Radiation-sensitive composition, hardened film and method for producing the same, semiconductor element, display element

Abstract

The present invention aims to provide a radiosensitive linear composition, a hardened film, a method for manufacturing the same, a semiconductor element, a display element, and a polymer that can produce a film with excellent adhesion. A radiosensitive linear composition comprises: a polymer containing a structural unit (I) having a base represented by formula (1), a photoacid generator, and an orthoester compound. In formula (1), R... 1 It can be a hydrogen atom, a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms. R 2 and R 3 Each of the following can be independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, an alkyl group with 1 to 10 carbon atoms, or a phenyl group. "*" indicates a bond.

Description

Technical Field

[0001] This invention relates to a radioactive linear composition, a hardening film and a method for manufacturing the same, a semiconductor element and a display element, and a polymer. Background Technology

[0002] The hardened films such as interlayer insulating films, spacers, and protective films of display elements are generally formed using a photosensitive linear composition. As a material for forming these hardened films, a photosensitive linear composition is proposed, comprising: a polymer having silicon-containing functional groups such as alkoxysilyl groups, a silicon-containing polymer such as a siloxane polymer, and a photoacid generator (for example, see Patent Document 1 and Patent Document 2).

[0003] When using the radiosensitive linear composition of Patent Document 1 to form a coating film, acid is generated from the photoacid generator during exposure in pattern formation. The generated acid decomposes alkoxy groups, making the exposed areas soluble in the developer. The unexposed areas are insoluble in alkali, and after development, they are dehydrated, condensed, and hardened by heating, thereby forming a hardened film. Furthermore, in the radiosensitive linear composition of Patent Document 2, the acid generated from the photoacid generator during exposure acts as a catalyst, promoting the self-crosslinking of the siloxane polymer, thereby forming a hardened film.

[0004] [Existing Technical Documents]

[0005] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2017-107024

[0007] [Patent Document 2] International Publication No. 2011 / 065215 Summary of the Invention

[0008] [The problem the invention aims to solve]

[0009] When using the radioactive linear composition of Patent Document 1 and Patent Document 2 to form a hardened film, there is a concern that the adhesion of the unexposed portion to the substrate may be reduced.

[0010] The present invention was made in view of the aforementioned issues, and its main objective is to provide a radiosensitive linear composition capable of forming a film with excellent imaging adhesion.

[0011] [Technical means to solve the problem]

[0012] The inventors have discovered that the aforementioned problem can be solved by incorporating specific compounds into a radiosensitive linear composition. Specifically, according to the present invention, the following radiosensitive linear composition, curing film, method for manufacturing the same, semiconductor element, and display element are provided.

[0013] [1] A radiosensitive linear composition comprising: a polymer and / or a siloxane polymer comprising a structural unit (I) having a base represented by the following formula (1), a photoacid generator, and an orthoester compound.

[0014] [Chemistry 1]

[0015]

[0016] (In equation (1), R) 1 It can be a hydrogen atom, a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms. R 2 and R 3 Each of the following is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, or an alkyl or phenyl group with 1 to 10 carbon atoms. (* indicates a bond)

[0017] [2] A radiosensitive linear composition comprising: a silicon-containing polymer, which is selected from at least one of polymers comprising a structural unit (I) having a base represented by the formula (1) and siloxane polymers; a photoacid generator; and an orthoester compound having a boiling point of 105°C or higher.

[0018] [3] A method for manufacturing a hardened film includes: a step of forming a coating film using the radiosensitive linear composition of [1] or [2]; a step of irradiating at least a portion of the coating film with radiation; a step of developing the irradiated coating film; and a step of heating the developed coating film.

[0019] [4] A hardened film formed using the radiosensitive linear composition of [1] or [2].

[0020] [5] A semiconductor device comprising the hardened film of [4].

[0021] [6] A display element comprising the semiconductor element of [5].

[0022] [7] A polymer comprising a structural unit (I) having a base represented by the formula (1), wherein the proportion of the structural unit (I) in the polymer is 5% by mass or more and 50% by mass or less relative to all structural units constituting the polymer.

[0023] [The effects of the invention]

[0024] According to the radiosensitive linear composition of the present invention, by comprising the silicon-containing polymer, photoacid generator and orthoester compound, a coating film with excellent development adhesion can be formed. Detailed Implementation

[0025] The following provides a detailed description of matters related to the implementation method. Furthermore, in this specification, the numerical range indicated by “~” means the values ​​before and after the “~” are considered as lower and upper limits. A “structural unit” refers to a unit that primarily constitutes the main chain structure, and specifically refers to a main chain structure containing at least two or more units.

[0026] [Radiosensitive linear composition]

[0027] The radiosensitive linear composition disclosed herein is used, for example, as a curing film for forming display elements. The radiosensitive linear composition is a positive resin composition containing [A] a polymer component, [B] an orthoester compound, and [C] a photoacid generator. Hereinafter, the components contained in the radiosensitive linear composition of this disclosure, as well as other components formulated as needed, will be described. Furthermore, unless otherwise specified, each component may be used alone or in combination of two or more.

[0028] Here, in this specification, "hydrocarbon group" refers to a group comprising chain-like hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Chain-like hydrocarbon group" refers to a straight-chain hydrocarbon group or branched hydrocarbon group that does not contain a ring structure in its main chain and is composed only of a chain structure. It can be saturated or unsaturated. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as its ring structure and does not contain an aromatic ring structure. It does not need to consist solely of an alicyclic hydrocarbon structure; it may also include groups with a chain structure in a portion thereof. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as its ring structure. It does not need to consist solely of an aromatic ring structure; it may also contain a chain structure or an alicyclic hydrocarbon structure in a portion thereof. Furthermore, the ring structure of alicyclic hydrocarbon groups and aromatic hydrocarbon groups may also have substituents containing hydrocarbon structures. "Cyclic hydrocarbon group" refers to a group comprising alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0029] <[A] Polymer Components>

[0030] [A] The polymer component contains a silicon-containing polymer, which is at least one selected from the group consisting of polymers (hereinafter also referred to as "polymer (S)") comprising a structural unit (I) having a base represented by the following formula (1) and siloxane polymers.

[0031] [Chemistry 2]

[0032]

[0033] (In equation (1), R) 1 It can be a hydrogen atom, a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms. R 2 and R 3Each of the following is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, or an alkyl or phenyl group with 1 to 10 carbon atoms. (* indicates a bond)

[0034] (Polymer(S))

[0035] • Structural Unit (I)

[0036] In equation (1), R is used as 1 ~R 3 Alkyl groups with 1 to 6 carbon atoms include, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy. Among these, R... 1 ~R 3 The alkoxy group is preferably methoxy or ethoxy.

[0037] R 2 R 3 The alkyl group having 1 to 10 carbon atoms can be either straight-chain or branched. As R 2 R 3 Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc., are examples. Among these, R... 2 R 3 The alkyl group is preferably methyl, ethyl, or propyl.

[0038] From the perspective of obtaining a hardened film with excellent heat resistance and chemical resistance by forming a cross-linked structure, and from the perspective of improving the storage stability of radiosensitive linear compositions, R 1 ~R 3 Preferably, at least one of these is an alkoxy group having 1 to 6 carbon atoms, more preferably two or more are alkoxy groups, and particularly preferably all of them are alkoxy groups.

[0039] In the above, R 1 Preferably, it is an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms. When the group represented by formula (1) is bonded to an aromatic ring group, R... 1 Preferably, it is methoxy. When the group represented by formula (1) is bonded to a chain hydrocarbon group, R 1 Preferably, it is ethoxylated. R 2 and R 3 Preferably, it is a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, an alkyl group with 1 to 10 carbon atoms, or a phenyl group; more preferably, it is a hydroxyl group, an alkoxy group with 1 to 3 carbon atoms, or an alkyl group with 1 to 3 carbon atoms.

[0040] In structural unit (I), the group represented by formula (1) is preferably bonded to an aromatic cyclic group or a chain hydrocarbon group. Here, the term "aromatic cyclic group" in this specification refers to a group formed by removing n (n is an integer) hydrogen atoms from the ring portion of an aromatic ring. Examples of such aromatic rings include benzene rings, naphthalene rings, and anthracene rings. The ring may also have substituents such as alkyl groups. Examples of such chain hydrocarbon groups bonded to the group represented by formula (1) include alkane diesters and alkene diesters.

