CN115268214A

CN115268214A - Radiation-sensitive composition, cured film and method for producing the same, semiconductor and display device

Info

Publication number: CN115268214A
Application number: CN202210464152.1A
Authority: CN
Inventors: 中西拓也; 蛸岛薫; 浅冈高英
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2021-04-30
Filing date: 2022-04-29
Publication date: 2022-11-01
Also published as: JP2022171636A; KR20220149450A; TW202244136A

Abstract

The invention provides a radiation-sensitive composition capable of forming a cured film with excellent development adhesion, a cured film and a manufacturing method thereof, a semiconductor and a display element. A radiation-sensitive composition comprising: a polymer which is at least one selected from the group consisting of a polymer comprising a structural unit (I) having a group represented by the formula (1) or an acid-dissociable group, and a siloxane polymer; a photoacid generator; and having a bond between a hydrophobic group and a hydroxyl groupA silanol compound having a partial structure of silicon atoms bonded thereto and having no alkoxy group. In the formula (1), R¹、R²And R³Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms or a phenyl group. Wherein R is¹、R²And R³At least one of them is an alkoxy group having 1 to 6 carbon atoms. "" indicates a bond.

Description

Radiation-sensitive composition, cured film and method for producing the same, semiconductor and display device

Technical Field

The invention relates to a radiation-sensitive composition, a cured film and a manufacturing method thereof, a semiconductor element and a display element.

Background

A cured film (for example, an interlayer insulating film, a spacer, a protective film, or the like) included in a semiconductor element or a display element is generally formed using a radiation-sensitive composition containing a polymer component and a radiation-sensitive compound (for example, a photoacid generator, a photopolymerization initiator, or the like). For example, a cured film having a pattern shape can be obtained by forming a pattern by subjecting a coating film formed of a radiation-sensitive composition to radiation irradiation and development treatment, and then heat-curing the pattern by heat treatment.

As a material for forming a cured film of a semiconductor device or a display device, patent documents 1 and 2 propose a radiation-sensitive composition including: a polymer having a silicon-containing functional group such as an alkoxysilane group, a silicon-containing polymer such as a siloxane polymer, and a photoacid generator.

When a coating film is formed using the radiation-sensitive composition of patent document 1, an acid is generated from the photoacid generator by exposure at the time of pattern formation, and the generated acid decomposes the alkoxy group to solubilize the exposed portion with respect to a developing solution. The unexposed portion is insoluble in alkali, and after development, it is heated to be dehydrated and condensed and hardened to form a hardened film. In addition, in the radiation-sensitive composition of patent document 2, an acid generated from the photoacid generator by exposure participates in the composition to promote self-crosslinking of the siloxane polymer, thereby forming a cured film.

As a material for forming a cured film of a semiconductor device or a display device, patent document 3 proposes a radiation-sensitive composition containing: a polymer containing a structural unit having an acidic group, a polymerizable monomer, and a photopolymerization initiator. Patent document 4 proposes a chemically amplified radiation-sensitive composition containing: a polymer comprising a structural unit having an acid-dissociable group, and a photoacid generator. Patent document 5 proposes a radiation-sensitive composition containing: a polymer containing a structural unit having an acidic group, and a quinone diazide compound.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open publication No. 2017-107024

[ patent document 2] International publication No. 2011/065215

[ patent document 3] Japanese patent laid-open No. 2003-5357

[ patent document 4] Japanese patent laid-open publication No. 2011-232632

[ patent document 5] Japanese patent laid-open No. 2014-186300

Disclosure of Invention

[ problems to be solved by the invention ]

When the adhesion between the coating film and the substrate after the irradiation with radiation is insufficient, a developing solution may enter from the interface between the film and the substrate during the development treatment, and the pattern of the film may peel off. In particular, in recent years, further improvement in quality of display devices has been demanded, and with the thinning of patterns due to the demand for further improvement in quality of display devices, pattern peeling of films tends to occur easily during development processing. In view of suppressing a reduction in production yield, it is required that the radiation-sensitive composition is less likely to cause peeling of the film from the substrate during development treatment (i.e., has good development adhesion).

The present invention has been made in view of the above problems, and an object thereof is to provide a radiation-sensitive composition capable of forming a cured film having excellent development adhesion.

[ means for solving problems ]

The present inventors have found that the above problems can be solved by formulating a specific compound in a radiation-sensitive composition. That is, the present invention provides the following radiation-sensitive composition, cured film and method for producing the same, semiconductor device, and display device.

[1] A radiation-sensitive composition comprising: a polymer which is at least one selected from the group consisting of a polymer containing a structural unit (I) having a group represented by the following formula (1) or an acid-dissociable group, and a siloxane polymer; a photoacid generator; and silanol (silanol) compounds having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group.

[ solution 1]

(in the formula (1), R¹、R²And R³Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms or a phenyl group. Wherein R is¹、R²And R³At least one of them is an alkoxy group having 1 to 6 carbon atoms. "+" indicates a bond)

[2] A radiation-sensitive composition comprising: a polymer comprising a structural unit having an acidic group (wherein a polymer having a structural unit represented by the formula (1) is excluded); a quinone diazide compound; a silanol compound which has a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and which does not have an alkoxy group; a basic compound; and a solvent.

[3] A radiation-sensitive composition comprising: a polymer comprising a structural unit having an acidic group; a polymerizable monomer; a photopolymerization initiator; a silanol compound which has a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and which has no alkoxy group; a basic compound; and a solvent.

[4] A method for manufacturing a hardened film, comprising: a step of forming a coating film using the radiation-sensitive composition according to any one of [1] to [3 ]; irradiating at least a part of the coating film with radiation; developing the coating film irradiated with the radiation; and heating the developed coating film.

[5] A cured film formed using the radiation-sensitive composition according to any one of [1] to [3 ].

[6] A semiconductor element comprising the hardened film of [5 ].

[7] A display element comprising the hardened film of [5 ].

[ Effect of the invention ]

According to the radiation-sensitive composition of the present disclosure, a cured film having excellent development adhesion can be formed.

Detailed Description

The following describes details of the embodiments. In the present specification, the numerical range described by "to" is used to mean that the numerical values described before and after "to" are included as the lower limit value and the upper limit value. The "structural unit" means a unit mainly constituting the main chain structure, and means that two or more units are contained in at least the main chain structure.

The term "hydrocarbon group" as used herein includes chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain and are composed of only a chain structure. The polymer may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. The alicyclic hydrocarbon group does not necessarily have to be constituted by only the alicyclic hydrocarbon structure, and includes a group having a chain structure in a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. In addition, the structure may not necessarily be composed of only an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in a part thereof. The ring structure of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent including a hydrocarbon structure. The term "cyclic hydrocarbon group" is intended to include alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

Radiation sensitive composition

The radiation-sensitive composition of the present disclosure (hereinafter, also referred to as "the present composition") is used, for example, for forming a cured film of a display element. The composition is a resin composition containing [ A ] a polymer component and [ B ] a silanol compound. Hereinafter, each component contained in the first composition, the second composition and the third composition, which are specific embodiments of the present composition, and other components blended as necessary will be described. In addition, as for each component, one kind may be used alone or two or more kinds may be used in combination as long as they are not particularly mentioned.

[ first composition ]

The first composition is a positive type resin composition containing [ A ] a polymer component, [ B ] a silanol compound, and [ C ] a photoacid generator.

[ A ] Polymer component ]

[A] The polymer component contains at least one polymer selected from the group consisting of a polymer containing a structural unit (I) having a group represented by the following formula (1) or an acid-dissociable group and a siloxane polymer (hereinafter, also referred to as "a-1 polymer").

[ solution 2]

(in the formula (1), R¹、R²And R³Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms or a phenyl group. Wherein R is¹、R²And R³At least one of them is an alkoxy group having 1 to 6 carbon atoms. "" indicates a bond)

Specific examples of the polymer component contained in the first composition include a polymer containing a structural unit (I-1) having a group represented by the formula (1) (hereinafter, also referred to as "polymer (a 1-1)"), a polymer containing a structural unit (I-2) having an acid-dissociable group (hereinafter, also referred to as "polymer (a 1-2)"), and a silicone polymer. In addition, at least one selected from the group consisting of polymers containing a structural unit having a group represented by the formula (1) and siloxane polymers among the polymers (a-1) is hereinafter also referred to as "silicon-containing polymer".

Here, it is considered that the hardened film formed using the radiation-sensitive composition of patent document 1 or patent document 2 absorbs water from the end of the unexposed portion during the development treatment, and thereby the alkoxy group in the unexposed portion is changed to a silanol group, and the hydrophilicity of the unexposed portion increases. In such a case, the adhesion (development adhesion) of the unexposed portion to the substrate may be reduced, and the pattern may be easily peeled off from the substrate.

In addition, in the cured films formed using the radiation-sensitive compositions of patent documents 1 and 2, when water absorption occurs from the end portions of the unexposed portions during the development treatment and the alkoxy groups of the unexposed portions are changed to silanol groups, the dielectric constant of the cured films may be increased due to the presence of hydroxyl groups in the polymer side chains. Accordingly, an object of the present disclosure is to provide a radiation-sensitive composition that can form a cured film having excellent development adhesion and a low dielectric constant when the composition contains a silicon-containing polymer as a polymer component.

In the above aspect, a cured film having excellent development adhesion and a low dielectric constant can be formed from the radiation-sensitive composition containing the silicon-containing polymer, the photoacid generator, and the silanol compound, wherein the silicon-containing polymer is at least one selected from the group consisting of a polymer containing a structural unit having a group represented by the formula (1) and a siloxane polymer.

[ concerning the polymer (a 1-1) ]

Structural unit (I-1)

In the formula (1), as R¹～R³Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy groups. In these, R¹～R³The alkoxy group preferably has 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group. In particular, in the case where the group represented by the formula (1) is bonded to an aromatic ring group, R¹～R³The alkoxy group represented is preferably a methoxy group. When the group represented by the formula (1) is bonded to a chain hydrocarbon group, R¹～R³Alkoxy group represented byEthoxy is preferred.

