Parts by weight, more preferably 200 parts by weight to 1000 parts by weight.

式(6) 式(6)中，R¹ 及R² 各自獨立為碳數1至4的烷基；n₆ 為0至2的整數；L¹ 為單鍵或二價連結基；X¹ 為-S-或-NH-；R³ 為一價有機基。Preferably, the chemically amplified positive photosensitive resin composition of the present invention may further include a compound (D) represented by formula (6) or formula (7):

Formula (6) In formula (6), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms; n ₆ is an integer from 0 to 2; L ¹ is a single bond or a divalent linking group; X ¹ is -S- or -NH-; R ³ is a monovalent organic group.

R ¹ and R ^{2 are} preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. R ¹ and R ² preferably represent the same group.

n _{6 is} preferably an integer of 0 or 1, more preferably 0.

L ^{1 is} preferably a divalent linking group, for example, an alkylene group, an arylene group, etc., and an alkylene group is preferred.

The ^{alkylene group of L 1} is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and still more preferably an alkylene group having 3 to 5 carbon atoms. The alkylene group may have a substituent, but is preferably unsubstituted. Specific examples of alkylene include: methylene, ethylene, propylene, butylene, pentylene, hexylene, cyclohexylene, heptylene, octylene, nonylylene, and decylene Wait.

The ^{arylene group of L 1} is preferably an arylene group having 6 to 20 carbons, and more preferably an arylene group having 6 to 10 carbons. Specifically, a phenylene group, a naphthylene group, etc. can be mentioned.

The ^{alkylene group and arylene group of L 1} may contain an ether-based oxygen atom to become an alkoxy group and an aryloxy group.

X ^{1 is} preferably -NH-.

Examples of the R ³ monovalent organic group include: alkyl, aryl, alkoxy, aryloxy, acyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, etc. Among them, alkyl is preferred. ,Aryl.

The alkyl group of R ³ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. are mentioned.

The aryl group of R ³ is preferably an aryl group having 6 to 20 carbons, and more preferably an aryl group having 6 to 10 carbons. Specifically, a phenyl group, a naphthyl group, an anthryl group, etc. are mentioned.

The alkoxy group of R ³ is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms. Specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tertiary butoxy group, a pentoxy group, etc. can be mentioned.

The aryloxy group of R ³ is preferably an aryloxy group having 6 to 30 carbon atoms. Specifically, a phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecylaminophenoxy group, etc. are mentioned.

The anooxy group of R ³ is preferably a formoxy group, an alkylcarbonyloxy group having 2 to 30 carbon atoms, or an arylcarbonyloxy group having 6 to 30 carbon atoms. Specifically, an acetoxy group, a trimethylacetoxy group, a hard acetoxy group, a phenyloxy group, a p-methoxyphenylcarbonyloxy group, etc. can be mentioned.

The alkoxycarbonyloxy group of R ³ is preferably an alkoxycarbonyloxy group having 2 to 30 carbon atoms. Specifically, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, an n-octylcarbonyloxy group, etc. can be mentioned.

The ^{aryloxycarbonyloxy group of R 3} is preferably an aryloxycarbonyloxy group having 7 to 30 carbon atoms. Specifically, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a p-n-hexadecyloxyphenoxycarbonyloxy group, etc. are mentioned.

The R ³ monovalent organic group may have a substituent. Examples of the substituent include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), linear, branched or cyclic alkyl groups (for example, methyl, ethyl, propyl, etc.), alkenyl, and alkynyl groups. , Aryl, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, cyano, carboxy, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, heterocyclic oxy, Amino groups, amine groups, nitro groups, hydrazine groups, heterocyclic groups and the like. In addition, these groups may be further substituted.

R ^{3 is} preferably an alkyl group having 1 to 10 carbons or an aryl group having 6 to 20 carbons, so that the chemically amplified positive photosensitive resin composition of the present invention can further improve the development adhesion.