[0041] In this embodiment, the group represented by formula (1) is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. That is, the structural unit (I) is preferably composed of at least one group selected from the group represented by formula (3-1), formula (3-2), and formula (3-3).

[0042] [Chemistry 3]

[0043]

[0044] In equations (3-1), (3-2), and (3-3), A 1 and A 2 Each is independently a halogen atom, a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms. n1 is an integer from 0 to 4. n2 is an integer from 0 to 6. Where n1 is 2 or more, multiple A atoms... 1 They can be either the same basis or different basis. When n² is greater than 2, multiple A's... 2 For bases that are the same as each other or different bases. R 6 It is an alkyldiyl group. R 1 R 2 and R 3 This has the same meaning as equation (1). "*" indicates a bond.

[0045] In equations (3-1) and (3-2), regarding A 1 and A 2 Examples of alkoxy groups having 1 to 6 carbon atoms and alkyl groups having 1 to 6 carbon atoms, applicable to R of formula (1). 1 ~R 3 Explanation. The group "-SiR" bonded to the aromatic ring. 1 R 2 R 3 The position of " relative to A" 1 and A 2 Other bases besides these can be in any position. For example, in the case of equation (3-1), "-SiR" 1 R 2 R 3The position of “ can be any one of adjacent, intermediate, or opposite, preferably opposite. n1 is preferably 0 or 1, more preferably 0. n2 is preferably 0 to 2, more preferably 0.

[0046] In the above equation (3-3), R 6 Preferably, it is linear. From the viewpoint of improving the heat resistance of the resulting hardened film, R... 6 Preferably, it has 1 to 6 carbon atoms, more preferably 1 to 4.

[0047] Regarding the improvement of the heat resistance, chemical resistance, and hardness of the hardened film, in formulas (3-1) to (3-3), the structural unit (I) is preferably composed of at least one group selected from the group consisting of the base represented by formula (3-1) and the base represented by formula (3-2). Furthermore, in the base "-SiR..." 1 R 2 R 3 "When directly bonded to an aromatic ring, the silanol group generated in the presence of water can be stabilized. This is preferable in terms of improving the solubility of the exposure section in the alkaline developer and forming good patterns. Among these, structural unit (I) is particularly preferred to be a structural unit having the group represented by the formula (3-1)."

[0048] The structural unit (1) is preferably a structural unit derived from a monomer having polymerizable carbon-carbon unsaturated bonds (hereinafter also referred to as "unsaturated monomer"), and more specifically, preferably at least one of the group consisting of the structural unit represented by the following formula (4-1) and the structural unit represented by the following formula (4-2).

[0049] [Chemistry 4]

[0050]

[0051] (In equations (4-1) and (4-2), R) A It can be a hydrogen atom, methyl, hydroxymethyl, cyano, or trifluoromethyl. R 7 and R 8 Each is independently a divalent aromatic cyclic group or a chain hydrocarbon group. R 1 R 2 and R 3 (This has the same meaning as equation (1))

[0052] In equations (4-1) and (4-2), R 7 R 8 The divalent aromatic cyclic group is preferably a substituted or unsubstituted phenylene or a substituted or unsubstituted naphthylene. The divalent chain hydrocarbon group is preferably an alkyldiyl group having 1 to 6 carbon atoms, more preferably an alkyldiyl group having 1 to 4 carbon atoms.

[0053] In terms of obtaining hardened films with higher heat resistance, chemical resistance, and hardness, and in terms of improving the solubility of the exposure section in alkaline developer, R 7 R 8 The preferred group is a divalent aromatic cyclic group, and more particularly preferred is a substituted or unsubstituted phenylene group.

[0054] As specific examples of the structural unit represented by equation (4-1), structural units represented by equations (4-1-1) and (4-1-2) can be listed below. Furthermore, as specific examples of the structural unit represented by equation (4-2), structural units represented by equations (4-2-1) and (4-2-2) can be listed below.

[0055] [Chemistry 5]

[0056]

[0057] In equations (4-1-1), (4-1-2), (4-2-1), and (4-2-2), R 11 and R 12 Each is an alkyl group having 1 to 4 carbon atoms, R 13 It is an alkyl group, an alkoxy group, or a hydroxyl group having 1 to 4 carbon atoms. n3 is an integer from 1 to 4. A 1 A 2 n1 and n2 have the same meaning as in equations (3-1) and (3-2). R A (This has the same meaning as equations (4-1) and (4-2) mentioned above)

[0058] Specific examples of monomers constituting structural unit (I), and compounds having the group represented by the formula (3-1), include styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloyloxyphenyltrimethoxysilane, (meth)acryloyloxyphenyltriethoxysilane, (meth)acryloyloxyphenylmethoxydimethoxysilane, (meth)acryloyloxyphenylethyldiethoxysilane, etc.

[0059] Examples of compounds having the group represented by formula (3-2) include trimethoxy(4-vinylnaphthyl)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloyloxynaphthyltrimethoxysilane, etc.

[0060] Examples of compounds having the group represented by formula (3-3) include 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, and 4-(meth)acryloyloxybutyltrimethoxysilane. Furthermore, in this specification, "(meth)acrylic acid" means that it includes both "acrylic acid" and "methacrylic acid".

[0061] The content of structural unit (I) in polymer (S) is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 10% by mass or more, relative to all structural units constituting polymer (S). Furthermore, the content of structural unit (I) is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, relative to all structural units constituting polymer (S). Setting the content of structural unit (I) within the aforementioned range is preferable in terms of sufficiently improving the heat resistance and chemical resistance of the obtained cured film, improving the low dielectric constant, and exhibiting better resolution of the coating film.

[0062] Other structural units

[0063] The polymer (S) may also contain structural units other than structural unit (I) (hereinafter also referred to as "other structural units"). Examples of other structural units include structural units (II) having at least one of oxetyl and oxetyl, structural units (III) having an acid group, etc. In addition, oxetyl and oxetyl are also included in this specification and referred to as "epoxy groups".

[0064] • Structural Unit (II)

[0065] The inclusion of structural unit (II) in the polymer (S) is preferred in terms of further improving the membrane's resolution or adhesion. Furthermore, the presence of epoxy groups as crosslinking groups is preferred in terms of forming a hardened membrane with high chemical resistance and long-term inhibition of degradation. Structural unit (II) is preferably derived from an unsaturated monomer having epoxy groups, and more specifically, is preferably the structural unit represented by the following formula (5).

[0066] [Chemistry 6]

[0067]

[0068] (In equation (5), R) 20 It is a monovalent group having an oxetine propyl or oxetine butyl group. R A It can be a hydrogen atom, methyl group, hydroxymethyl group, cyano group, or trifluoromethyl group. X 1(For single-bond or divalent linkages)

[0069] In equation (5), R is used as 20 Examples include oxacyclopropyl, oxacyclobutyl, 3,4-epoxycyclohexyl, and 3,4-epoxytricyclic [5.2.1.0]. 2,6 Decyl, 3-ethyloxetyl, etc.

[0070] As X 1 The divalent linker is preferably a alkyl dimethyl group, such as methylene, ethylene, or 1,3-propanediyl.

[0071] Specific examples of monomers having epoxy groups include: glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, methyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo(meth)acrylate [5.2.1.0]. 2,6 [Decayl ester; (meth)acrylate (3-methyloxetane-3-yl)methyl ester, (meth)acrylate (3-ethyloxetane-3-yl) ester, (meth)acrylate (oxetane-3-yl)methyl ester, (meth)acrylate (3-ethyloxetane-3-yl)methyl ester, etc.

[0072] The content of structural unit (II) in polymer (S) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to all structural units constituting polymer (S). Furthermore, the content of structural unit (II) is preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less, relative to all structural units constituting polymer (S). Setting the content of structural unit (II) within the aforementioned range is preferable in terms of exhibiting better resolution in the coating film, while also significantly improving the heat resistance and chemical resistance of the obtained cured film.