R¹～R³The alkyl group having 1 to 10 carbon atoms may be straight or branched. As R¹～R³Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. In these, R¹～R³The alkyl group represented is preferably a methyl group, an ethyl group or a propyl group.

R¹～R³One of the groups is an alkoxy group having 1 to 6 carbon atoms. The remaining group is preferably a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms or a phenyl group, more preferably a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and still more preferably an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms.

From the viewpoint of obtaining a cured film excellent in heat resistance by formation of a crosslinked structure, R¹～R³Two or more of these are preferably alkoxy groups having 1 to 6 carbon atoms, and particularly preferably all alkoxy groups having 1 to 6 carbon atoms.

In the structural unit (I-1), the group represented by the formula (1) is preferably bonded to an aromatic ring group or a chain hydrocarbon group. Here, the "aromatic ring group" in the present specification means a group obtained by removing n (n is an integer) hydrogen atoms from the ring portion of an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. These rings may have a substituent such as an alkyl group. When the group represented by the formula (1) is bonded to a chain hydrocarbon group, examples of the chain hydrocarbon group include an alkanediyl group and an alkenediyl group.

In the above, the group represented by the formula (1) is preferably bonded to a benzene ring, a naphthalene ring or an alkyl chain. Specifically, the structural unit (I-1) preferably has at least one selected from the group consisting of a group represented by the following formula (3-1), a group represented by the following formula (3-2), and a group represented by the following formula (3-3).

[ solution 3]

(formula (3-1), formula (3-2) and formula (3-3) wherein A¹And A²Respectively and independently represent a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. n1 is an integer of 0 to 4. n2 is an integer of 0 to 6. Wherein, when n1 is 2 or more, a plurality of A¹The same or different from each other. When n2 is 2 or more, a plurality of A²The same or different from each other. R⁶Is an alkanediyl group. R is¹、R²And R³The same as the formula (1). "+" indicates a bond)

In the formulae (3-1) and (3-2), the structural formula is represented by formula A¹And A²Examples of the alkoxy group having 1 to 6 carbon atoms and the alkyl group having 1 to 6 carbon atoms include R in the formula (1)¹～R³The same groups as those exemplified above are exemplified. radicals-SiR bound to aromatic rings¹R²R³"is located relative to the other components except A¹And A²The bonding position of other groups (i.e., the bonding position indicated by "+") may be any position. For example, "-SiR in the case of said formula (3-1)¹R²R³The position of "may be any of ortho, meta and para positions with respect to the bond represented by". X ". Preferably para. n1 is preferably 0 or 1, more preferably 0. n2 is preferably 0 to 2, more preferably 0.

In the formula (3-3), R⁶Preferably straight chain. From the viewpoint of improving the heat resistance of the obtained cured film, R⁶The carbon number is preferably 1 to 6, more preferably 1 to 4.

In the formulae (3-1) to (3-3), the structural unit (I-1) preferably has at least one selected from the group consisting of the group represented by the formula (3-1) and the group represented by the formula (3-2), in terms of improving the heat resistance, chemical resistance and hardness of the cured film. In addition, in the radical-SiR¹R²R³"directly bonding to an aromatic ring stabilizes silanol groups generated in association with the presence of water. This is advantageous in that the solubility of the exposed portion in an alkali developing solution can be improved and a good pattern can be formedAnd (5) selecting. Among these, the structural unit (I-1) is particularly preferably a structural unit having a group represented by the above formula (3-1).

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

[ solution 4]

(in the formulae (4-1) and (4-2), R^AIs a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group or a trifluoromethyl group. R⁷And R⁸Each independently is a divalent aromatic ring group or chain hydrocarbon group. R¹、R²And R³The same as the above formula (1)

In the formulas (4-1) and (4-2), R⁷、R⁸The divalent aromatic ring group represented is preferably a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthalenediyl group. The substituent includes at least one selected from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The divalent chain hydrocarbon group is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.

R is a group capable of improving the solubility of an exposed portion in an alkali developing solution, in order to obtain a cured film having higher heat resistance, chemical resistance and hardness⁷、R⁸Among them, a divalent aromatic cyclic group is preferable, and a substituted or unsubstituted phenylene group is particularly preferable.

Specific examples of the structural unit represented by the above formula (4-1) include structural units represented by the following formulae (4-1-1) and (4-1-2), respectively. Specific examples of the structural unit represented by the above formula (4-2) include structural units represented by the following formulae (4-2-1) and (4-2-2), respectively.

[ solution 5]

(formula (4-1-1), formula (4-1-2), formula (4-2-1) and formula (4-2-2) wherein R¹¹And R¹²Each independently is an alkyl group having 1 to 4 carbon atoms. R¹³Is alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms or hydroxyl group. n3 is an integer of 1 to 4. A. The¹、A²N1 and n2 are as defined for the above formulae (3-1) and (3-2). R^AThe same as the above-mentioned formula (4-1) and formula (4-2)

Specific examples of the monomer constituting the structural unit (I-1) include compounds having a group represented by the above formula (3-1), such as styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth) acryloyloxyphenyltrimethoxysilane, (meth) acryloyloxyphenyltriethoxysilane, (meth) acryloyloxyphenyldimethoxysilane, (meth) acryloyloxyphenylethyldiethoxysilane, and the like;

examples of the compound having a group represented by the formula (3-2) include trimethoxy (4-vinylnaphthyl) silane, triethoxy (4-vinylnaphthyl) silane, methyldimethoxy (4-vinylnaphthyl) silane, ethyldiethoxy (4-vinylnaphthyl) silane, (meth) acryloyloxynaphthyltrimethoxysilane, and the like;

examples of the compound having a group represented by the above formula (3-3) include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, and 4- (meth) acryloyloxybutyltrimethoxysilane. In the present specification, "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid" as inclusive.

The content ratio of the structural unit (I-1) in the polymer (a 1-1) is preferably 5% by mass or more, more preferably 7% by mass or more, and still more preferably 10% by mass or more, relative to the total structural units constituting the polymer (a 1-1). The content of the structural unit (I-1) is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less, relative to the total structural units constituting the polymer (a 1-1). Setting the content ratio of the structural unit (I-1) in the above range is preferable in terms of sufficiently improving the heat resistance and chemical resistance of the obtained cured film, achieving high sensitivity, and exhibiting better resolution of the coating film.

Other structural units

The polymer (a 1-1) may further contain a structural unit other than the structural unit (I-1) (hereinafter, also referred to as "other structural unit (1)"). Examples of the other structural unit (1) include a structural unit (II-1) having at least one member selected from the group consisting of an oxetanyl group and an oxetanyl group, a structural unit (III-1) having an acidic group, and the like. In the present specification, an oxetanyl group and an oxetanyl group are also included and referred to as an "epoxy group".

Structural unit (II-1)

When the polymer (a 1-1) contains the structural unit (II-1), the film is preferably improved in resolution and adhesion. Further, the epoxy group functions as a crosslinkable group, and thus a cured film having high chemical resistance and suppressed deterioration for a long period of time can be preferably formed. The structural unit (II-1) is preferably a structural unit derived from an unsaturated monomer having an epoxy group, and more specifically, is preferably at least one selected from the group consisting of a structural unit represented by the following formula (5-1) and a structural unit represented by the following formula (5-2).

[ solution 6]

(in the formulae (5-1) and (5-2), R²⁰Is a monovalent radical having an oxetanyl or oxetanyl group. R^AIs hydrogen atom, methyl, hydroxymethyl, cyano or trifluoromethyl. X¹Is a single bond or a divalent linking group)

In the above formulas (5-1) and (5-2), R is²⁰Examples thereof include an oxetanyl group, a3, 4-epoxycyclohexyl group, and a3, 4-epoxytricyclo [5.2.1.0^2,6]Decyl, 3-ethyloxetanyl, and the like.

As X¹The divalent linking group of (3) is preferably an alkanediyl group such as a methylene group, an ethylene group, or a1, 3-propanediyl group; a divalent group in which an arbitrary methylene group of the alkanediyl group is substituted with an oxygen atom, and the like.

Specific examples of the monomer having an epoxy group include: glycidyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 2- (3, 4-epoxycyclohexyl) ethyl (meth) acrylate, 3, 4-epoxytricyclo [5.2.1.0 ] meth) acrylate^2,6]Decyl ester; (3-methyloxetan-3-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) acrylate, (oxetan-3-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.

The content ratio of the structural unit (II-1) in the polymer (a 1-1) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more, relative to the total structural units constituting the polymer (a 1-1). The content of the structural unit (II-1) is preferably 65% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less, relative to the total structural units constituting the polymer (a 1-1). When the content ratio of the structural unit (II-1) is in the above range, the coating film preferably exhibits better resolution and the heat resistance and chemical resistance of the resulting cured film are sufficiently improved.

Structural Unit (III-1)

The polymer (a 1-1) preferably further contains a structural unit (III-1) having an acidic group. By introducing the structural unit (III-1), the solubility of the polymer (a 1-1) in an alkali developing solution (alkali solubility) or the hardening reactivity can be improved. In the present specification, the term "alkali-soluble" means that the compound is soluble in an aqueous alkali solution such as a 2.38 mass% aqueous tetramethylammonium hydroxide solution.

The structural unit (III-1) is not particularly limited as long as it has an acidic group. The structural unit (III-1) is preferably at least one member selected from the group consisting of a structural unit having a carboxyl group, a structural unit having a sulfonic acid group, a structural unit having a phenolic hydroxyl group, and a maleimide unit. In the present specification, the "phenolic hydroxyl group" refers to a hydroxyl group directly bonded to an aromatic ring (for example, a benzene ring, a naphthalene ring, an anthracene ring, or the like).