式(7) 式(7)中，R⁵ 及R⁶ 各自獨立為碳數1至4的烷基；n₇ 為0至2的整數；L² 為單鍵或二價連結基；X² 為-S-或-NH-；A為包含碳原子及氮原子的雜環。The compound (D) represented by formula (7) is as follows:

Formula (7) In formula (7), R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbons; n ₇ is an integer from 0 to 2; L ² is a single bond or a divalent linking group; X ² is -S- or -NH-; A is a heterocyclic ring containing a carbon atom and a nitrogen atom.

R ⁵ and R ^{6 have the same meaning as R 1} and R ² in the general formula (6), and their preferred ranges are also the same.

n _{7 has the same meaning as n 6} in the general formula (6), and the preferred range is also the same.

L ^{2 has the same meaning as L 1} in the general formula (6), and the preferred range is also the same.

X ^{2 has the same meaning as X 1} in the general formula (6), and the preferred range is also the same.

The heterocyclic ring containing a carbon atom and a nitrogen atom represented by A may be aromatic or non-aromatic, and is usually an aromatic heterocyclic ring. The heterocyclic ring containing a carbon atom and a nitrogen atom may contain heteroatoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, in addition to a nitrogen atom. Furthermore, the heterocyclic ring may be either a monocyclic ring or a condensed ring, but it is preferably a monocyclic ring. The heterocyclic ring is preferably a 3-membered ring to a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring.

The heterocyclic ring containing a carbon atom and a nitrogen atom represented by A specifically includes: pyridyl, thiazolyl, 2-furyl group, thienyl group, pyrimidinyl, and benzothiazole Group, morpholinyl, pyrrolyl, indolyl, carbazolyl, furan group, thiophene group, etc.

The heterocyclic ring containing a carbon atom and a nitrogen atom represented by A may have a substituent. The substituent has the same meaning as the substituent ^{that R 3} in the general formula (6) may have.

式(S-1)至(S-24)中，Me表示甲基，Et表示乙基。The following formulas (S-1) to (S-24) represent the compound (D) used in the present invention, but the present invention is of course not limited to these compounds:

In formulas (S-1) to (S-24), Me represents a methyl group, and Et represents an ethyl group.

Among the formulas (S-1) to (S-24), the formulas (S-1) to (S-24) are preferred, the formula (S-1) and the formula (S-8) are more preferred, and the formula (S-8) is particularly preferred. (S-1) to (S-2).

Among the compounds (D) represented by formula (6) and formula (7), the compound (D) represented by formula (7) is preferred.

The molecular weight of the compound (D) represented by formula (6) and formula (7) is preferably 1000 or less, more preferably 500 or less, and particularly preferably 400 or less. The lower limit is not particularly limited, and may be 100 or more, for example. By setting the molecular weight of the compound (D) represented by the formula (6) and the formula (7) in the above range, the present invention can achieve a better effect.

Based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the compound (D) is 0.05 parts by weight to 0.8 parts by weight; preferably 0.06 parts by weight to 0.75 parts by weight Parts; more preferably 0.07 parts by weight to 0.7 parts by weight. The compound (D) can be used alone or in combination of two or more kinds. When there are two or more components of the compound (D), it is preferable that the total amount falls within the above-mentioned range. If the compound (D) is not used in the chemically amplified positive photosensitive resin composition of the present invention, there is a problem of poor sensitivity.

式(e1)The hindered amine compound (E) of the present invention can be represented by the following formula (e1):

Formula (e1)

In formula (e1), n is an integer of 4 or more, for example, an integer of 4 to 12, or an integer of 4 to 8. Preferably, n is an integer of 5 or more.

In formula (e1), E ₁ is an n-valent organic group. The organic group includes, for example, an aliphatic hydroxyl group, an aromatic hydroxyl group, a heterocyclic group, or a group formed by a combination of one or more of a nitrogen atom, an oxygen atom, -C(=O)-, and -NH-. The molecular weight of E ₁ can be 50 to 5,000, preferably 200 to 4,000.

In formula (e1), E ₂ to E ₅ are each independently a monovalent organic group having 1 to 12 carbons. The monovalent organic group having 1 to 12 carbons includes, for example, an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons. Such an organic group may additionally have a substituent, but preferably has no substituent. Preferably, E ₂ to E ₅ are alkyl groups having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms, and still more preferably methyl groups.