[0073] • Structural Unit (III)

[0074] The polymer (S) preferably also contains a structural unit (III) having an acid group. The structural unit (III) can improve the solubility (alkali solubility) of the polymer (S) in alkaline developing solutions, or improve its curing reactivity. Furthermore, in this specification, "alkali solubility" means the ability to dissolve or swell in an alkaline aqueous solution such as a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0075] Structural unit (III) is not particularly limited as long as it has an acid group, but is preferably selected from at least one of the group consisting of structural units having a carboxyl group, structural units having a sulfonic acid group, structural units having a phenolic hydroxyl group, and maleimide units. Furthermore, the term "phenolic hydroxyl group" in this specification refers to a hydroxyl group that is directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, an anthracene ring, etc.).

[0076] Structural unit (III) is preferably derived from an unsaturated monomer having an acid group. Specific examples of unsaturated monomers having an acid group include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, succinic acid, and itaconic acid; monomers constituting structural units having a sulfonic acid group include vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, and (meth)acryloyloxyethylsulfonic acid; and monomers constituting structural units having a phenolic hydroxyl group include 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, and hydroxyphenyl (meth)acrylate. Additionally, maleimide may also be used as a monomer constituting structural unit (III).

[0077] From the viewpoint of imparting good solubility to alkaline developer, the content of structural unit (III) in polymer (S) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, relative to all structural units constituting polymer (S). On the other hand, if the content of structural unit (III) is too high, the difference in solubility of alkaline developer between the exposed and unexposed areas becomes smaller, which may make it difficult to obtain a good pattern shape. From this viewpoint, the content of structural unit (III) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to all structural units constituting polymer (S).

[0078] Other structural units include those derived from at least one monomer selected from the group consisting of alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, aromatic vinyl compounds, N-substituted maleimide compounds, vinyl compounds having a heterocyclic structure, conjugated diene compounds, nitrogen-containing vinyl compounds, and dialkyl dicarboxylic acid esters. By incorporating these structural units into the polymer, the glass transition temperature of the polymer composition can be adjusted, thereby improving the pattern shape and chemical resistance of the obtained cured film.

[0079] Specific examples of the monomers mentioned above, as alkyl methacrylates, include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate.

[0080] Examples of (meth)acrylates with an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclic (meth)acrylate [5.2.1.0]. 2,6 ] Decane-8-yl ester, (meth)acrylate tricyclic [5.2.1.0] 2,5 Decane-8-yloxyethyl ester, isobornyl acrylate, etc.

[0081] Examples of (meth)acrylates having an aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0082] Examples of aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, etc.

[0083] Examples of N-substituted maleimide compounds include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, and N-naphthylmaleimide.

[0084] Examples of vinyl compounds with heterocyclic structures include tetrahydrofurfuryl acrylate, tetrahydropyranyl acrylate, 5-ethyl-1,3-dioxane-5-yl methyl acrylate, 5-methyl-1,3-dioxane-5-yl methyl acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methyl acrylate, 2-(meth)acryloyloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (γ-butyrolactone-2-yl) acrylate, (meth)acrylic acid glycerol carbonate, (γ-lactam-2-yl) acrylate, and N-(meth)acryloyloxyethyl hexahydrophthalimide.

[0085] Examples of conjugated diene compounds include 1,3-butadiene and isoprene.

[0086] Examples of nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide;

[0087] Examples of unsaturated dialkyl dicarboxylic acid esters include diethyl itaconic acid. In addition to the above, other monomers constituting other structural units include, for example, vinyl chloride, vinylidene chloride, and vinyl acetate.

[0088] From the viewpoint of suppressing melt flow during thermosetting by adjusting the glass transition temperature of the polymer composition, the polymer (S) is preferably composed of structural units other than structural units (II) and (III), which are derived from at least one monomer selected from the group consisting of alkyl methacrylates, methacrylates having an alicyclic structure, and methacrylates having an aromatic ring structure.

[0089] From the viewpoint of moderately increasing the glass transition temperature of the polymer (S), the content of structural units other than structural units (II) and (III) is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to all structural units constituting the polymer (S). Furthermore, the content of said structural units is preferably 50% by mass or less, and more preferably 40% by mass or less, relative to all structural units constituting the polymer (S).

[0090] The polymer (S) can be manufactured, for example, using unsaturated monomers capable of incorporating the structural units, in a suitable solvent and in the presence of a polymerization initiator, according to existing methods such as free radical polymerization. Examples of polymerization initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), and dimethyl 2,2'-azobis(isobutyric acid) ester. The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the total amount of monomers used in the reaction. Examples of polymerization solvents include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of polymerization solvent used is preferably set to be 0.1% to 60% by mass relative to the total amount of the reaction solution and the total amount of monomers used in the reaction.

[0091] In polymerization, the reaction temperature is typically between 30°C and 180°C. The reaction time varies depending on the type of polymerization initiator and monomer, or the reaction temperature, and is generally between 0.5 hours and 10 hours. The polymer obtained through polymerization can be used in the preparation of radiosensitive linear compositions while dissolved in the reaction solution, or it can be used in the preparation of radiosensitive linear compositions after separation from the reaction solution. Polymer separation can be achieved, for example, by existing separation methods such as injecting the reaction solution into a large volume of undesirable solvent and drying the resulting precipitate under reduced pressure, or by removing the reaction solution by vacuum distillation using an evaporator.

[0092] When polymer component [A] contains polymer (S), polymer component [A] may consist solely of polymer (S) having structural unit (I), or it may contain polymers without structural unit (I) along with polymer (S). For example, when polymer component [A] contains structural units (I), (II), and (III), the same polymer may contain all of structural units (I), (II), and (III), or at least a portion of structural units (II) and (III) may be contained in a polymer different from the polymer having structural unit (I). Furthermore, when two or more different polymers have structural units (I), (II), and (III), it is preferable that the proportion of each structural unit contained in polymer component [A] satisfies the aforementioned range. In terms of reducing the number of components constituting the radiosensitive linear composition while obtaining improved imaging adhesion and chemical resistance, polymer component [A] is preferably a polymer containing structural units (I), (II), and (III). The polymers constituting the polymer components are preferably alkali-soluble resins.

[0093] Regarding the polymer (S), the weight-average molecular weight (Mw) of the polystyrene obtained by gel permeation chromatography (GPC) is preferably 2000 or more. If Mw is 2000 or more, it is preferable in terms of sufficiently high heat resistance or chemical resistance, and the ability to obtain a hardened film exhibiting good developability. Mw is more preferably 5000 or more, further preferably 6000 or more, and particularly preferably 7000 or more. Furthermore, from the viewpoint of achieving good film-forming properties, Mw is preferably 50000 or less, more preferably 30000 or less, further preferably 20000 or less, and particularly preferably 15000 or less.

[0094] Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. In addition, when the polymer component [A] comprises two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer respectively satisfy the aforementioned range.

[0095] (Siloxane polymer)

[0096] There are no particular limitations on the siloxane polymer as long as it can form a hardened film through hydrolysis and condensation. The siloxane polymer is preferably a polymer obtained by hydrolyzing a hydrolyzable silane compound represented by the following formula (6).

[0097] [Chemistry 7]

[0098]

[0099] (In equation (6), R) 21 It is a non-hydrolyzable monovalent group. R 22 It is an alkyl group having 1 to 4 carbon atoms. r is an integer from 0 to 3. Where r is 2 or 3, the multiple Rs in the formula... 21 These are either the same basis or different basis. When r is 0 to 2, the multiple R's in the equation... 22 (Whether they are the same base or different bases)

[0100] As R 21 Examples include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, groups having (meth)acryloyl groups, and groups having epoxy groups.

[0101] As R 22 Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. Among these, R is the most hydrolyzable. 22 Methyl or ethyl is preferred.

[0102] r is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1.

[0103] Specific examples of monomers constituting siloxane polymers include silane compounds having four hydrolyzable groups, such as tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzoxysilane, and tetran-n-propoxysilane.

[0104] Examples of silane compounds having three hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane.

[0105] Examples of silane compounds having two hydrolyzable groups include dimethyldimethoxysilane and diphenyldimethoxysilane.

[0106] Examples of silane compounds having a hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane.