The structural unit (III-1) is preferably a structural unit derived from an unsaturated monomer having an acidic group. Specific examples of the unsaturated monomer having an acidic group include monomers constituting a structural unit having a carboxyl group, such as unsaturated monocarboxylic acids (e.g., (meth) acrylic acid, crotonic acid, and 4-vinylbenzoic acid); unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; examples of the monomer constituting the structural unit having a sulfonic acid group include vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, (meth) acryloyloxyethylsulfonic acid, and the like; examples of the monomer constituting the structural unit having a phenolic hydroxyl group include 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth) acrylate, and the like. Further, as the monomer constituting the structural unit (III-1), maleimide may also be used.

From the viewpoint of imparting good solubility in an alkaline developing solution, the content ratio of the structural unit (III-1) in the polymer (a 1-1) is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass or more, relative to the total structural units constituting the polymer (a 1-1). On the other hand, if the content ratio of the structural unit (III-1) is too high, the difference in solubility in an alkali developer between the exposed portion and the unexposed portion may be small, and it may be difficult to obtain a good pattern shape. From this viewpoint, the content ratio of the structural unit (III-1) to the total structural units constituting the polymer (a 1-1) is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.

The other structural unit (1) may be further exemplified by a structural unit derived from at least one monomer selected from the group consisting of an alkyl (meth) acrylate, a (meth) acrylate having an alicyclic structure, a (meth) acrylate having an aromatic ring structure, an aromatic vinyl compound, an N-substituted maleimide compound, a vinyl compound having a heterocyclic structure, a conjugated diene compound, a nitrogen-containing vinyl compound, and an unsaturated dicarboxylic acid dialkyl ester compound. By introducing these structural units into the polymer, the glass transition temperature of the polymer component can be adjusted, and the pattern shape and chemical resistance of the cured film obtained can be improved.

Specific examples of the monomer include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, and n-stearyl (meth) acrylate;

examples of the (meth) acrylate having an alicyclic structure include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ] meth (acrylate)^2,6]Decan-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,5]Decan-8-yloxyethyl ester, isobornyl (meth) acrylate, etc.;

examples of the (meth) acrylate having an aromatic ring structure include phenyl (meth) acrylate, benzyl (meth) acrylate, and the like;

examples of the aromatic vinyl compound 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-dimethylaminoethylstyrene, N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine and the like;

examples of the N-substituted maleimide compound include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N- (2-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-ethylphenyl) maleimide, N- (2, 6-dimethylphenyl) maleimide, N-benzylmaleimide, N-naphthylmaleimide and the like;

examples of the vinyl compound having a heterocyclic ring structure include tetrahydrofurfuryl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 5-ethyl-1, 3-dioxan-5-ylmethyl (meth) acrylate, 5-methyl-1, 3-dioxan-5-ylmethyl (meth) acrylate, (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, 2- (meth) acryloyloxymethyl-1, 4, 6-trioxaspiro [4,6] undecane, (meth) acrylate (. Gamma. -butyrolactone-2-yl) ester, (meth) acrylate glycerol carbonate, (meth) acrylate (. Gamma. -lactam-2-yl) ester, and N- (meth) acryloyloxyethyl hexahydrophthalimide;

examples of the conjugated diene compound include 1, 3-butadiene, isoprene, and the like;

examples of the nitrogen-containing vinyl compound include (meth) acrylonitrile, (meth) acrylamide and the like;

examples of the unsaturated dicarboxylic acid dialkyl ester compound include diethyl itaconate. Examples of the monomer constituting the other structural unit (1) include, in addition to the above, monomers such as vinyl chloride, vinylidene chloride, and vinyl acetate.

From the viewpoint of adjusting the glass transition temperature of the polymer component to suppress melt flow during thermal curing, the polymer (a 1-1) preferably contains, as the structural unit (1) other than the structural unit (II-1) and the structural unit (III-1), a structural unit derived from at least one monomer selected from the group consisting of an alkyl (meth) acrylate, a (meth) acrylate having an alicyclic structure, and a (meth) acrylate having an aromatic ring structure.

The content ratio of the structural unit (1) other than the structural unit (II-1) and the structural unit (III-1) is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total structural units constituting the polymer (a 1-1), from the viewpoint of appropriately increasing the glass transition temperature of the polymer (a 1-1). The content ratio of the structural unit is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total structural units constituting the polymer (a 1-1).

The polymer (a 1-1) can be produced by a known method such as radical polymerization in an appropriate solvent in the presence of a polymerization initiator or the like, using an unsaturated monomer capable of introducing each of the above-mentioned structural units. Examples of the polymerization initiator include azo compounds such as 2,2' -azobis (isobutyronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), and dimethyl 2,2' -azobis (isobutyrate). The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the total amount of the monomers used in the reaction. Examples of the polymerization solvent include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of the polymerization solvent used is preferably such that the total amount of the monomers used in the reaction is 0.1 to 60% by mass based on the total amount of the reaction solution.

In the polymerization, the reaction temperature is usually from 30 ℃ to 180 ℃. The reaction time varies depending on the kinds of the polymerization initiator and the monomer and the reaction temperature, and is usually 0.5 to 10 hours. The polymer obtained by the polymerization reaction can be used in the preparation of the radiation-sensitive composition in a state of being dissolved in the reaction solution, and can also be used in the preparation of the radiation-sensitive composition after being separated from the reaction solution. The polymer can be isolated by a known isolation method such as a method of injecting the reaction solution into a large amount of a poor solvent and drying the precipitate obtained thereby under reduced pressure, a method of distilling off the reaction solution under reduced pressure using an evaporator, or the like.

When the [ A ] polymer component comprises the polymer (a 1-1), the [ A ] polymer component may be composed of only the polymer (a 1-1) having the structural unit (I-1) as long as it comprises the structural unit (I-1), or may comprise the polymer (a 1-1) and further a polymer not having the structural unit (I-1). For example, when the [ A ] polymer component comprises the structural unit (I-1), the structural unit (II-1) and the structural unit (III-1), the same polymer may have all of the structural unit (I-1), the structural unit (II-1) and the structural unit (III-1), or a polymer different from the polymer having the structural unit (I-1) may have at least one selected from the group consisting of the structural unit (II-1) and the structural unit (III-1). When two or more different polymers in the [ A ] polymer component have the structural unit (I-1), the structural unit (II-1) and the structural unit (III-1), the content ratio of each structural unit contained in the [ A ] polymer component preferably satisfies the above range. The [ A ] polymer component is preferably a polymer containing a structural unit (I-1), a structural unit (II-1) and a structural unit (III-1) in order to reduce the number of components constituting the radiation-sensitive composition and to obtain the effect of improving development adhesion and chemical resistance. The respective polymers constituting the polymer component [ A ] are preferably alkali-soluble resins.

The weight average molecular weight (Mw) of the polymer (a 1-1) in terms of polystyrene obtained by Gel Permeation Chromatography (GPC) is preferably 2,000 or more. When Mw is 2,000 or more, it is preferable that the cured film has sufficiently high heat resistance and chemical resistance and exhibits good developability. The Mw of the polymer (a 1-1) is more preferably 5,000 or more, still more preferably 6,000 or more, particularly preferably 7,000 or more. In addition, mw is preferably 50,000 or less, more preferably 30,000 or less, further preferably 20,000 or less, and particularly preferably 15,000 or less, from the viewpoint of improving film formability.

The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 4.0 or less, more preferably 3.0 or less, and still more preferably 2.5 or less. When the [ a ] polymer component contains two or more polymers, the Mw and Mw/Mn of each polymer preferably satisfy the above ranges.

[ concerning the polymer (a 1-2) ]

The polymer (a 1-2) is a polymer comprising a structural unit (I-2) having an acid-dissociable group. The acid-dissociable group is a group that substitutes for a hydrogen atom of an acidic group such as a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, or a sulfonic acid group, and dissociates by the action of an acid. According to the present composition containing the polymer (a 1-2), an acid is generated by irradiating the present composition with radiation, and an acid group is generated by removing an acid-dissociable group with the generated acid. This makes it possible to change the solubility of the polymer component in the developer, and to obtain a cured film having a pattern formed thereon.

Among these, the structural unit (I-2) is preferably a structural unit (hereinafter, also referred to as "structural unit (I-2-1)") in which an acid-dissociable group is dissociated by the action of an acid to generate a carboxyl group, or a structural unit (hereinafter, also referred to as "structural unit (I-2-2)") in which an acid-dissociable group is dissociated by the action of an acid to generate a phenolic hydroxyl group.

Concerning the structural unit (I-2-1)

As the structural unit (I-2-1), a structural unit derived from a protected unsaturated carboxylic acid is exemplified. The unsaturated carboxylic acid to be used is not particularly limited, and examples thereof include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated anhydrides, and unsaturated polycarboxylic acids.

Specific examples of these include (meth) acrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, 2-carboxyethyl (meth) acrylate, and 4-vinylbenzoic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and citraconic acid. Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of the unsaturated polycarboxylic acid include ω -carboxy polycaprolactone mono (meth) acrylate and the like.

Examples of the acid-dissociable group contained in the structural unit (I-2-1) include an acetal functional group, a tertiary alkyl group, and a tertiary alkyl carbonate group. Among these, an acetal functional group is preferable in terms of easy dissociation by an acid.

When the acid-dissociable group is an acetal functional group, the structural unit (I-2-1) preferably has an acetal ester structure of a carboxylic acid as a protected carboxyl group, and more specifically, preferably has a group represented by the following formula (X-1).

[ solution 7]

(in the formula (X-1), R³¹、R³²And R³³The following (1) or (2). (1) R is³¹Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. R³²And R³³Each independently is an alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. (2) R is³¹Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. R is³²And R³³Represent a combination with each other and with R³²And OR³³The carbon atoms bonded to form a cyclic ether structure. "" indicates a bond)

R³¹、R³²And R³³The alkyl group having 1 to 12 carbon atoms may be straight or branched. The carbon number of the alkyl group is preferably 1 to 6, more preferably 1 to 4. As R³¹、R³²And R³³Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.