In the formula (e1), E ₆ is a hydrogen atom or a monovalent alkyl group having 1 to 12 carbons, and among them, a monovalent alkyl group having 1 to 12 carbons is preferred. Preferably, E ₆ is an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.

式(e11)

式(e12)

式(e13)

式(e14)Examples of the hindered amine compound (E) can include compounds represented by formula (e11) to formula (e14):

Formula (e11)

Formula (e12)

Formula (e13)

Formula (e14)

式(e15)In formula (e12), BTC is the structure of the following formula (e15):

Formula (e15)

In addition, examples of the hindered amine compound (E) include, for example, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-tert-octyl The linear or cyclic condensate of 2-amino-2,6-dichloro-1,3,5-triazine (CHIMASSORB 944); N,N'-bis(2,2,6,6-tetramethyl- 4-piperidinyl) hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine linear or cyclic condensate (CYASORB UV-3346); N, N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) hexamethylene diamine and 4-cyclohexylamino-2,6-dichloro-1,3,5- Condensation product of triazine; N,N'-bis(2,2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and morpholine-2,4, The methylation reaction product of the polymer of 6-trichloro-1,3,5-triazine (CYASORB UV 3529); N,N'-bis(2,2,6,6-tetramethyl-4-piper (Pyridinyl) -1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine polymer, and N-butyl-1-butylamine and N-butyl-2 ,2,6,6-Tetramethyl-4-piperidinamine reaction product (CHIMASSORB 2020); N,N'1,2-ethylenediylbis-1,3-propanediamine and 2,4,6- Trichloro-1,3,5-triazine polymer, and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reaction product (UVASORB HA 88); 1,2, Copolymerization of 3,4-butanetetracarboxylic acid and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol The product of the reaction with 2,2,6,6-pentamethyl-4-piperidinyl ester (ADK STAB LA 68). Based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the hindered amine compound (E) is 0.02 parts by weight to 0.2 parts by weight; preferably 0.02 parts by weight to 0.19 parts by weight; more preferably 0.03 parts by weight to 0.18 parts by weight.

If the hindered amine compound (E) is not used in the chemically amplified positive photosensitive resin composition of the present invention, there is a problem of poor stability over time.

If the amount of the hindered amine compound (E) used in the chemically amplified positive photosensitive resin composition of the present invention falls within the above range, it will have better stability over time.

In the hindered amine compound (E) used in the chemically amplified positive photosensitive resin composition of the present invention, if n in the formula (e1) is an integer of 5 or more and E ₆ is a monovalent alkyl group having 1 to 12 carbons At this time, the stability with time of the chemically amplified positive photosensitive resin composition of the present invention can be further improved.

When the usage ratio (D)/(E) of the compound (D) and the hindered amine compound (E) is 0.5 to 10, the sensitivity and stability over time can be further improved at the same time.

The chemically amplified positive photosensitive resin composition of the present invention may further include an additive (F). Specifically, specific examples of the additive (F) are a sensitizer, an adhesion auxiliary agent, a surfactant, a solubility promoter, and a defoamer ( defoamer) or a combination thereof.

The type of sensitizer is not particularly limited. The sensitizer is preferably a compound containing phenolic hydroxy, and 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-dimethylphenyl) Phenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylbenzene Yl)-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 (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-di 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'-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 phenolic formula Combinations of hydroxy compounds.

Based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the sensitizer is 5 parts by weight to 50 parts by weight; preferably 8 parts by weight to 40 parts by weight; and More preferably, it is 10 to 35 parts by weight.

Specific examples of the adhesion aid are melamine compounds, silane-based compounds, and the like.

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- manufactured by Sanwa Chemicals. 001, MX-750 or MX-706, etc.

When a melamine compound is used as an adhesion aid, based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the melamine compound is 0 parts by weight to 20 parts by weight; It is preferably from 0.5 part by weight to 18 parts by weight; and more preferably from 1.0 part by weight to 15 parts by weight.