[0107] Siloxane polymers can be obtained by hydrolyzing or condensing one or more hydrolyzable silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent. During the hydrolysis or condensation reaction, the hydrolytic group (-OR) of the hydrolyzable silane compound... 22 The total amount of water used is 1 mole, and the preferred proportion of water is 0.1 mole to 3 moles, more preferably 0.2 moles to 2 moles, and even more preferably 0.5 moles to 1.5 moles. By using this amount of water, the hydrolysis-condensation reaction rate can be optimized.

[0108] Catalysts used in hydrolysis and condensation reactions include, for example, acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, etc. The amount of catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and can be set appropriately. It is preferably 0.0001 mol to 0.2 mol relative to 1 mol of hydrolyzable silane compound, and more preferably 0.0005 mol to 0.1 mol.

[0109] Examples of organic solvents used in the hydrolysis and condensation reactions include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, non-water-soluble or poorly water-soluble organic solvents are preferred, such as ethylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propionate esters. The proportion of organic solvent used is preferably 10 to 10,000 parts by mass relative to a total of 100 parts by mass of the hydrolyzable silane compound used in the reaction, more preferably 50 to 1,000 parts by mass.

[0110] During the hydrolysis and condensation reactions, it is preferable to set the reaction temperature to below 130°C, more preferably to 40°C to 100°C. The reaction time is preferably 0.5 hours to 24 hours, more preferably 1 hour to 12 hours. During the reaction, the mixture can be stirred or placed under reflux. After the hydrolysis and condensation reactions, a dehydrating agent can be added to the reaction solution, followed by evaporation, thereby removing water and the generated alcohol from the reaction system.

[0111] Regarding the siloxane polymer, the weight-average molecular weight (Mw) of the polystyrene obtained by GPC is preferably 500 or more. If Mw is 500 or more, it is preferable to obtain a hardened film with sufficiently high heat resistance or solvent resistance and good developability. Mw is more preferably 1000 or more. Furthermore, from the viewpoint of good film-forming properties and suppression of reduced radiosensitivity, Mw is preferably 10000 or less, more preferably 5000 or less. Additionally, the molecular weight distribution (Mw / Mn) is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

[0112] Relative to the total amount of solid components contained in the radiosensitive linear composition, the content of polymer component [A] is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. Furthermore, relative to the total amount of solid components contained in the radiosensitive linear composition, the content of polymer component is preferably 99% by mass or less, more preferably 95% by mass or less. By setting the content of polymer component within the aforementioned range, a hardened film exhibiting sufficiently high heat resistance and chemical resistance, as well as good developability and transparency, can be obtained.

[0113] <[B]orthoester compounds>

[0114] [B] Orthoester compounds are compounds with three groups "-OR" 30 (where R) 30 Compounds with a structure consisting of a monovalent hydrocarbon group and the same carbon atom bonded together, defined by the general formula: R 31 -C(OR 30 )3 represents this. Here, R31 It is a hydrogen atom or a monovalent organic group. [B] Orthoester compounds exhibit hygroscopic properties in the presence of acid and hydrolyze to become esters. By including such orthoester compounds together with silicon-containing polymers in a radiosensitive linear composition, the hygroscopic effect of the orthoester compounds is achieved by utilizing the acid generated from the [C] photoacid generator (in other words, radiation irradiation), thereby improving the development adhesion of the coating film. In addition, orthoester compounds are preferred in that they are stable to alkaline developers, hydrophobic, and have minimal impact on unexposed areas (e.g., on sensitivity).

[0115] The "-OR" group present in orthoester compounds 30 Examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, phenoxy, and methylphenyl. Among these, orthoester compounds possess the group "-OR". 30 "Preferably, it is an alkoxy group, more preferably an alkoxy group having 1 to 4 carbon atoms. Furthermore, the orthoester compound possesses three groups 'R'..." 30 "Bases that are the same as each other or different bases."

[0116] As R 31 Examples include hydrogen atoms, monovalent chain hydrocarbon groups, halogenated chain hydrocarbon groups in which at least one hydrogen atom of the chain hydrocarbon group is substituted by a halogen atom, monovalent aromatic cyclic groups, etc. Among these, R... 31 Preferably, it is a hydrogen atom, a monovalent chain hydrocarbon group, or a monovalent aromatic cyclic group. Specifically, examples include hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms.

[0117] Specific examples of [B] orthoester compounds include: triethyl orthochloroacetate, trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, diethylphenyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthochloroacetate, trimethyl orthobutyrate, triethyl orthobutyrate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthovalerate, triethyl orthovalerate, trimethyl orthoisobutyrate, trimethyl orthobenzoate, triethyl orthobenzoate, etc.

[0118] As a [B] orthoester compound, the compound represented by the following formula (2) may preferably be used.

[0119] R 33 -C-(OR 32 )3…(2)

[0120] (In equation (2), R) 32 It is an alkyl or phenyl group having 1 to 4 carbon atoms. R 33It is a monovalent chain hydrocarbon group with 1 to 4 carbon atoms or a monovalent aromatic ring group with 6 to 12 carbon atoms. The three Rs in the formula... 32 (Whether they are the same base or different bases)

[0121] In equation (2), R 32 The alkyl group can be linear or branched. In terms of significantly improving the development adhesion of the coating film and having less impact on sensitivity, R... 32 Preferably, it is methyl, ethyl, or phenyl, more preferably methyl or ethyl.

[0122] R 33 The chain-like hydrocarbon group is preferably a chain-like or branched alkyl group having 1 to 4 carbon atoms. As R 33 Aromatic cyclic groups, such as phenyl, methylphenyl, dimethylphenyl, ethylphenyl, naphthyl, etc., can be listed.

[0123] In terms of its high effectiveness in improving the adhesion of the coating to the surface, R 33 Preferably, it is a monovalent aromatic cyclic group, and particularly preferably phenyl.

[0124] Regarding the potential to further improve the development adhesion of the coating film, compounds having aromatic ring groups are preferably used as [B] orthoester compounds. Specific examples of compounds having aromatic ring groups include R in formula (2). 32 and R 33 At least one of the compounds is an aromatic ring group. Furthermore, in the case where the [B] orthoester compound has an aromatic ring, the orthoester compound tends to remain in the film due to the increased hydrophobicity of the orthoester compound, which is believed to be caused by sufficient dehydration of the unexposed end.

[0125] Specific examples of orthoester compounds having aromatic ring groups include trimethyl orthobenzoate, triethyl orthobenzoate, and diethylphenyl orthoformate. Among these, trimethyl orthobenzoate and triethyl orthobenzoate are particularly preferred in terms of improving the adhesion of the coating film and maintaining sensitivity better.

[0126] The [B] orthoester compound preferably has a boiling point higher than the pre-baking temperature. By using an orthoester compound with a sufficiently high boiling point relative to the pre-baking temperature, the development adhesion of the coating film can be further improved. Specifically, the boiling point of the [B] orthoester compound is preferably 105°C or higher, more preferably 110°C or higher, and even more preferably 115°C or higher. Furthermore, when the boiling point of the [B] orthoester compound is sufficiently high relative to the pre-baking temperature, the volatilization of the [B] orthoester compound during pre-baking is suppressed, and the orthoester compound tends to remain in the film even after pre-baking, which is believed to be caused by sufficient dehydration of the unexposed ends.

[0127] Specific examples of [B] orthoester compounds with a boiling point of 105°C or higher include: triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthodichloroacetate, trimethyl orthobutyrate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthovalerate, trimethyl orthobenzoate, and triethyl orthobenzoate. Furthermore, in this specification, the boiling point is a value at one atmosphere.

[0128] In the radiosensitive linear composition, the content of the [B] orthoester compound is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, particularly preferably 2 parts by mass or more, relative to 100 parts by mass of the [A] polymer component. Furthermore, the content of the [B] orthoester compound is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, relative to 100 parts by mass of the [A] polymer component. When the content of the [B] orthoester compound is 0.1 parts by mass or more, it is preferable to sufficiently obtain the improved coating adhesion resulting from the presence of the [B] orthoester compound in the film. Furthermore, when the content of the [B] orthoester compound is 30 parts by mass or less, it is preferable to suppress the decrease in sensitivity caused by the [B] orthoester compound.