As R³¹、R³²And R³³Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, isobornyl, and adamantyl. As R³²And R³³Examples of the aralkyl group having 7 to 20 carbon atoms include a phenylmethyl group, a phenylethyl group, a methylphenylmethyl group and the like.

R³²And R³³The cyclic ether structure formed by bonding to each other preferably has a ring number of 5 or more. Specific examples thereof include a tetrahydrofuran ring structure and a tetrahydropyran ring structure.

In terms of being easily dissociated by an acid, wherein R³¹Preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.

Specific examples of the acetal ester structure of the carboxylic acid represented by the above formula (X-1) include 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-propoxyethoxycarbonyl group, 1-butoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydrofuryloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, 1-phenylmethoxyethoxycarbonyl group, and the like.

Among these, the structural unit (I-2-1) is preferably a structural unit represented by the following formula (Y-1) or a structural unit represented by the following formula (Y-2).

[ solution 8]

(in the formula (Y-1), R³⁰Is a hydrogen atom or a methyl group. X³⁰Is a single bond or an arylene group. R⁴⁰Is a hydrogen atom or an alkyl group. R⁴¹And R⁴²Independently represents an alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms)

[ solution 9]

(in the formula (Y-2), R³⁰Is a hydrogen atom or a methyl group. X³¹Is a single bond or an arylene group. R is⁴³～R⁴⁹Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. k is 1 or 2)

As a preferred specific example of the structural unit (I-2-1), a structural unit represented by the following formula can be mentioned. In addition, in the formula, R³⁰Is a hydrogen atom or a methyl group.

[ solution 10]

Concerning the structural unit (I-2-2)

The structural unit (I-2-2) is not particularly limited as long as it has a protected phenolic hydroxyl group. Among them, from the viewpoint of the sensitivity of the present composition, the structural unit (I-2-2) is preferably at least one selected from the group consisting of a structural unit derived from hydroxystyrene or a derivative thereof and a structural unit derived from a (meth) acrylic acid compound having a hydroxyphenyl structure.

The acid-dissociable group of the structural unit (I-2-2) is not particularly limited. The acid-dissociable group of the structural unit (I-2-2) is preferably an acetal functional group from the viewpoints of sensitivity, pattern shape, storage stability, and the like of the present composition. Examples of the acetal functional group that can be used in the structural unit (I-2-2) include the same acid-dissociable groups that can be used in the structural unit (I-2-1). Among them, preferred is a copolymer of N, N' -O-C (R)³¹)(R³²)(OR³³) "(wherein, R is³¹、R³²And R³³The same as that of the formula (X-1). In this case, the protected phenolic hydroxyl group contained in the structural unit (I-2-2) can be represented by the following formula (Z-1).

[ solution 11]

(in the formula (Z-1))，Ar¹Is an arylene group. R³¹、R³²And R³³The same as in the formula (X-1). "+" indicates a bond)

-C (R) contained as a constituent unit (I-2-2)³¹)(R³²)(OR³³) Preferable examples of the group "include 1-alkoxyalkyl group and 1-arylalkoxyalkyl group. Specific examples thereof include 1-ethoxyethyl, 1-methoxyethyl, 1-butoxyethyl, 1-isobutoxyethyl, 1- (2-ethylhexyloxy) ethyl, 1-propoxyethyl, 1-cyclohexyloxyethyl, 1- (2-cyclohexylethoxy) ethyl and 1-benzyloxyethyl.

As a preferred specific example of the structural unit (I-2-2), a structural unit represented by the following formula can be mentioned. In addition, in the formula, R³⁰Is a hydrogen atom or a methyl group.

[ solution 12]

The content ratio of the structural unit (I-2) in the polymer (a 1-2) to the total structural units constituting the polymer (a 1-2) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. The content ratio of the structural unit (I-2) is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less, relative to the total structural units constituting the polymer (a 1-2). When the content ratio of the structural unit (I-2) is in the above range, it is preferable that the first composition has high sensitivity and that the coating film has better resolution.

When the first composition contains the polymer (a 1-2), [ A ] the polymer component may further contain a structural unit other than the structural unit (I-2) (hereinafter, also referred to as "other structural unit (2)"). Examples of the other structural unit (2) include a structural unit (II-2) having a crosslinkable group, a structural unit (III-2) having an acidic group, and the like. The other structural unit (2) may be introduced into the polymer (a 1-2), may be introduced as a structural unit of a polymer different from the polymer (a 1-2), or may be introduced into both a polymer different from the polymer (a 1-2) and the polymer (a 1-2). The polymer (a 1-2) preferably contains the structural unit (I-2) and also contains the structural unit (II-2) and the structural unit (III-2) in terms of minimizing the amount of the components constituting the first composition while obtaining the effect of improving the development adhesion and the curing adhesion.

Structural unit (II-2)

The crosslinkable group of the structural unit (II-2) is not particularly limited as long as it is a group which causes a curing reaction by heat treatment. Among these, the crosslinkable group is preferably one or both of an oxetanyl group and an oxetanyl group in view of high thermosetting property. Specific examples and preferred examples of the structural unit (II-2) include the same examples as those described for the structural unit (II-1).

When the polymer (a 1-2) contains the structural unit (II-2), the content of the structural unit (II-2) is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more, based on the total structural units constituting the polymer (a 1-2). The content ratio of the structural unit (II-2) is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less, relative to the total structural units constituting the polymer (a 1-2).

Structural unit (III-2)

The polymer (a 1-2) preferably further contains a structural unit (III-2) having an acidic group, from the viewpoint that the solubility in an alkali developing solution can be improved or the hardening reactivity can be improved. Specific examples and preferred examples of the structural unit (III-2) include the same examples as those described for the structural unit (III-1).

When the polymer (a 1-2) contains the structural unit (III-2), the content ratio of the structural unit (III-2) to the total structural units constituting the polymer (a 1-2) is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more, from the viewpoint of imparting good solubility in an alkaline developer. The content ratio of the structural unit (III-2) is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less, relative to the total structural units constituting the polymer (a 1-2).

When the first composition contains the polymer (a 1-2), examples of the other structural unit (2) that can be contained in the [ a ] polymer component include structural units exemplified by the other structural unit (1). When the polymer (a 1-2) contains a structural unit other than the structural unit (II-2) and the structural unit (III-2) as the other structural unit (2), the content ratio of the structural unit is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the entire structural units constituting the polymer (a 1-2).

The polymer (a 1-2) can be produced by a known method such as radical polymerization in an appropriate solvent in the presence of a polymerization initiator or the like using, for example, an unsaturated monomer capable of introducing each structural unit. The details of the polymerization method are the same as those of the polymer (a 1-1).

The weight average molecular weight (Mw) of the polymer (a 1-2) in terms of polystyrene obtained by GPC is preferably 1,000 or more. The Mw of the polymer (a 1-2) is more preferably 2,000 or more, and still more preferably 5,000 or more. In addition, the Mw of the polymer (a 1-2) is preferably 200,000 or less, more preferably 50,000 or less, from the viewpoint of improving film formability. In addition, with respect to the polymer (a 1-2), the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 5.0 or less, more preferably 3.0 or less.

[ with regard to the siloxane polymers ]

The siloxane polymer is not particularly limited as long as it can form a cured film by hydrolytic condensation. The siloxane polymer is preferably a polymer obtained by hydrolyzing a hydrolyzable silane compound represented by the following formula (6).

(R²¹)_rSi(OR²²)_4-r…(6)

(in the formula (6), R²¹Is a non-hydrolyzable monovalent radical. R is²²Is an alkyl group having 1 to 4 carbon atoms. r is an integer of 0 to 3. Wherein r is 2 or 3In the case of (2), a plurality of R in the formula²¹The same or different from each other. When R is 0 to 2, a plurality of R in the formula²²Same or different from each other)

As R²¹Examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a group having a (meth) acryloyl group and a group having an epoxy group.

As R²²Examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Among these, R is highly hydrolyzable²²Preferably methyl or ethyl.

r is preferably 0 to 2, more preferably 0 or 1, and still more preferably 1.

Specific examples of the monomer constituting the siloxane polymer include silane compounds having four hydrolyzable groups, such as tetramethoxysilane, tetraethoxysilane, triethoxymethoxy silane, tetrabutoxy silane, tetraphenoxysilane, tetrabenzyloxy silane, tetra-n-propoxysilane, and the like;

examples of the silane compound 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, 3- (meth) acryloyloxypropyltriethoxysilane, and the like;

examples of the silane compound having two hydrolyzable groups include dimethyldimethoxysilane, diphenyldimethoxysilane, and the like;

examples of the silane compound having one hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane.

The siloxane polymer can be prepared by reacting the aboveOne or more hydrolyzable silane compounds are obtained by hydrolyzing and condensing water, preferably in the presence of a suitable catalyst and an organic solvent. A hydrolyzable group (-OR) possessed by a hydrolyzable silane compound during hydrolysis and condensation reaction²²) The total amount of (3) and the proportion of water to be used is preferably 0.1 to 3 moles, more preferably 0.2 to 2 moles, and still more preferably 0.5 to 1.5 moles. By using such an amount of water, the reaction rate of the hydrolytic condensation can be optimized.

Examples of the catalyst used in the hydrolysis and condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, and the like. The amount of the catalyst to be used varies depending on the kind of the catalyst, reaction conditions such as temperature, and the like, and is preferably 0.0001 to 0.2 mol, more preferably 0.0005 to 0.1 mol, based on 1 mol of the hydrolyzable silane compound.

Examples of the organic solvent used in the hydrolysis and condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Of these, it is preferable to use a water-insoluble or hardly water-soluble organic solvent, and examples thereof include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether acetate, propionate compounds, and the like. The amount of the organic solvent used is preferably 10 to 10,000 parts by mass, more preferably 50 to 1,000 parts by mass, based on 100 parts by mass of the total amount of the hydrolyzable silane compounds used in the reaction.