Specific examples of silane-based compounds are vinyl trimethoxy silane, vinyl triethoxy silane, 3-propenyloxypropyl trimethoxy silane, vinyl tris (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 (trade name such as KBM403) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

When silane-based compounds are used as adhesion aids, based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the silane-based compounds is 0 parts by weight to 2 parts by weight; Preferably it is 0.05 part by weight to 1 part by weight; and more preferably 0.1 part by weight to 0.8 part by weight.

Specific examples of the surfactant are anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorine surfactants, or combinations thereof.

Examples of surfactants include (1) polyethylene oxide alkyl ethers (polyoxyethylene alkyl ethers): polyethylene oxide dodecyl ether, etc.; (2) polyethylene oxide alkyl phenyl ethers (polyoxyethylene phenyl ethers): polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, etc.; (3) polyethylene glycol diesters: polyethylene glycol two Laurate, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; and (5) fatty acid modified poly esters ; And (6) Tertiary amine modified polyurethanes and so on. 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 Zhongnichi Synthetic Chemical), F-475 (manufactured by Dainippon Ink Chemical Industry), or a combination thereof .

Based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the surfactant is 0.5 to 50 parts by weight; preferably 1 to 40 parts by weight; and More preferably, it is 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 DF66 and Surfynol DF70, Surfynol DF37, Surfynol DF66 and Surfynol DF70 Air products (manufactured by Air products), etc.

Based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the defoamer is 1 part by weight to 10 parts by weight; preferably 2 parts by weight to 9 parts by weight; and More preferably, it is 3 to 8 parts by weight.

Examples of dissolution promoters include N-hydroxydicarboxylic imide compounds and compounds containing phenolic hydroxyl groups.

Based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the usage amount of the 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, it is 3 parts by weight to 10 parts by weight.

A specific example of the chemically amplified positive photosensitive resin composition of the present invention is prepared in the following manner: the first resin (A1), the second resin (A2), the photoacid generator (B), and the solvent (C) , The compound (D) and the hindered amine compound (E) are placed in a stirrer and stirred to make them uniformly mixed into a solution state. If necessary, additives (E) can be added.

The present invention also provides a protective film, which is formed by coating the aforementioned chemically amplified positive photosensitive resin composition on a substrate, and then undergoing pre-baking, exposure, development and post-baking treatments.

The present invention also provides a device with a protective film, comprising a substrate and the aforementioned protective film, and the protective film is attached to the substrate.

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. 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 for forming the protective film includes the following steps: 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)"); The step of irradiating at least a part of radiation (hereinafter also referred to as "step (2)"); the step of developing the above-mentioned coating film after radiation exposure (hereinafter also referred to as "step (3)"); and the above-mentioned after development The step of heating the 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 coated 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 base material, 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 vary according to the types of ingredients, blending ratios, etc., and can be set at 70°C to 120°C for about 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 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, and more preferably radiation including ultraviolet rays of 365 nm. The exposure level is a value obtained by measuring the intensity of 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 , More preferably 1,500 J/m ² to 1,800 J/m ² .

Step (3): In this step, the above-mentioned coating film after irradiation with radiation is developed. By developing the exposed coating film, unnecessary parts (radiation irradiated parts) 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, and the like.

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 depending on the composition of the chemically amplified positive photosensitive resin composition, and is 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 machine, 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 step-by-step 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 also be used as a spacer or an interlayer insulating film.

The thickness of the formed protective film for a display element 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.