[0129] <[C] Photoacid Generator>

[0130] Photoacid generators are any compounds that produce acid through radiation exposure; there are no particular limitations. Examples of photoacid generators include: oxime sulfonates, onium salts, sulfonylimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylic acid ester compounds, and quinone diazide compounds.

[0131] Specific examples of oxime sulfonate compounds, onium salts, sulfonylimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, and carboxylic acid ester compounds include compounds described in paragraphs 0078 to 0106 of Japanese Patent Application Publication No. 2014-157252 and compounds described in International Publication No. 2016 / 124493. As a photoacid generator, from the viewpoint of radiation sensitivity, it is preferable to use at least one selected from the group consisting of oxime sulfonate compounds and sulfonylimide compounds.

[0132] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (7).

[0133] [Chemistry 8]

[0134]

[0135] (In equation (7), R) 23 A monovalent hydrocarbon group, or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted by a substituent. (* indicates a bond)

[0136] In equation (7), R is used as 23 Monovalent hydrocarbon groups, such as alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 4 to 12 carbon atoms, and aryl groups having 6 to 20 carbon atoms, can be used as substituents, such as alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, side oxygen groups, and halogen atoms.

[0137] Examples of oxime sulfonate compounds include: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, [2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in International Publication No. 2016 / 124493, etc. Commercially available oxime sulfonate compounds include BASF's Irgacure PAG121.

[0138] If sulfonylimide compounds are to be exemplified, the following can be listed: N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalenediamide.

[0139] As a photoacid generator, one or more of the following compounds can be used in combination with a quinone diazide compound: oxime sulfonate compounds, onium salts, sulfonylimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, and carboxylic acid ester compounds. Alternatively, a quinone diazide compound can be used alone.

[0140] Quinone diazide compounds are radiosensitive linear acid producers that generate carboxylic acids through radiation irradiation. Examples of quinone diazide compounds include condensates of phenolic or alcoholic compounds (hereinafter also referred to as "cores") with o-naphthoquinone diazide compounds. Among these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the core and an o-naphthoquinone diazide compound. Specific examples of cores include the compounds described in paragraphs 0065 to 0070 of Japanese Patent Application Publication No. 2014-186300.

[0141] Specific examples of quinone diazide compounds include compounds containing phenolic hydroxyl groups selected from 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene and 4,4'-[1-[4-[1-[4-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, and ester compounds with 1,2-naphthoquinone diazide-4-sulfonyl chloride or 1,2-naphthoquinone diazide-5-sulfonyl chloride.

[0142] In the radiosensitive linear composition, the content of the photoacid generator (C) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the polymer component (A). Furthermore, the content of the photoacid generator (C) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, relative to 100 parts by mass of the polymer component (A). Setting the content of the photoacid generator (C) to 0.05 parts by mass or more ensures sufficient acid generation upon irradiation with radiation, significantly increasing the difference in solubility of the irradiated and unirradiated portions in the alkaline solution. This allows for good pattern formation. Additionally, increasing the amount of acid participating in the reaction with the polymer component (A) ensures adequate heat resistance and solvent resistance. On the other hand, setting the content of the photoacid generator (C) to 20 parts by mass or less is preferable in that it significantly reduces the amount of unreacted photoacid generator after exposure, suppressing the decrease in developability caused by residual photoacid generator (C).

[0143] Here, when water is absorbed at the end of the unexposed portion during development, the base R in formula (1) present at the end of the unexposed portion... 1The coating becomes silanol-based, thereby increasing the hydrophilicity of the unexposed ends and reducing the development adhesion of the coating. To suppress this reduction in development adhesion, it is possible to incorporate hydrophobic additives into the radiosensitive linear composition or introduce structural units derived from hydrophobic monomers into the polymer component. However, increasing the hydrophobicity of the coating tends to reduce the development solubility of the exposed portions or lead to a decrease in sensitivity. In this regard, by incorporating a [B] orthoester compound into the radiosensitive linear composition using a silicone polymer, the development adhesion of the coating can be improved. In addition, sufficient margins can be ensured for the time from pre-baking to exposure, i.e., the post-coating delay (PCD) margin, and the time margin from exposure to development, i.e., the post-exposure delay (PED) margin.

[0144] <Other Ingredients>

[0145] In addition to the [A] polymer component, [B] orthoester compound and [C] photoacid generator described above, the radiosensitive linear composition disclosed herein may also contain other components (hereinafter also referred to as "other components").

[0146] (solvent)

[0147] The radiosensitive linear composition disclosed herein is a liquid composition comprising [A] a polymer component, [B] an orthoester compound, [C] a photoacid generator, and other components formulated as needed, preferably dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves each component formulated in the radiosensitive linear composition and does not react with any of the components.

[0148] Specific examples of solvents include: alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Among these, the solvent is preferably at least one selected from the group consisting of ethers and esters, more preferably at least one selected from the group consisting of ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates.

[0149] (Adhesive agent)

[0150] Adhesion enhancers are components that improve the adhesion between the hardened film formed using the radioactive linear composition and the substrate. As adhesion enhancers, functionalized silane coupling agents having reactive functional groups are preferably used. Examples of reactive functional groups in functionalized silane coupling agents include carboxyl groups, (meth)acryloyl groups, epoxy groups, vinyl groups, and isocyanate groups.

[0151] Specific examples of functional coupling agents include: trimethoxysilylbenzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, etc.

[0152] When a bonding agent is incorporated into a radiosensitive linear composition, its content is preferably 0.01 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of polymer component [A].

[0153] (Acid diffusion control agent)

[0154] An acid diffusion control agent is a component that controls the diffusion length of acid generated from a [C] photoacid generator upon exposure. By incorporating an acid diffusion control agent into the radiosensitive linear composition of this disclosure, the diffusion length of the acid can be appropriately controlled, resulting in good pattern developability. Furthermore, the formulation of an acid diffusion control agent is preferred in terms of improving developability and chemical resistance.

[0155] As an acid diffusion control agent, it can be arbitrarily selected from the basic compounds used in chemically amplified resists. Examples of basic compounds include fatty acid amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of basic compounds include compounds described in paragraphs 0128 to 0147 of Japanese Patent Application Publication No. 2011-232632. As an acid diffusion control agent, at least one selected from the group consisting of aromatic amines and heterocyclic amines is preferably used.

[0156] Examples of aromatic amines and heterocyclic amines include: aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, and other aniline derivatives; imidazoles, 4-methylimidazolium, 4-methyl-2-phenylimidazolium, benzimidazole, 2-phenylbenzimidazole, triphenylimidazolium, and other imidazole derivatives; and pyrroles, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-diphenylimidazolium, etc. Pyrrole derivatives such as methylpyrrole and N-methylpyrrole; pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 3-methyl-4-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinylpyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, nicotine, and other pyridine derivatives, as well as compounds described in Japanese Patent Application Publication No. 2011-232632.

[0157] When an acid diffusion control agent is incorporated into a radiosensitive linear composition, from the viewpoint of fully obtaining the improved chemical resistance effect brought about by the incorporation of the acid diffusion control agent, its content ratio relative to 100 parts by mass of polymer component [A] is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more. Furthermore, relative to 100 parts by mass of polymer component [A], the content ratio of the acid diffusion control agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

[0158] Other components, besides those described above, may include, for example, multifunctional polymerizable compounds (multifunctional (meth)acrylates, etc.), surfactants (fluorinated surfactants, silicone surfactants, nonionic surfactants, etc.), polymerization inhibitors, antioxidants, chain transfer agents, etc. The proportions of these components may be appropriately selected based on the individual components, without impairing the effects of this disclosure.

[0159] The solid content concentration (the proportion of the total mass of the components other than the solvent in the radiosensitive linear composition relative to the total mass of the radiosensitive linear composition) of the disclosed radiosensitive linear composition can be appropriately selected considering viscosity, volatility, etc. The solid content concentration of the radiosensitive linear composition is preferably in the range of 5% to 60% by mass. If the solid content concentration is 5% by mass or more, sufficient film thickness can be ensured when coating the radiosensitive linear composition onto a substrate. Furthermore, if the solid content concentration is 60% by mass or less, the film thickness will not be excessive, thereby moderately increasing the viscosity of the radiosensitive linear composition and ensuring good coatability. The solid content concentration of the radiosensitive linear composition is more preferably 10% to 55% by mass, and more preferably 12% to 50% by mass.