In the hydrolysis and condensation reaction, the reaction temperature is preferably 130 ℃ or lower, more preferably 40 to 100 ℃. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. In the reaction, the mixture may be stirred or may be refluxed. After the hydrolytic condensation reaction, a dehydrating agent may be added to the reaction solution, followed by evaporation (evaporation) to remove water and the formed alcohol from the reaction system.

The silicone polymer preferably has a weight average molecular weight (Mw) of 500 or more in terms of polystyrene obtained by GPC. When Mw is 500 or more, a cured film having sufficiently high heat resistance and solvent resistance and exhibiting good developability is preferably obtained. More preferably, mw is 1000 or more. Further, mw is preferably 10000 or less, more preferably 5000 or less, from the viewpoint of improving film formability and from the viewpoint of suppressing a decrease in radiation sensitivity. The molecular weight distribution (Mw/Mn) is preferably 4.0 or less, more preferably 3.0 or less, and still more preferably 2.5 or less.

The content ratio of the (a-1) polymer is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, relative to the total amount of solid components contained in the radiation-sensitive composition (i.e., the total mass of components other than the solvent in the radiation-sensitive composition). The content of the polymer (a-1) is preferably 99% by mass or less, and more preferably 95% by mass or less, based on the total amount of solid components contained in the radiation-sensitive composition. By setting the content ratio of the polymer (A-1) in the above range, a cured film having sufficiently high heat resistance and chemical resistance and exhibiting good developability and transparency can be obtained.

[ B ] silanol Compound

[B] The silanol compound is a compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to the same silicon atom. Wherein [ B ] the silanol compound has no alkoxy group. When the [ B ] silanol compound is contained in the radiation-sensitive composition together with the (A-1) polymer, a cured film having a low dielectric constant and excellent development adhesion can be obtained. The [ B ] silanol compound is preferably stable to an alkali developing solution, is hydrophobic, and has little influence on an unexposed portion (for example, influence on sensitivity).

Examples of the hydrophobic group of the [ B ] silanol compound include a hydrocarbon group and a fluorinated hydrocarbon group. Among these, the hydrophobic group of [ B ] silanol compound is preferably a hydrocarbon group, and examples thereof include a monovalent chain hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. Among these, the hydrophobic group of the [ B ] silanol compound is preferably a monovalent chain hydrocarbon group or a monovalent aromatic hydrocarbon group, and more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The alkyl group having 1 to 10 carbon atoms may be straight or branched. Specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, and a tert-pentyl group. Among these, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, a linear or branched alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is further preferable.

Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a trimethylphenyl group, and a naphthyl group. Of these, phenyl, methylphenyl, or ethylphenyl are preferred, and phenyl or methylphenyl are more preferred.

Specifically, the [ B ] silanol compound is preferably a compound represented by the following formula (2).

(R⁴)_mSi(OH)_4-m…(2)

(in the formula (2), R⁴Is a monovalent hydrocarbon group. m is an integer of 1 to 3)

In the formula (2), R⁴The monovalent hydrocarbon group is preferably a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. Of these, monovalent chain hydrocarbon groups or aromatic hydrocarbon groups are more preferable, and alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 12 carbon atoms are still more preferable.

In order to further improve the effect of reducing the dielectric constant and the development adhesiveness of the cured film, m in the formula (2) is preferably 1 or 2.

Specific examples of [ B ] silanol compounds include: trimethylsilanol, ethyldimethylsilanol, diethylmethylsilanol, triethylsilanol, methylsilanetriol, diphenylsilandiol, phenylsilanetriol, triphenylsilanol, bis (4-tolyl) silandiol, tris (4-tolyl) silandiol, and the like.

In forming the film, a treatment of removing a solvent component contained in the radiation-sensitive composition by heating (prebaking) the coating film containing the radiation-sensitive composition is generally performed. From the viewpoint of suppressing the volatilization of the [ B ] silanol compound at the pre-baking and leaving a large amount of the [ B ] silanol compound in the film after the pre-baking, a compound having a sufficiently high boiling point can be preferably used as the [ B ] silanol compound. Specifically, the boiling point of the [ B ] silanol compound is preferably 80 ℃ or higher, more preferably 95 ℃ or higher, still more preferably 120 ℃ or higher, still more preferably 150 ℃ or higher, and particularly preferably 180 ℃ or higher. Further, in the present specification, the boiling point of a compound is a value at one atmospheric pressure.

[B] The silanol compound is preferably a compound having a boiling point higher than the prebaking temperature. By using a silanol compound having a boiling point higher than the prebaking temperature, the amount of [ B ] silanol compound remaining in the film after prebaking can be increased, and the effect of improving the development adhesion and lowering the dielectric constant of the cured film can be further improved. Specifically, the boiling point of the [ B ] silanol compound is preferably 5 ℃ or higher, more preferably 10 ℃ or higher, still more preferably 20 ℃ or higher, yet more preferably 30 ℃ or higher, and particularly preferably 50 ℃ or higher than the prebaking temperature.

Among these, the [ B ] silanol compound is particularly preferably a compound having an aromatic ring in terms of having a high boiling point and high hydrophobicity, and being capable of improving the development adhesiveness of the cured film and the effect of reducing the dielectric constant. Specific examples of the [ B ] silanol compound include diphenylsilanediol, phenylsilane triol, triphenylsilanol, bis (4-tolyl) silanediol, and tris (4-tolyl) silanediol. Among these, a compound having two or more aromatic rings is preferable, and a compound having three or more aromatic rings is more preferable, in terms of further improving the development adhesiveness and the low dielectric constant of the cured film.

[B] The molecular weight of the silanol compound is preferably 90 or more, more preferably 100 or more, and further preferably 150 or more. The molecular weight of the [ B ] silanol compound is preferably 500 or less, more preferably 450 or less, and still more preferably 400 or less. When the [ B ] silanol compound is in the above range, it is preferable that the reduction in sensitivity and development solubility of the radiation-sensitive composition is suppressed, the development adhesion of the cured film is improved, and the dielectric constant is reduced.

In the first composition, the content of the [ B ] silanol compound is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, and particularly preferably 3 parts by mass or more, relative to 100 parts by mass of the (A-1) polymer. The content of the [ B ] silanol compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less, based on 100 parts by mass of the (A-1) polymer. When the content of the [ B ] silanol compound is 0.5 parts by mass or more, it is preferable that the effect of improving the development adhesion and the reduction in dielectric constant of the coating film, which is caused by the presence of the [ B ] silanol compound in the film, can be sufficiently obtained. When the content of the [ B ] silanol compound is 25 parts by mass or less, it is preferable that the decrease in sensitivity due to the [ B ] silanol compound is suppressed.

[ C ] photoacid generators

The photoacid generator is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation. Examples of the photoacid generator include: oxime sulfonate (oxime sulfonate compound) compound, onium salt, sulfonimide (sulfonimide) compound, halogen-containing compound, diazomethane compound, sulfone compound, sulfonate compound, carboxylate compound, quinone diazide compound.

Specific examples of the oxime sulfonate compound, the onium salt, the sulfonimide compound, the halogen-containing compound, the diazomethane compound, the sulfone compound, the sulfonate compound and the carboxylate compound include compounds described in paragraphs 0078 to 0106 of Japanese patent laid-open publication No. 2014-157252 and compounds described in International publication No. 2016/124493. As the photoacid generator, at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds is preferably used from the viewpoint of radiation sensitivity.

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

[ solution 13]

(in the formula (7), R²³Is a monovalent hydrocarbon group, or a monovalent group in which a part or all of hydrogen atoms contained in the hydrocarbon group are substituted with a substituent. "+" indicates a bond)

In the formula (7), as R²³Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a pendant oxy group, and a halogen atom.

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, a compound described in International publication No. 2016/124493, and the like. Examples of commercially available oxime sulfonate compounds include Irgacure (PAG 121) manufactured by BASF corporation.

Examples of the sulfonimide compound include: n- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, (4-methylphenylsulfonyloxy) diphenylmaleimide, trifluoromethanesulfonic acid-1, 8-naphthalimide.

As the photoacid generator, one or more of an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonate compound, and a carboxylate compound may be used in combination with a quinone diazide compound. In addition, a quinone diazide compound may be used alone.

The quinone diazide compound is a radiation-sensitive acid generator that generates a carboxylic acid by irradiation with radiation. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter, also referred to as a "core") and an o-naphthoquinonediazide compound. Among these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as a parent nucleus and an o-naphthoquinone diazide compound. Specific examples of the core include compounds described in paragraphs 0065 to 0070 of Japanese patent laid-open publication No. 2014-186300. The o-naphthoquinone diazide compound is preferably 1, 2-naphthoquinone diazide sulfonyl halide.

The quinone diazide compound is preferably a condensate of a phenolic compound or an alcoholic compound as a mother nucleus and 1, 2-naphthoquinone diazide sulfonyl halide, and more preferably a condensate of a phenolic compound and 1, 2-naphthoquinone diazide sulfonyl halide.

Specific examples of the quinone diazide compound include compounds containing a phenolic hydroxyl group selected from 4,4' -dihydroxydiphenylmethane, 2,3,4,2',4' -pentahydroxybenzophenone, 2,3, 4' -tetrahydroxybenzophenone, tris (p-hydroxyphenyl) methane, 1-tris (p-hydroxyphenyl) ethane, 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-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylidene ] bisphenol, esterified with 1, 2-naphthoquinone diazide or 1, 2-naphthoquinone diazide sulfonyl chloride.

In the condensation reaction for obtaining the condensate, the ratio of the parent nucleus to the 1, 2-naphthoquinone diazide sulfonyl halide is such that the amount of the 1, 2-naphthoquinone diazide sulfonyl halide used corresponds to an amount of preferably 30 to 85 mol%, more preferably 50 to 70 mol%, with respect to the number of OH groups in the parent nucleus. Further, the condensation reaction may be carried out according to a known method.