The following examples are used to illustrate the present invention in detail, but it does not mean that the present invention is limited to the content disclosed by these examples. Preparation of the first resin (A1) Preparation Example A1-1

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. 1-ethoxyethyl acrylate (hereinafter referred to as MAEVE), 1 part by weight of the compound of formula (3-24) (hereinafter referred to as a131), 40 parts by weight of dicyclopentyl methacrylate (hereinafter referred to as FA-513M), 20 parts by weight of glycidyl methacrylate (hereinafter referred to as GMA), 6 parts by weight of 3-(methacryloylmethoxy)oxetane (hereinafter referred to as GXMA), 10 parts by weight of styrene ( (Hereinafter referred to as SM), 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter referred to as ADVN) and 200 parts by weight of diethylene glycol dimethyl ether (hereinafter referred to as Diglyme) Solvent. Then, slowly stir the above ingredients to raise the temperature of the solution to 70°C, and polycondensate at this temperature for 6 hours. Then, after the solvent is devolatilized, the first resin (A1-1) can be obtained. Preparation examples A1-2 to A1-10 and preparation comparative examples A1'-1 to A1'-2

表 1-2 ：

表 1-1 、表 1-2 中： AMBN 2,2’-偶氮雙-2-甲基丁腈    HEMA 甲基丙烯酸2-羥基乙酯 ADVN 2,2’-偶氮雙(2,4-二甲基戊腈)    FA-513M 甲基丙烯酸雙環戊酯 MAA 甲基丙烯酸    GMA 甲基丙烯酸環氧丙酯 AA 丙烯酸    OXMA 3-(甲基丙烯醯甲氧基)氧雜環丁烷 HOMS 2-甲基丙烯醯乙氧基丁二酸酯    BzMA 甲基丙烯酸苯甲酯 MAEVE 甲基丙烯酸1-乙氧基乙酯    SM 苯乙烯 MAEVB 甲基丙烯酸1-正丁氧基乙酯    Diglyme 二乙二醇二甲醚 MATHF 甲基丙烯酸四氫糠酯    PGMEA 丙二醇甲醚醋酸酯 MATHP 甲基丙烯酸2-四氫吡喃基酯          a131 式(3-24)之化合物          a132 式(3-25)之化合物          a133 式(3-26)之化合物          a134 式(3-27)之化合物          a135 式(3-28)之化合物      a136 式(3-29)之化合物      製備第二樹脂 (A2) 製備例 A2-1 至 A2-10 以及製備比較例 A2’-1 The preparation of the first resin (A1-2) to (A1-10) and the preparation comparative examples (A1'-1) to (A1'-2) is similar to the preparation example of the aforementioned first resin (A1-1), wherein, The types and usage of monomers are 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 (A1-1), as shown in Table 1-1 and Table 1-2. Table 1-1 :

Table 1-2 :

In Table 1-1 and Table 1-2 : AMBN 2,2'-Azobis-2-methylbutyronitrile HEMA 2-hydroxyethyl methacrylate ADVN 2,2'-Azobis(2,4-Dimethylvaleronitrile) FA-513M Dicyclopentyl methacrylate MAA Methacrylate GMA Glycidyl methacrylate AA acrylic acid OXMA 3-(Methylpropenylmethoxy)oxetane HOMS 2-methacrylic acid ethoxy succinate BzMA Benzyl methacrylate MAEVE 1-ethoxyethyl methacrylate SM Styrene MAEVB 1-n-Butoxyethyl methacrylate Diglyme Diethylene glycol dimethyl ether MATHF Tetrahydrofurfuryl methacrylate PGMEA Propylene Glycol Methyl Ether Acetate MATHP 2-tetrahydropyranyl methacrylate a131 Compound of formula (3-24) a132 Compound of formula (3-25) a133 Compound of formula (3-26) a134 Compound of formula (3-27) a135 Compound of formula (3-28) a136 Compound of formula (3-29) Preparation of the second resin (A2) Preparation Examples A2-1 to A2-10 and Preparation Comparative Example A2'-1