[0160] <Curing film and its manufacturing method>

[0161] The hardened film disclosed herein is formed from a radiosensitive linear composition prepared in the manner described. The radiosensitive linear composition exhibits high radiation sensitivity and excellent storage stability. Furthermore, by using the radiosensitive linear composition, a patterned film exhibiting high adhesion to the substrate even after development and excellent chemical resistance can be formed. Therefore, the radiosensitive linear composition is preferably used as a forming material for, for example, interlayer insulating films, planarization films, spacers, protective films, colored patterned films for color filters, isolation walls, and banks.

[0162] In manufacturing the curing film, a positive curing film can be formed depending on the type of photosensitizer by using the aforementioned radiosensitive linear composition. The curing film can be manufactured using the aforementioned radiosensitive linear composition, for example, by a method comprising steps 1 to 4 below.

[0163] (Step 1) Step of forming a coating film using the said radiosensitive linear composition.

[0164] (Step 2) A step of exposing at least a portion of the coating.

[0165] (Step 3) The process of developing the exposed coating.

[0166] (Step 4) The process of heating the developed coating.

[0167] The following is a detailed description of each process.

[0168] [Process 1: Coating Process]

[0169] In this process, the radioactive linear composition is coated onto the surface on which the film is to be formed (hereinafter also referred to as the "film-forming surface"). Preferably, the solvent is removed by heat treatment (pre-baking), thereby forming a coating on the film-forming surface. The material of the film-forming surface is not particularly limited. For example, in the case of forming an interlayer insulating film, the radioactive linear composition is coated onto a substrate on which switching elements such as thin film transistors (TFTs) are provided to form a coating. As the substrate, for example, a glass substrate, a silicon substrate, or a resin substrate is used. A metal thin film, depending on the application, may also be formed on the surface of the substrate on which the coating is formed, and various surface treatments such as hexamethyldisilazane (HMDS) treatment may also be performed.

[0170] Examples of coating methods for the radiosensitive linear composition include spray coating, roller coating, spin coating, slot die coating, rod coating, and inkjet coating. Among these methods, spin coating, slot die coating, or rod coating are preferred. Pre-baking conditions vary depending on the type and proportion of each component in the radiosensitive linear composition, and for example, are performed at 60°C to 130°C for 0.5 to 10 minutes. The film thickness formed (i.e., the film thickness after pre-baking) is preferably 0.1 μm to 12 μm. For the radiosensitive composition coated on the film-forming surface, vacuum drying (VCD) can also be performed before pre-baking.

[0171] [Process 2: Exposure Process]

[0172] In this process, at least a portion of the coating film formed in step 1 is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a patterned hardened film can be formed. Examples of radiation include ultraviolet light, far ultraviolet light, visible light, X-rays, and charged particle beams such as electron beams. Ultraviolet light is preferred among these, such as gamma rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The exposure dose of the radiation is preferably 0.1 J / m². 2 ~20,000 J / m 2 .

[0173] [Process 3: Developing Process]

[0174] In this process, the coating film irradiated with radiation in step 2 is developed. Specifically, the irradiated coating film in step 2 is subjected to positive development using a developing solution to remove the irradiated portion. Examples of developing solutions include aqueous solutions of alkalis (alkaline compounds). Examples of alkalis include sodium hydroxide, tetramethylammonium hydroxide, and the alkalis exemplified in paragraph

[0127] of Japanese Patent Application Publication No. 2016-145913. The alkali concentration of the aqueous solution is preferably 0.1% to 5% by mass from the viewpoint of obtaining adequate developability. Suitable developing methods include liquid coating, immersion, shaking immersion, and spraying. The developing time also varies depending on the composition of the composition, for example, from 30 seconds to 120 seconds. Furthermore, it is preferable to perform a rinsing treatment with running water after the developing step.

[0175] [Process 4: Heating Process]

[0176] In this process, the developed coating from step 3 is heated (post-baking). Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding post-baking conditions, the heating temperature is, for example, 120°C to 250°C. For example, when heating on a hot plate, the heating time is 5 minutes to 40 minutes; when heating in an oven, the heating time is 10 minutes to 80 minutes. Performed as described above, a hardened film with a target pattern can be formed on the substrate. The shape of the pattern in the hardened film is not particularly limited; examples include line and space patterns, dot patterns, hole patterns, and grid patterns.

[0177] <Semiconductor Components>

[0178] The semiconductor device disclosed herein includes a hardened film formed using the aforementioned radioactive linear composition. The hardened film is preferably an interlayer insulating film that insulates the wiring within the semiconductor device. The semiconductor device of this disclosure can be manufactured using existing methods.

[0179] <Display Components>

[0180] The display element disclosed herein includes a hardened film formed using the aforementioned linearly emitting composition. The display element includes a semiconductor element of this disclosure, thereby including the hardened film formed using the aforementioned linearly emitting composition. Alternatively, the display element of this disclosure may also include a planarization film formed on a TFT substrate as the hardened film formed using the aforementioned linearly emitting composition. Examples of display elements include liquid crystal display elements and organic electroluminescence (EL) display elements.

[0181] [Example]

[0182] The present invention will be specifically described below through examples, but the present invention is not limited to these examples. Furthermore, unless otherwise specified, "parts" and "%" in the examples and comparative examples refer to mass. In this example, the weight average molecular weight (Mw) and number average molecular weight of the polymer were determined by the following methods.

[0183] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)]

[0184] The Mw and Mn of the polymer were determined by the following method.

[0185] • Determination method: Gel permeation chromatography (GPC)

[0186] • Device: Showa Denko GPC-101

[0187] • GPC tubing: Combining Shimadzu GLC's GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

[0188] • Mobile phase: Tetrahydrofuran

[0189] • Column temperature: 40℃

[0190] • Flow rate: 1.0 mL / min

[0191] • Sample concentration: 1.0% by mass

[0192] • Sample injection volume: 100 μL

[0193] • Detector: Differential refractometer

[0194] • Standard reference material: Monodisperse polystyrene

[0195] [monomer]

[0196] The abbreviations for the monomers used in the synthesis of polymers are as follows.

[0197] Monomers having the base represented by formula (1)

[0198] MPTMS: 3-Methacryloxypropyltrimethoxysilane

[0199] MPTES: 3-Methacryloxypropyltriethoxysilane

[0200] STMS: p-Styrenetrimethoxysilane

[0201] SDMS: p-Styrene dimethoxyhydroxysilane

[0202] STES: p-Styrenetriethoxysilane

[0203] Other Individuals

[0204] AA: Acrylic acid

[0205] MA: Methacrylic acid

[0206] MI: Maleimide

[0207] OXMA: OXE-30 (manufactured by Osaka Organic Chemicals Co., Ltd.) Methyl methacrylate (3-ethyloxetane-3-yl)

[0208] GMA: Glycidyl methacrylate

[0209] ECHMA: 3,4-Epoxycyclohexyl methyl methacrylate

[0210] EDCPMA: Methacrylate [3,4-epoxytricyclic (5.2.1.0)] 2,6 )decane-9-yl] ester

[0211] MMA: Methyl methacrylate

[0212] ST: Styrene

[0213] <Synthesis of Polymer (A)>

[0214] [Synthesis Example 1] Synthesis of Polymer (A-1)

[0215] 24 parts of propylene glycol monomethyl ether were added to a flask equipped with a cooling tube and a stirrer, followed by 39 parts of methyltrimethoxysilane and 18 parts of 3-methacryloyloxypropyltrimethoxysilane. The solution was heated to 60°C. After reaching 60°C, 0.1 parts of formic acid and 19 parts of water were added, and the solution temperature was raised to 75°C while stirring slowly. This temperature was maintained for 2 hours. After cooling to 45°C, 28 parts by mass of trimethyl orthoformate were added as a dehydrating agent, and the mixture was stirred for 1 hour. The solution temperature was then lowered to 40°C, and evaporation was carried out while maintaining the temperature to remove water and methanol produced during hydrolysis and condensation, thereby obtaining a polymer solution containing polymer (A-1). The solid content concentration of the polymer solution was 35% by mass, the weight average molecular weight (Mw) of polymer (A-1) was 1,800, and the molecular weight distribution (Mw / Mn) was 2.2.