In the first composition, the content ratio of the [ C ] photoacid generator 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 (A-1) polymer. The content of the [ C ] photoacid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, per 100 parts by mass of the (A-1) polymer. When the content of the [ C ] photoacid generator is 0.05 parts by mass or more, an acid is sufficiently generated by irradiation with radiation, and the difference in solubility in an alkaline solution between the irradiated portion and the non-irradiated portion of radiation can be sufficiently increased. This enables favorable pattern formation. Further, the amount of the acid to be reacted with the [ A ] polymer component can be increased, and the heat resistance and the solvent resistance can be sufficiently ensured. On the other hand, it is preferable to set the content of the [ C ] photoacid generator to 20 parts by mass or less, because the amount of unreacted photoacid generator after exposure can be sufficiently reduced, and the deterioration of developability due to the residue of the [ C ] photoacid generator can be suppressed.

Here, it is considered that when water absorption occurs at the end portions of the unexposed portions during development, the alkoxy groups present at the end portions of the unexposed portions are changed to silanol groups, and thereby the hydrophilicity of the end portions of the unexposed portions is increased, and the development adhesion of the coating film is lowered. In order to suppress such a decrease in development adhesion, it is conceivable to increase the hydrophobicity of the film by blending a hydrophobic additive in the radiation-sensitive composition or by introducing a structural unit derived from a hydrophobic monomer into the polymer component. However, increasing the hydrophobicity of the membrane tends to decrease the sensitivity of the radiation-sensitive composition. In contrast, in the present disclosure, by blending [ B ] a silanol compound in a radiation-sensitive composition using the polymer (a-1), the development adhesion of a cured film formed from the radiation-sensitive composition can be improved while maintaining high sensitivity of the radiation-sensitive composition.

Further, it is considered that when water absorption occurs at the end of the unexposed portion during development and the alkoxy group in the unexposed portion is changed to a silanol group, the dielectric constant of the cured film is increased because a hydroxyl group is present in the side chain of the polymer. In contrast, in the present disclosure, the dielectric constant of the cured film can be reduced by blending [ B ] silanol compound in the radiation-sensitive composition using the (a-1) polymer.

Further, it is inferred that the effect of the present disclosure is based on the following cases: the substrate surface is hydrophobized by the hydrophobic group of the [ B ] silanol compound, or the silanol group present at the end of the unexposed portion is covered with the [ B ] silanol compound. Wherein such inference does not set forth any limitations on the disclosure.

< other ingredients >

The first composition may contain other components (hereinafter, also referred to as "other components") in addition to the polymer component [ A ], the silanol compound [ B ] and the photoacid generator [ C ].

(solvent)

The first composition is a liquid composition preferably containing the polymer component [ A ], the silanol compound [ B ], the photoacid generator [ C ] and, if necessary, a component dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent which dissolves each component formulated in the first composition and does not react with each component.

Specific examples of the solvent 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, ethyl 3-ethoxypropionate, etc.; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and the like; amides such as dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Among these, the solvent preferably contains at least one selected from the group consisting of ethers and esters, and 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.

(Tight-lock auxiliary)

The adhesion promoter is a component for improving the adhesion between a cured film formed using the radiation-sensitive composition and a substrate. As the adhesion promoter, a functional silane coupling agent having a reactive functional group can be preferably used. Examples of the reactive functional group of the functional silane coupling agent include a carboxyl group, (meth) acryloyl group, epoxy group, vinyl group, and isocyanate group.

Specific examples of the functional coupling agent include: trimethoxysilylbenzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.

When the adhesion promoter is blended in the first composition, the content thereof 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, with respect to 100 parts by mass of the (a-1) polymer.

(acid diffusion controller)

The acid diffusion controller is a component that controls the diffusion length of the acid generated from the [ C ] photoacid generator by exposure. By blending an acid diffusion controlling agent in the first composition, the diffusion length of the acid can be appropriately controlled, and the pattern developability can be improved. In addition, by blending an acid diffusion controlling agent, the development adhesion can be improved and the chemical resistance can be improved.

The acid diffusion controller can be selected and used as desired from basic compounds used as an acid diffusion controller in a chemically amplified resist. Examples of such basic compounds include aliphatic amines, aromatic amines, heterocyclic aromatic amines, quaternary ammonium hydroxides, quaternary ammonium carboxylates, and the like. Specific examples of the basic compound used as an acid diffusion controller in a chemically amplified resist include compounds described in paragraphs 0128 to 0147 of Japanese patent laid-open publication No. 2011-232632. As the acid diffusion controller formulated in the first composition, at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines can be preferably used.

As the aromatic amine and the heterocyclic aromatic amine, at least one selected from the group consisting of aniline derivatives, imidazole derivatives, and pyrrole derivatives can be preferably used. Specific examples of the aromatic amine and heterocyclic aromatic amine include: aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, 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, and N, N-dimethyltoluidine; imidazole derivatives such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, triphenylimidazole, and N- (tert-butoxycarbonyl) -2-phenylbenzimidazole; pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2, 4-dimethylpyrrole, 2, 5-dimethylpyrrole and N-methylpyrrole; pyridine derivatives such as pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, lutidine, collidine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 3-methyl-4-phenylpyridine, 4-t-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinylpyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, and nicotine, and compounds disclosed in Japanese patent application laid-open No. 2011-232632.

In the case where the acid diffusion controlling agent is blended in the first composition, the content ratio thereof is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, per 100 parts by mass of the (a-1) polymer, from the viewpoint of sufficiently obtaining the effect of improving the chemical resistance by blending the acid diffusion controlling agent. The content of the acid diffusion-controlling agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of the (a-1) polymer.

(basic Compound)

The first composition may also contain a basic compound (wherein the acid diffusion controlling agent is excluded. Hereinafter, also referred to as "[ E ] basic compound"). The development adhesion of the cured film can be further improved by using the [ B ] silanol compound and the [ E ] basic compound in combination. In addition, according to the first composition further containing the [ E ] basic compound, a cured film having a lower dielectric constant can be obtained.

[E] The basic compound may be an inorganic base (sodium carbonate, etc.), an organic base, or both of them. The [ E ] basic compound is preferably an organic base in terms of high effect of improving development adhesion.

[E] The basic compound is preferably an organic base having an acid dissociation constant (pKa) of 8 or more. Examples of such organic bases include primary chain amines, secondary chain amines, tertiary chain amines, alicyclic amines, aromatic amines, amidines (amidines), guanidines (guanidines), and organophosphonitriles (organic phosphonites). Of these organic bases, [ E ] the basic compound is preferably at least one selected from the group consisting of amidines, guanidines, and organophosphorous nitriles, in terms of suppressing the decrease in sensitivity and sufficiently obtaining the effect of improving the development adhesion.

Specific examples of the amidines include cyclic amidines such as diazabicyclononene (1, 5-diazabicyclo [4.3.0] non-5-ene, DBN (1, 5-diazabicyclo [4.3.0] non-5-ene)), diazabicycloundecene (1, 8-diazabicyclo [5.4.0] undec-7-ene, DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene)), 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undec-7-ene (dibutylamino (DBA) -DBU).

Examples of the guanidine include chain or cyclic guanidines such as guanidine, tetramethylguanidine (TMG), butylguanidine, diphenylguanidine (DPG), 7-methyl-1,5, 7-triazabicyclodec-5-ene (7-methyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene), MTBD (7-methyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene), 1,5, 7-triazabicyclo-dec-5-ene (1, 5,7-triazabicyclo [4.4.0] dec-5-ene), TBD (1, 5,7-triazabicyclo [4.4.0] dec-5-ene) and the like.

Examples of the organophosphorous nitrile include 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3, 2-diazaphosphole (2-tert-butylimine-2-diazhylimine-1, 3-dimethyl-perhydro-1,3, 2-diazaphosphone, BEMP).

Among the above, the [ E ] basic compound is preferably an organic base having an acid dissociation constant (pKa) of 9 or more. Particularly preferred is at least one compound selected from the group consisting of amidines, guanidines and organophosphorus nitriles and having an acid dissociation constant (pKa) of 9 to 14, and more preferred is at least one compound selected from the group consisting of cyclic amidines, chain guanidines and cyclic organophosphorus nitriles and having an acid dissociation constant (pKa) of 10 to 14.

In the present specification, the acid dissociation constant means an acid dissociation constant (pKa) in water at 25 ℃. The acid dissociation constant (pKa) is defined by pKa = -log₁₀And Ka represents. When two or more stages of dissociation are considered, the initial dissociation is considered. As the inorganic base, there is a hydrogen ion H⁺Dissociate from the electrically neutral molecule (HA) and become a monovalent anion (A)^-) Acid dissociation constant (pKa) of the stage(s). With respect to the organic base, the molecule (B) which is electrically neutral accepts a hydrogen ion H⁺And become a monovalent cation (BH)⁺) Acid dissociation constant (pKa) of the stage(s). More specifically, [ E ]]The acid dissociation constant (pKa) of the basic compound is [ E ]]Conjugate acids (BH) of basic compounds⁺) When dissociated as an acid (BH)⁺→B+H⁺) Acid dissociation constant (pKa).

When the [ E ] basic compound is contained in the radiation-sensitive composition, the content ratio of the [ E ] basic compound is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more, relative to 100 parts by mass of the (a-1) polymer, from the viewpoint of sufficiently obtaining the effect of improving the development adhesion. The content of the [ E ] basic compound is preferably 5 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the (A-1) polymer.

As other components, in addition to the above, for example, there can be mentioned: a polyfunctional polymerizable compound (polyfunctional (meth) acrylate, etc.), a surfactant (fluorine-based surfactant, silicone-based surfactant, nonionic surfactant, etc.), a polymerization inhibitor, an antioxidant, a chain transfer agent, a orthoester, etc. The blending ratio of these components may be appropriately selected depending on each component within a range not impairing the effects of the present disclosure.