表 2-2 ：

表 2-1 、表 2-2 中： AMBN 2,2’-偶氮雙-2-甲基丁腈    HEMA 甲基丙烯酸2-羥基乙酯 ADVN 2,2’-偶氮雙(2,4-二甲基戊腈)    FA-513M 甲基丙烯酸雙環戊酯 MAA 甲基丙烯酸    GMA 甲基丙烯酸環氧丙酯 AA 丙烯酸    OXMA 3-(甲基丙烯醯甲氧基)氧雜環丁烷 HOMS 2-甲基丙烯醯乙氧基丁二酸酯    BzMA 甲基丙烯酸苯甲酯 MAEVE 甲基丙烯酸1-乙氧基乙酯    SM 苯乙烯 MAEVB 甲基丙烯酸1-正丁氧基乙酯    Diglyme 二乙二醇二甲醚 MATHF 甲基丙烯酸四氫糠酯    PGMEA 丙二醇甲醚醋酸酯 MATHP 甲基丙烯酸2-四氫吡喃基酯          a221 式(4-1)之化合物          a222 式(4-2)之化合物          a223 式(4-3)之化合物          a224 式(4-4)之化合物          a225 式(4-5)之化合物          實施例 1 The preparation of the second resin (A2-1) to (A2-10) and the preparation comparative example (A2'-1) is similar to the preparation example of the aforementioned first resin (A1-1), in which the type and amount of monomer As shown in Table 1. However, the usage amount of solvent and catalyst, reaction temperature and polycondensation reaction time are different from the aforementioned resin (A1-1), as shown in Table 2-1 and Table 2-2. Table 2-1 :

Table 2-2 :

In Table 2-1 and Table 2-2 : AMBN 2,2'-Azobis-2-methylbutyronitrile HEMA 2-hydroxyethyl methacrylate ADVN 2,2'-Azobis(2,4-Dimethylvaleronitrile) FA-513M Dicyclopentyl methacrylate MAA Methacrylate GMA Glycidyl methacrylate AA acrylic acid OXMA 3-(Methylpropenylmethoxy)oxetane HOMS 2-methacrylic acid ethoxy succinate BzMA Benzyl methacrylate MAEVE 1-ethoxyethyl methacrylate SM Styrene MAEVB 1-n-Butoxyethyl methacrylate Diglyme Diethylene glycol dimethyl ether MATHF Tetrahydrofurfuryl methacrylate PGMEA Propylene Glycol Methyl Ether Acetate MATHP 2-tetrahydropyranyl methacrylate a221 Compound of formula (4-1) a222 Compound of formula (4-2) a223 Compound of formula (4-3) a224 Compound of formula (4-4) a225 Compound of formula (4-5) Example 1

90 parts by weight of the first resin (A1-1), 10 parts by weight of the second resin (A2-1), 0.3 parts by weight of N-(4-methylphenylsulfonyloxy) succinimide (B-1), 0.25 parts by weight of the compound (D-1) represented by formula (S-23) and 0.02 parts by weight of the compound (E-1) represented by formula (e11), adding 300 parts by weight of propylene glycol After mixing the methyl ether acetate (C-1) uniformly with a shaking type stirrer, the chemically amplified positive photosensitive resin composition of Example 1 can be obtained.

The specific conditions and evaluation results of Example 1 are shown in Table 3-1. Examples 2 to 12 and Comparative Examples 1 to 7

表 3-2 ：

表 4 ：

評價方式 1. 感度 The chemically amplified positive photosensitive resin composition and protective film of Examples 2 to 12 and Comparative Examples 1 to 7 were obtained in the same manner as in Example 1. The difference is that Examples 2 to 12 and Comparative Examples 1 to 7 changed conditions such as composition or usage amount. The specific conditions and evaluation results of Examples 2 to 12 and Comparative Examples 1 to 7 are shown in Table 3-1, Table 3-2, and Table 4. Table 3-1 :

Table 3-2 :

Table 4 :

Evaluation method 1. Sensitivity

After the chemically amplified positive photosensitive resin composition of the examples and comparative examples was coated on a glass substrate (100 mm×100 mm), it was heated at 110°C for 120 seconds with a gap of about 1 mm. Heat and preheat to form a photoresist film with a thickness of 3 μm. Next, using an i-line exposure device (device name: FX-702J, manufactured by Nikon, NA=0.14), a test using a photoresist pattern capable of simultaneously drawing a 2.0 μm L&S (line and space) and a 3.0 μm L&S photoresist pattern Chart mask (scale line) for selective exposure. Next, 23° C., 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution was used for 70 seconds of development treatment, rinsed with pure water for 15 seconds, and spin-dried. The exposure level (Eop, unit: mJ) that can faithfully reproduce the 2.0 μm L&S photoresist pattern is used as a sensitivity evaluation index. The evaluation criteria are as follows: ◎: exposure level <60 mJ ○: 60 mJ≦exposure level <150 mJ △: 150 mJ≦Exposure amount <300 mJ ╳: Exposure amount≧300 mJ. 2. Stability over time