[0216] [Synthesis Example 2] Synthesis of Polymer (A-2)

[0217] The monomers used were changed to 39 parts of phenyltrimethoxysilane and 18 parts of 3-methacryloyloxypropyltrimethoxysilane. Otherwise, a polymer (A-2) with the same solid content concentration, weight average molecular weight and molecular weight distribution as polymer (A-1) was obtained by using the same method as in Synthesis Example 1.

[0218] [Synthesis Example 3] Synthesis of Polymer (A-3)

[0219] Ten parts of 2,2'-azobis(2,4-dimethylpentanonitrile) and 200 parts of diethylene glycol methyl ethyl ether were charged into a flask equipped with a cooling tube and a stirrer. Then, 15 parts of 3-methacryloyloxypropyltrimethoxysilane, 10 parts of methacrylic acid, 20 parts of methyl methacrylate (3-ethyloxetane-3-yl) methacrylate, 30 parts of glycidyl methacrylate, and 25 parts of methyl methacrylate were added. After nitrogen purging, the solution temperature was raised to 70°C while stirring slowly and maintained at this temperature for 5 hours, thereby obtaining a polymer solution containing polymer (A-3). The solid content concentration of the polymer solution was 34.0% by mass, the Mw of polymer (A-3) was 10,500, and the molecular weight distribution (Mw / Mn) was 2.2.

[0220] [Synthesis Examples 4 to 12, Comparative Synthesis Example 1, Comparative Synthesis Example 2] Synthesis of polymers (A-4) to (A-12), (CA-1), and (CA-2)

[0221] Using the types and proportions (parts by mass) of each component shown in Table 1, except for the same method as in Synthesis Example 3, a polymer solution containing polymers (A-4) to (A-12), polymer (CA-1), and polymer (CA-2) having the same solid component concentration, weight average molecular weight, and molecular weight distribution as polymer (A-3) was obtained.

[0222]

[0223] <Preparation of Radiosensitive Linear Compositions>

[0224] The polymer (A), orthoester compound (B), photoacid generator (C), additive (X), and solvent (G) used in the preparation of the radiosensitive linear composition are shown below.

[0225] Polymer (A)

[0226] A-1 to A-12: Polymers (A-1) to (A-12) synthesized in Synthetic Examples 1 to 12.

[0227] CA-1~CA-2: Polymers (CA-1) and (CA-2) synthesized in Comparative Synthesis Example 1 and Comparative Synthesis Example 2.

[0228] Orthoester compounds (B)

[0229] B-1: Trimethyl orthoformate

[0230] B-2: Trimethyl orthoacetate

[0231] B-3: Triethyl orthoacetate

[0232] B-4: Trimethyl orthobenzoate

[0233] B-5: Triethyl orthobenzoate

[0234] Photoacid Generator (C)

[0235] C-1: Irgacure PAG121 (manufactured by BASF)

[0236] C-2: OS-17 as described in International Publication No. 2016 / 124493

[0237] C-3: OS-25 as described in International Publication No. 2016 / 124493

[0238] Additives (X)

[0239] X-1: 3-Glycidoxypropyltrimethoxysilane

[0240] X-2: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane

[0241] X-3: 2-Phenylenibimidazole

[0242] X-4: N-(tert-butoxycarbonyl)-2-phenylbenzimidazole

[0243] X-5: 4-Methyl-2-phenylbenzimidazole

[0244] Solvent (G)

[0245] G-1: Diethylene glycol ethyl methyl ether

[0246] G-2: Propylene glycol monomethyl ether

[0247] G-3: Propylene glycol monomethyl ether acetate

[0248] <Preparation of Radiosensitive Linear Compositions>

[0249] [Example 1]

[0250] In a polymer solution containing the polymer (A-1) obtained in Synthesis Example 1, 5 parts of orthoester compound (B-4), 1 part of photoacid generator (C-2), and 5 parts of additive (x-1) are mixed in an amount equivalent to 100 parts (solid component) of polymer (A-1), and diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether are added in a 1:1 mass ratio to achieve a final solid component concentration of 20% by mass. The mixture is then filtered using a membrane filter with a pore size of 0.2 μm to prepare a radiosensitive linear composition.

[0251] [Examples 2-20, Comparative Examples 1-5]

[0252] Using the types and proportions (parts by mass) of each component shown in Table 2, except for the method used in Example 1, radiosensitive linear compositions of Examples 2 to 20 and Comparative Examples 1 to 5 were prepared respectively.

[0253]

[0254] <Evaluation>

[0255] The radiosensitive linear compositions of Examples 1 to 20 and Comparative Examples 1 to 5 were used to evaluate the following items using the methods described below. The evaluation results are shown in Table 3.

[0256] [Radiation sensitivity]

[0257] Using a spinner, the radiosensitive linear composition was coated onto a silicon substrate that had undergone HMDS treatment at 60°C for 60 seconds. The substrate was then pre-baked at 90°C for 2 minutes on a hot plate to form a coating with an average thickness of 3.0 μm. A pattern mask with a 10 μm wide line and spatial pattern was used as a separator, and the coating was irradiated with a predetermined amount of ultraviolet light using a mercury lamp. Next, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used as the developer, and the substrate was developed at 25°C for 60 seconds, followed by rinsing with ultrapure water for 1 minute. At this point, the minimum exposure required to form a 10 μm wide line and spatial pattern was determined. The minimum exposure value was less than 300 J / m. 2 Under these conditions, the radiation sensitivity can be evaluated as good, at 300 J / m 2 In the above cases, poor radiation sensitivity can be assessed.

[0258] [Evaluation of PCD (Post-coating Delay) Margin]

[0259] Using a spinner, a radiosensitive linear composition was coated onto a silicon substrate that had undergone HMDS treatment at 60°C for 60 seconds. The substrate was then pre-baked at 90°C for 2 minutes on a hot plate to form a coating with an average thickness of 3.0 μm. After the coating was left to stand at room temperature for 1 hour (this standing is not performed in the PED margin evaluation below), a pattern mask with a line and spatial pattern of 10 μm width was used as a separator, and the coating was irradiated with a specified amount of ultraviolet light using a mercury lamp. After ultraviolet irradiation, the coating was developed at 25°C for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as the developer, followed by rinsing with ultrapure water for 1 minute. This series of operations was performed by varying the exposure amount, and the minimum exposure amount required to form a line and spatial pattern of 10 μm width was determined. The measured value of the minimum exposure is compared with the measured value of the [radiation sensitivity]. A case where the increase in minimum exposure is less than 5% is classified as "AA", a case where it is 5% or more but less than 10% is classified as "A", a case where it is 10% or more but less than 20% is classified as "B", a case where it is 20% or more but less than 30% is classified as "C", and a case where it is 30% or more is classified as "D". Cases of AA, A, or B are considered to have good PCD margin, while cases of C or D are considered to have poor PCD margin.

[0260] [Evaluation of PED (Post-Exposure Delay) Margin]

[0261] Using a spinner, a radiosensitive linear composition was coated onto a silicon substrate that had undergone HMDS treatment at 60°C for 60 seconds. The substrate was then pre-baked at 90°C for 2 minutes on a hot plate to form a coating with an average thickness of 3.0 μm. A pattern mask with a 10 μm wide line and spatial pattern was used as a separator, and the coating was irradiated with a predetermined amount of ultraviolet light using a mercury lamp. After the UV-irradiated coating was left at room temperature for 1 hour (this period was not performed in the PCD margin evaluation), it was developed at 25°C for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as the developer, followed by rinsing with ultrapure water for 1 minute. This series of operations was performed by varying the exposure amount, and the minimum exposure amount required to form a 10 μm wide line and spatial pattern was determined. The measured value of minimum exposure is compared with the measured value of [radiation sensitivity]. A rate of increase of less than 5% in minimum exposure is classified as "AA", 5% or more but less than 10% as "A", 10% or more but less than 20% as "B", 20% or more but less than 30% as "C", and 30% or more as "D". Cases of AA, A, or B indicate good PED margin, while cases of C or D indicate poor PED margin.