The solid content concentration of the first composition (the ratio of the total mass of the components excluding the solvent in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) may be appropriately selected in consideration of viscosity, volatility, and the like. The solid content concentration of the first composition is preferably in the range of 5 to 60% by mass. When the solid content concentration is 5% by mass or more, the film thickness of the coating film can be sufficiently ensured when the radiation-sensitive composition is applied to a substrate. When the solid content concentration is 60 mass% or less, the film thickness of the coating film is not excessively large, and the viscosity of the radiation-sensitive composition can be appropriately increased, so that good coatability can be ensured. The solid content concentration of the first composition is more preferably 10 to 55 mass%, and still more preferably 12 to 50 mass%.

[ second composition ]

Next, the second composition will be described. The second composition is a resin composition containing [ A ] a polymer component, [ B ] a silanol compound, [ Dq ] a quinonediazide compound, [ E ] a basic compound, and a solvent. The second composition is preferably a positive-type resin composition.

[ A ] Polymer component ]

The second composition contains, as the [ a ] polymer component, a polymer (hereinafter, also referred to as "(a-2) polymer") that is at least one selected from the group consisting of a polymer containing a structural unit having an acidic group (hereinafter, also referred to as "polymer (a 2)") and a siloxane polymer.

[ with respect to the polymer (a 2) ]

The polymer (a 2) is a polymer containing a structural unit having an acidic group (hereinafter, also referred to as "structural unit (III-3)"). Specific examples and preferred examples of the structural unit (III-3) are the same as those shown in the description of the structural unit (III-1) that the polymer (a 1-1) may contain.

In the polymer (a 2), the content ratio of the structural unit (III-3) to the entire structural units constituting the polymer (a 2) is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass or more, from the viewpoint of providing good solubility in an alkaline developing solution. The content ratio of the structural unit (III-3) is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less, relative to the total structural units constituting the polymer (a 2).

When the polymer (a 2) is contained, the [ A ] polymer component may further contain a structural unit other than the structural unit (III-3) (hereinafter, also referred to as "other structural unit (3)"). As a preferred specific example of the other structural unit (3), a structural unit (II-3) having a crosslinkable group can be mentioned. The other structural unit (3) may be introduced into the polymer (a 2), may be introduced as a structural unit of a polymer different from the polymer (a 2), or may be introduced into both of these polymers. The polymer (a 2) preferably further contains the structural unit (II-3) in terms of minimizing the amount of the component constituting the second composition and obtaining the effect of improving the development adhesion.

Structural unit (II-3)

The crosslinkable group of the structural unit (II-3) is not particularly limited as long as it is a group which causes a curing reaction by heat treatment. Among them, at least one selected from the group consisting of an oxetanyl group and an oxetanyl group is preferable in terms of high thermosetting property. Specific examples and preferred examples of the structural unit (II-3) are the same as those shown in the description of the structural unit (II-1).

When the polymer (a 2) contains the structural unit (II-3), the content ratio of the structural unit (II-3) to the entire structural units constituting the polymer (a 2) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. The content ratio of the structural unit (II-3) is preferably 65% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less, relative to the total structural units constituting the polymer (a 2). When the content ratio of the structural unit (II-3) is in the above range, the coating film preferably exhibits better resolution and the heat resistance and chemical resistance of the resulting cured film are sufficiently improved.

When the second composition contains the polymer (a 2), examples of the other structural unit (3) that can be contained in the [ a ] polymer component include structural units exemplified by the other structural unit (1). When the polymer (a 2) contains a structural unit other than the structural unit (II-3) as another structural unit (3), the content ratio of the structural unit is preferably 80% by mass or less, more preferably 70% by mass or less, relative to the entire structural units constituting the polymer (a 2).

The polymer (a 2) can be produced by a known method such as radical polymerization in an appropriate solvent in the presence of a polymerization initiator or the like using an unsaturated monomer capable of introducing each structural unit. The details of the polymerization method are the same as those of the polymer (a 1-1).

The weight average molecular weight (Mw) of the polymer (a 2) in terms of polystyrene obtained by GPC is preferably 1,000 or more. The Mw of the polymer (a 2) is more preferably 2,000 or more, and still more preferably 5,000 or more. From the viewpoint of improving the film-forming property, the Mw of the polymer (a 2) is preferably 200,000 or less, and more preferably 50,000 or less.

As for the polymer (a 2), the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 5.0 or less, more preferably 3.0 or less.

[ with regard to the siloxane polymers ]

The silicone polymer contained in the second composition is the same as the specific examples and preferred examples of the silicone polymer contained in the first composition.

< quinone diazide Compound >

The second composition contains [ Dq ] quinonediazide compound as a radiation-sensitive compound which generates carboxylic acid upon irradiation with radiation. The [ Dq ] quinonediazide compound includes the same compounds as the specific examples and preferred examples of the quinonediazide compound exemplified as the [ C ] photoacid generator in the description of the first composition.

In the second composition, the content ratio of the quinonediazide compound is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more, relative to 100 parts by mass of the (a-2) polymer contained in the second composition. The content ratio of the quinonediazide compound is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 40 parts by mass or less, based on 100 parts by mass of the (a-2) polymer contained in the second composition.

When the content ratio of the quinonediazide compound is 2 parts by mass or more, an acid can be sufficiently formed by irradiation with actinic rays, and the difference in solubility in an alkaline solution between the irradiated portion and the non-irradiated portion of actinic rays can be sufficiently increased. Thus, good patterning can be performed. Further, the amount of acid participating in the reaction with the (A-2) polymer can be increased, and the heat resistance and chemical resistance can be sufficiently ensured. On the other hand, when the content ratio of the quinonediazide compound is 60 parts by mass or less, it is preferable that the amount of the unreacted quinonediazide compound is sufficiently reduced and the deterioration of the developability and transparency due to the residual quinonediazide compound is suppressed.

< silanol Compound >

The second composition comprises said [ B ] silanol compound. Specific examples and preferable examples of the [ B ] silanol compound contained in the second composition are the same as those of the first composition.

In the second composition, the content ratio of the [ B ] silanol compound is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and still more preferably 1 part by mass or more, relative to 100 parts by mass of the (a-2) polymer contained in the second composition. The content of the [ B ] silanol compound is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, per 100 parts by mass of the (a-2) polymer contained in the second composition.

< basic Compound >

The second composition comprises [ E ] a basic compound. Specific examples and preferred examples of the [ E ] basic compound contained in the second composition are the same as those of the first composition.

In the second composition, the content ratio of the [ E ] basic compound is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more, relative to 100 parts by mass of the (a-2) polymer contained in the second composition, from the viewpoint of sufficiently obtaining the effect of improving the developing adhesion. The content of the [ E ] basic compound is preferably 5 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the (A-2) polymer.

< solvent >

The second composition contains a solvent. The second composition is preferably a liquid composition in which the [ A ] polymer component, [ Dq ] quinonediazide compound, [ B ] silanol compound, [ E ] basic compound, and components formulated as necessary are dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent which dissolves each component formulated in the second composition and does not react with each component. Specific examples of the solvent contained in the second composition are the same as those contained in the first composition.

In the second composition, the content of the solvent (the total amount thereof when two or more solvents are included) is preferably 50 to 95 parts by mass, and more preferably 60 to 90 parts by mass, relative to 100 parts by mass of the total components of the second composition.

< other ingredients >

The second composition may contain components (other components) other than the above-mentioned [ A ] polymer component, [ Dq ] quinonediazide compound, [ B ] silanol compound, [ E ] basic compound, and solvent. Specific examples and preferred examples of the other components that can be contained in the second composition are the same as those of the first composition.

The concentration of the solid component of the second composition may be appropriately selected in consideration of viscosity, volatility, or the like. The solid content concentration of the second composition is preferably in the range of 5 to 60 mass%, more preferably 10 to 55 mass%, and still more preferably 12 to 50 mass%.

[ third composition ]

Next, the third composition will be described. The third composition is a resin composition containing [ A ] a polymer component, [ B ] a silanol compound, [ Di ] a photopolymerization initiator, [ M ] a polymerizable monomer, [ E ] a basic compound, and a solvent. The third composition is preferably a negative resin composition.

[ A ] Polymer component ]

The third composition contains, as the [ a ] polymer component, a polymer containing a structural unit having an acidic group (hereinafter, also referred to as "polymer (a 3)").

[ concerning the polymer (a 3) ]

The polymer (a 3) is a polymer containing a structural unit having an acidic group (hereinafter, also referred to as "structural unit (III-4)"). Specific examples and preferred examples of the structural unit (III-4) are the same as those shown in the description of the structural unit (III-1) that the polymer (a 1-1) may contain. In the polymer (a 3), the content ratio of the structural unit (III-4) to the entire structural units constituting the polymer (a 3) is preferably 1 mass% or more, and more preferably 2 mass% or more, from the viewpoint of imparting good solubility in an alkaline developing solution to the unexposed portion. The content of the structural unit (III-4) is preferably 35% by mass or less, more preferably 30% by mass or less, based on the total structural units constituting the polymer (a 3).

[A] The polymer component may further contain a structural unit other than the structural unit (III-4) (hereinafter, also referred to as "other structural unit (4)"). As a preferred specific example of the other structural unit (4), a structural unit (II-4) having a crosslinkable group can be mentioned. The other structural unit (4) may be introduced into the polymer (a 3), may be introduced as a structural unit of a polymer different from the polymer (a 3), or may be introduced into both of these polymers. The polymer (a 3) preferably further contains the structural unit (II-4) in terms of minimizing the amount of the component constituting the third composition and obtaining the effect of improving the development adhesion.

Structural unit (II-4)

The crosslinkable group of the structural unit (II-4) is not particularly limited as long as it is a group which causes a curing reaction by heat treatment. Among them, at least one selected from the group consisting of an oxetanyl group and an oxetanyl group is preferable in terms of high thermosetting property. Specific examples and preferred examples of the structural unit (II-4) are the same as those shown in the description of the structural unit (II-1).