The viscosity of the chemically amplified positive photosensitive resin composition of the Examples and Comparative Examples was measured using Toki Sangyo's RE85L viscometer at 25°C. The result was η1. Then, the temperature was 32°C and humidity After standing for a period of time at 55%, the viscosity is measured at 25℃. The result is η2, and the change of |η2-η1|/η1 is calculated within the time interval of ± 8%. The longer the interval, the longer the interval, the storage The better the stability. ◎: More than 4 weeks ○: More than 3 weeks, less than 4 weeks △: More than 2 weeks, less than 3 weeks ╳: Less than 2 weeks

Claims (14)

A chemically amplified positive photosensitive resin composition comprising: a first resin (A1) obtained by copolymerization of a first mixture, the first mixture containing unsaturated carboxylic acid monomer (a1-1), The acid-dissociable group-containing monomer (a1-2) of the acid-dissociable group represented by the structural formula (1) and the unsaturated monomer (a1-3) containing the lactone structure;

Formula (1) In formula (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 atom of the alkyl group, alicyclic hydrocarbon group or aryl group It may be partially or fully 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 the alkyl group, alicyclic hydrocarbon group, aralkyl group The hydrogen atoms of the group and the aryl group can be partially or fully substituted; R ₁₁ and R ₁₃ can be bonded to each other to form a cyclic ether structure with the carbon atom bonded _{to R 11 and the oxygen atom bonded to R 13} ; A second resin (A2), obtained by copolymerization of a second mixture, the second mixture containing unsaturated carboxylic acid monomer (a2-1) and phenolic hydroxyl-containing unsaturated monomer (a2-2) ; One photoacid generator (B); One solvent (C); One compound (D) represented by formula (6) or formula (7):

Formula (6) In formula (6), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms; n ₆ is an integer from 0 to 2; L ¹ is a single bond or a divalent linking group; X ¹ is -S- or -NH-; R ³ is a monovalent organic group;

Formula (7) In formula (7), R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbons; n ₇ is an integer from 0 to 2; L ² is a single bond or a divalent linking group; X ² is -S- or -NH-; A is a heterocyclic ring containing carbon atoms and nitrogen atoms; and a hindered amine compound (E) represented by formula (e1),

Formula (e1) In formula (e1), n is an integer of 4 or more; E ₁ is an n-valent organic group; E ₂ to E ₅ are each independently a monovalent organic group with 1 to 12 carbon _{atoms; E 6} is a hydrogen atom or A monovalent alkyl group having 1 to 12 carbons. The chemically amplified positive photosensitive resin composition described in item 1 of the scope of patent application, wherein the unsaturated monomer (a1-3) containing a lactone structure is a compound represented by formula (3):

Formula (3) In formula (3), R ^X1 is a hydrogen atom or an alkyl group; R ^A2 is an alkyl group having 1 to 8 carbons, a cycloalkyl group having 3 to 7 carbons, or an alkoxy group having 1 to 8 carbons , Alkoxycarbonyl group, carboxyl group, halogen atom, hydroxyl group, cyano group or acid-decomposable group with 2 to 8 carbon atoms, when n _{2 is} greater than 1, plural R ^A2 may be the same or different; A ¹ is a single bond or two Valence linking group; Z ² is a monocyclic or polycyclic structure containing -OC(=O)-; n ₂ is an integer of 0 or more. The chemically amplified positive photosensitive resin composition described in item 1 of the scope of patent application, wherein the phenolic hydroxyl-containing unsaturated monomer (a2-2) is a compound represented by formula (4):