[0262] [Evaluation of the chemical resistance of the hardened film]

[0263] The chemical resistance of the hardened film was evaluated based on the degree of swelling induced by the stripping solution. Using a spinner, the radiosensitive linear composition was coated onto a silicon substrate and pre-baked at 90°C for 2 minutes on a hot plate to form a coating with an average thickness of 3.0 μm. Subsequently, the entire surface of the substrate was irradiated with 3000 J / m² using a proximity irradiation machine (Canon's MA-1200 (ghi-ray hybrid)). 2 After exposure to light, the film is calcined (post-baked) in an oven heated to 230°C for 30 minutes to form a hardened film. The resulting hardened film is then immersed in N-methyl-2-pyrrolidone solvent heated to 40°C for 6 minutes, and the film thickness change rate (%) before and after immersion is calculated. The film thickness change rate is used as an indicator of chemical resistance and evaluated according to the following criteria.

[0264] AA: Film thickness change rate less than 2%

[0265] A: The film thickness variation rate is greater than 2% but less than 5%.

[0266] B: Film thickness variation rate is 5% or more but less than 10%.

[0267] C: Film thickness variation rate is 10% or more but less than 15%.

[0268] D: Film thickness variation rate is above 15%

[0269] Film resistance is rated as good under conditions AA, A, or B, and as poor under conditions C or D. Film thickness was measured at 25°C using an optical interferometric film thickness measuring device (Lambda Ace VM-1010).

[0270] [Evaluation of preservation stability]

[0271] The prepared radiosensitive composition was sealed in a light-proof, airtight container. After 7 days at 25°C, the container was opened, and the [radiosensitivity] was measured according to the aforementioned evaluation criteria. The increase rate of radiosensitivity (minimum exposure) before and after 7 days of storage was calculated. Values ​​less than 5% were classified as "AA", 5% or more but less than 10% as "A", 10% or more but less than 20% as "B", 20% or more but less than 30% as "C", and 30% or more as "D". Values ​​of AA, A, or B indicate good storage stability, while values ​​of C or D indicate poor storage stability.

[0272] Evaluation of substrate adhesion (developable adhesion)

[0273] Using a spinner, the radiosensitive linear composition was coated onto a silicon substrate that had not undergone HMDS treatment, and then pre-baked at 90°C for 2 minutes on a hot plate to form a coating with an average thickness of 3.0 μm. A pattern mask with line and spatial patterns of 1 μm to 50 μm width was used to irradiate the coating with a mercury lamp at an exposure dose of 400 J / m at 365 nm. 2 The substrate was then exposed to ultraviolet light. Next, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used as the developer. After development at 25°C for 60 seconds, the substrate was rinsed with ultrapure water for 1 minute. At this point, the minimum width of the residual lines and spatial patterns that did not peel off from the substrate was measured. A value of 2 μm or less was classified as "AA"; greater than 2 μm but less than 5 μm was classified as "A"; greater than 5 μm but less than 10 μm was classified as "B"; greater than 10 μm but less than 30 μm was classified as "C"; and greater than 30 μm was classified as "D". Cases of AA, A, or B indicate good substrate adhesion, while cases of C or D indicate poor substrate adhesion.

[0274] [Table 3]

[0275]

[0276] Furthermore, in Table 2, regarding the solvent (G), in the examples using two organic solvents (Examples 1, 2, 4-14, 18-20), solvent 1 and solvent 2 were mixed at a mass ratio of solvent 1:solvent 2 = 1:1. In the examples using three organic solvents (Examples 3, 15-17, Comparative Examples 1-5), solvent 1, solvent 2, and solvent 3 were mixed at a mass ratio of solvent 1:solvent 2:solvent 3 = 5:4:1. In Table 3, "-" indicates that the solvent was not resolved in the mask evaluation and therefore could not be evaluated.

[0277] As shown in Table 3, the radiosensitive linear compositions of Examples 1 to 20 exhibited good radiation sensitivity. As practical characteristics, their radiosensitivity, storage stability, substrate adhesion, PCD margin, PED margin, and chemical resistance were all good. In contrast, Comparative Examples 1 and 2 did not resolve upon exposure and showed poor chemical resistance. Furthermore, the radiosensitive linear compositions of Comparative Examples 3 to 5 showed worse storage stability, substrate adhesion, PCD margin, and PED margin compared to the examples.

Claims

1. A radiosensitive composition comprising: Polymers comprising structural units (I) having a base represented by the following formula (1); Photoacid generator; and orthoester compounds, The orthoester compound has an aromatic ring group. In formula (1), R 1 is a hydrogen atom, a halogen atom, a hydroxyl group, or an alkoxy group having a carbon number of 1 to 6; R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, an alkyl group having a carbon number of 1 to 10, or a phenyl group; and "*" represents a bond.

2. A radiosensitive composition comprising: Polymers comprising structural units (I) having a base represented by the following formula (1); Photoacid generator; and orthoester compounds, The orthoester compound has a boiling point above 105°C. In formula (1), R 1 is a hydrogen atom, a halogen atom, a hydroxyl group, or an alkoxy group having a carbon number of 1 to 6; R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, an alkyl group having a carbon number of 1 to 10, or a phenyl group; and "*" represents a bond.

3. The radiosensitive linear composition according to claim 1 or 2, wherein the group represented by formula (1) is bonded to an aromatic cyclic group or a chain hydrocarbon group.

4. The radiosensitive linear composition according to claim 1 or 2, wherein the structural unit (I) has at least one selected from the group consisting of a base represented by formula (3-1), a base represented by formula (3-2), and a base represented by formula (3-3). In formula (3-1), formula (3-2), and formula (3-3), A 1 and A 2 are each independently a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbons, or an alkoxy group having 1 to 6 carbons; n1 is an integer of 0 to 4; n2 is an integer of 0 to 6; and In the case where n1 is 2 or more, the plurality of A 1 are the same or different groups; in the case where n2 is 2 or more, the plurality of A 2 are the same or different groups; R 6 is an alkanediyl group; R 1 , R 2 , and R 3 have the same meanings as the formula (1); and "*" represents a bond.

5. A radiosensitive composition comprising: Siloxane polymers; Photoacid generator; and orthoester compounds, The orthoester compound has an aromatic ring group.

6. The radiosensitive linear composition according to claim 1 or 5, wherein the orthoester compound is a compound represented by the following formula (2), R 33 -C-(OR 32 )3…(2) In formula (2), R 32 is an alkyl group having 1 to 4 carbon atoms or a phenyl group; R 33 is a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 4 carbon atoms, or a monovalent aromatic ring group having 6 to 12 carbon atoms; three R 32 are the same or different groups; wherein, R 32 and at least one of R 33 is an aromatic ring group.

7. The radiosensitive composition according to claim 6, wherein the orthoester compound has a boiling point of 105°C or higher.

8. A radiosensitive composition comprising: Siloxane polymers; Photoacid generator; and orthoester compounds, The boiling point of the orthoester compound is above 105°C.

9. The radiosensitive linear composition according to claim 2 or 8, wherein the orthoester compound is a compound represented by the following formula (2), R 33 -C-(OR 32 )3…(2) In formula (2), R 32 is an alkyl group having 1 to 4 carbon atoms or a phenyl group; R 33 is a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 4 carbon atoms, or a monovalent aromatic ring group having 6 to 12 carbon atoms; and three R 32 are the same or different groups from each other.

10. The radiosensitive composition according to any one of claims 1, 2, 5, and 8, wherein the orthoester compound has a boiling point of 110°C or higher.

11. The radiosensitive linear composition according to any one of claims 1, 2, 5, and 8, wherein the photoacid generator comprises at least one selected from the group consisting of oxime sulfonate compounds and sulfonamide compounds.

12. The radiosensitive linear composition according to any one of claims 1, 2, 5, and 8, further comprising an acid diffusion control agent.

13. A method for manufacturing a hardened film, comprising: The process of forming a coating film using the radiosensitive linear composition as described in any one of claims 1 to 12; The process of irradiating at least a portion of the coating with radiation; The process of developing the coating film after it has been irradiated with radiation; and The process of heating the developed coating.

14. A hardened film formed using the radiosensitive linear composition as described in any one of claims 1 to 12.

15. A semiconductor device comprising the hardened film as claimed in claim 14.

16. A display element comprising the semiconductor element as claimed in claim 15.

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