Formula (4) In formula (4), R ²²⁰ is a hydrogen atom or a methyl group; R ²²¹ is a single bond or a divalent linking group; R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms When b is greater than 1, a plurality of R ²²² may be the same or different; b is an integer from 0 to 4, c is an integer from 1 to 5, and b+c is 5 or less. The chemically amplified positive photosensitive resin composition described in item 1 of the scope of the patent application, wherein the second mixture further includes an acid dissociable group-containing monomer containing an acid dissociable group represented by structural formula (2) Body (a2-3);

Formula (2) In formula (2), R ₂₁ and R ₂₂ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, wherein the hydrogen atom of the alkyl group, alicyclic hydrocarbon group or aryl group It may be partially or fully substituted, and R ₂₁ and R _{22 are} not hydrogen atoms at the same time; R ₂₃ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group or an aryl group, wherein the alkyl group, alicyclic hydrocarbon group, aralkyl group The hydrogen atoms of the group and the aryl group can be partially or completely substituted; R ₂₁ and R ₂₃ can be bonded to each other to form a cyclic ether structure with the carbon atom bonded _{to R 21 and the oxygen atom bonded to R 23} . 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 containing an oxime sulfonate group of the following formula (8):

Formula (8) In formula (8), R ¹⁶ is an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group or an aryl group, wherein the hydrogen atom of the alkyl group, alicyclic hydrocarbon group or aryl group may be Part or all of it is replaced; * is the junction. The chemically amplified positive photosensitive resin composition described in the first item of the scope of the patent application, wherein E ₆ of the formula (e1) is a monovalent alkyl group having 1 to 12 carbons. The chemically amplified positive photosensitive resin composition described in the first item of the scope of patent application, wherein n in the formula (e1) is an integer of 5 or more. The chemically amplified positive photosensitive resin composition described in the first item of the scope of patent application, wherein, based on the total usage amount of the first resin (A1) and the second resin (A2) being 100 parts by weight, the first The usage amount of the resin (A1) is 40 parts by weight to 90 parts by weight, the usage amount of the second resin (A2) is 10 parts by weight to 60 parts by weight, and the usage amount of the photoacid generator (B) is 0.3 parts by weight To 5 parts by weight, the usage amount of the solvent (C) is 150 to 1200 parts by weight, the usage amount of the compound (D) is 0.05 to 0.8 parts by weight, and the usage amount of the hindered amine compound (E) It is 0.02 parts by weight to 0.2 parts by weight. The chemically amplified positive photosensitive resin composition as described in item 1 of the scope of patent application, wherein the total usage amount of the first mixture based on the first resin (A1) is 100 parts by weight, and the unsaturated carboxylic acid mono The usage amount of the body (a1-1) is 3 to 30 parts by weight, the usage amount of the acid dissociable group-containing monomer (a1-2) is 15 to 75 parts by weight, and the lactone-containing structure The amount of the unsaturated monomer (a1-3) used is 1 part by weight to 15 parts by weight. The chemically amplified positive photosensitive resin composition as described in item 1 of the scope of the patent application, wherein the total usage amount of the second mixture based on the second resin (A2) is 100 parts by weight, and the unsaturated carboxylic acid The usage amount of the body (a2-1) is 1 to 20 parts by weight, and the usage amount of the phenolic hydroxyl-containing unsaturated monomer (a2-2) is 5 to 50 parts by weight. The chemically amplified positive photosensitive resin composition described in item 4 of the scope of patent application, wherein the total usage amount of the second mixture based on the second resin (A2) is 100 parts by weight, and the acid-dissociable group-containing The usage amount of the monomer (a2-3) is 0 parts by weight to 70 parts by weight. The chemically amplified positive photosensitive resin composition described in item 1 of the scope of patent application, wherein the usage ratio (D)/(E) of the compound (D) and the hindered amine compound (E) is 0.5 to 10. A protective film, which is coated on a substrate with the chemically amplified positive photosensitive resin composition described in any one of items 1 to 12 in the scope of the patent application, and then pre-baked, exposed, developed and post-baked Formed after processing. A device with a protective film includes a substrate and the protective film as described in item 13 of the scope of the patent application, and the protective film is attached to the substrate.