When the polymer (a 3) contains the structural unit (II-4), the content ratio of the structural unit (II-4) to the entire structural units constituting the polymer (a 3) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. The content ratio of the structural unit (II-4) is preferably 65% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less, relative to the total structural units constituting the polymer (a 3).

Examples of the other structural unit (4) that the polymer component [ A ] may contain include the same ones as those exemplified as the other structural unit (1).

The polymer (a 3) can be produced by a known method such as radical polymerization in an appropriate solvent in the presence of a polymerization initiator or the like using, for example, an unsaturated monomer capable of introducing each structural unit. The details of the polymerization method are the same as those of the polymer (a 1-1).

The weight average molecular weight (Mw) of the polymer (a 3) in terms of polystyrene obtained by GPC is preferably 1,000 or more. The Mw of the polymer (a 3) is more preferably 2,000 or more, and still more preferably 5,000 or more. In addition, the Mw of the polymer (a 3) is preferably 200,000 or less, more preferably 50,000 or less, from the viewpoint of improving film formability.

The polymer (a 3) preferably has a molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 5.0 or less, more preferably 3.0 or less.

< polymerizable monomer >

The third composition contains [ M ] a polymerizable monomer. The [ M ] polymerizable monomer contained in the third composition is a compound having one or more, preferably two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxetanyl group, and an N-alkoxymethylamino group. Among these, an ethylenically unsaturated group and an N-alkoxymethylamino group are preferable, and a vinyl group-containing group such as a (meth) acryloyl group, a vinyl group, and a vinylphenyl group is preferable, from the viewpoint of high polymerizability.

Specifically, the [ M ] polymerizable monomer is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups, and particularly preferably a compound having two or more (meth) acryloyl groups. [ M ] the number of polymerizable groups in one molecule of the polymerizable monomer is preferably 2 to 10, and more preferably 2 to 8.

Specific examples of the [ M ] polymerizable monomer include polyfunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydric compound with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, alkylene oxide-modified polyfunctional (meth) acrylates, polyfunctional (meth) acrylate urethanes obtained by reacting a hydroxyl group-containing (meth) acrylate with polyfunctional isocyanates, and polyfunctional (meth) acrylates having a carboxyl group obtained by reacting a hydroxyl group-containing (meth) acrylate with an acid anhydride.

Examples of the compound having two or more N-alkoxymethylamino groups include: compounds having a melamine structure, benzoguanamine structure, urea structure, and the like. The melamine structure and benzoguanamine structure are chemical structures having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are concepts including melamine, benzoguanamine, and condensates thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N ", N '-hexa (alkoxymethyl) melamine, N, N, N', N '-tetrakis (alkoxymethyl) benzoguanamine, N' -tetrakis (alkoxymethyl) glycoluril, and the like.

Among them, preferable as the [ M ] polymerizable monomer are polyfunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydric compound with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional (meth) acrylate urethanes, polyfunctional (meth) acrylates having a carboxyl group, N ', N ", N ″ -hexa (alkoxymethyl) melamine, N ', the N ' -tetra (alkoxymethyl) benzoguanamine is more preferably a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyol with (meth) acrylic acid, a polyfunctional (meth) acrylic urethane, or a polyfunctional (meth) acrylate having a carboxyl group, and still more preferably a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyol with (meth) acrylic acid.

Specific examples of the polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydric compound with (meth) acrylic acid include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol polyacrylate, and the like. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol polyacrylate are particularly preferable in terms of increasing the intermolecular or intramolecular crosslinking density and further improving the curing properties of the film even by low-temperature calcination.

The content ratio of the [ M ] polymerizable monomer in the third composition is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, with respect to 100 parts by mass of the polymer (a 3) contained in the third composition. The content of the [ M ] polymerizable monomer is preferably 1,000 parts by mass or less, and more preferably 500 parts by mass or less, per 100 parts by mass of the polymer (a 3). When the content ratio of the [ M ] polymerizable monomer is in the above range, it is preferable that sufficient hardenability and sufficient alkali developability as a cured film be secured and generation of scum, film residue, or the like on the substrate in the unexposed area or the light-shielding layer be sufficiently suppressed.

< photopolymerization initiator >

The third composition contains [ Di ] photopolymerization initiator as a radiation-sensitive compound. As the [ Di ] photopolymerization initiator (hereinafter, also simply referred to as "photopolymerization initiator") contained in the third composition, a compound that induces actinic rays having a wavelength of 300nm or more (preferably 300nm to 450 nm) and initiates and accelerates polymerization of the [ M ] polymerizable monomer is preferably used. When a photopolymerization initiator that does not directly sense actinic rays having a wavelength of 300nm or more is used, the polymerization of the [ M ] polymerizable monomer can be initiated and accelerated by sensing actinic rays having a wavelength of 300nm or more by using a sensitizer in combination therewith.

As the photopolymerization initiator, known compounds can be used. Specific examples thereof include oxime ester compounds, organohalogenated compounds, oxadiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organoperoxy compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organoboronic acid compounds, disulfonic acid compounds, α -aminoketone compounds, onium salt compounds, acylphosphine (oxide) compounds, and the like. Of these, at least one selected from the group consisting of an oxime ester compound, an α -aminoketone compound, and a hexaarylbiimidazole compound is preferable, and an oxime ester compound or an α -aminoketone compound is more preferable, in terms of further improving the sensitivity of the third composition. Further, as the photopolymerization initiator, commercially available products can be used, and examples thereof include brilliant good solid (IRGACURE) OXE01, brilliant good solid (IRGACURE) OXE02 (manufactured by BASF corporation, or more).

In the third composition, the content ratio of the photopolymerization initiator is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 5 parts by mass or more, relative to 100 parts by mass of the polymer (a 3) contained in the third composition. The content of the photopolymerization initiator is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less, per 100 parts by mass of the polymer (a 3) contained in the third composition.

< silanol Compound >

The third composition comprises [ B ] a silanol compound. Specific examples and preferable examples of the [ B ] silanol compound contained in the third composition are the same as those of the first composition.

In the third composition, the content ratio of the [ B ] silanol compound is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and still more preferably 1 part by mass or more, relative to 100 parts by mass of the polymer (a 3) contained in the third composition. The content of the [ B ] silanol compound is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, per 100 parts by mass of the polymer (a 3) contained in the third composition.

< basic Compound >

The third composition comprises [ E ] a basic compound. Specific examples and preferable examples of the [ E ] basic compound contained in the third composition are the same as those of the first composition.

In the third composition, the content ratio of the [ E ] basic compound is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more, relative to 100 parts by mass of the polymer (a 3) contained in the third composition, from the viewpoint of sufficiently obtaining the effect of improving the developing adhesion. The content of the [ E ] basic compound is preferably 5 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the polymer (a 3).

< solvent >

The third composition contains a solvent. The third composition is preferably a liquid composition in which the [ A ] polymer component, [ M ] polymerizable monomer, [ Di ] photopolymerization initiator, [ B ] silanol compound, [ E ] basic compound, and optionally formulated components are dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent which dissolves each component formulated in the third composition and does not react with each component. Specific examples of the solvent contained in the third composition are the same as those contained in the first composition.

In the third composition, the content of the solvent (the total amount thereof when two or more solvents are included) is preferably 50 to 95 parts by mass, and more preferably 60 to 90 parts by mass, relative to 100 parts by mass of the total components of the third composition.

< other ingredients >

The third composition may contain other components (other components) than the above-mentioned [ A ] polymer component, [ M ] polymerizable monomer, [ Di ] photopolymerization initiator, [ B ] silanol compound, [ E ] basic compound, and solvent. Specific examples and preferred examples of the other components that can be contained in the third composition are the same as those of the first composition.

The solid content concentration of the third composition may be appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 5 to 60 mass%, more preferably 10 to 55 mass%, and still more preferably 12 to 50 mass%.

According to the present disclosure, the following radiation-sensitive composition is provided.

[1] A radiation-sensitive composition comprising: a polymer selected from at least one of the group consisting of a polymer containing a structural unit (I) having a group represented by the formula (1) or an acid-dissociable group, and a siloxane polymer;

a photoacid generator; and

a silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom, and having no alkoxy group.

[2] the radiation-sensitive composition according to [1], wherein the silanol compound has a boiling point of 80 ℃ or higher.

[3] the radiation-sensitive composition according to [1] or [2], wherein the silanol compound is a compound represented by the following formula (2).

(R⁴)_mSi(OH)_4-m…(2)

[4] the radiation-sensitive composition according to any one of [1] to [3], wherein the silanol compound has an aromatic ring.

[5] the radiation-sensitive composition according to any one of [1] to [4], wherein the group represented by the formula (1) is bonded to an aromatic ring group or a linear hydrocarbon group.

[6] the radiation-sensitive composition according to any one of [1] to [5], wherein the structural unit (I) has at least one selected from the group consisting of the group represented by the formula (3-1), the group represented by the formula (3-2) and the group represented by the formula (3-3).

The radiation-sensitive composition according to any one of [1] to [6], wherein the photoacid generator comprises at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds.

The radiation-sensitive composition according to any one of [1] to [7], further comprising an acid diffusion controller.

A radiation-sensitive composition according to [ 8], wherein the acid diffusion controlling agent is at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines.

[ 10] the radiation-sensitive composition according to any one of [1] to [ 9], further comprising a basic compound (excluding an acid diffusion controller).

[ 11] the radiation-sensitive composition according to [ 10], wherein the basic compound is an organic base.

[ 12] the radiation-sensitive composition according to [ 11], wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more.

[ 13] the radiation-sensitive composition according to [ 11] or [ 12], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphorous nitriles.

[ 14] the radiation-sensitive composition according to any one of [1] to [ 13], wherein the polymer comprising the structural unit (I) further comprises one or more structural units selected from the group consisting of an oxetanyl group and an oxetanyl group.

[ 15 ] the radiation-sensitive composition according to any one of [1] to [ 14], wherein the polymer comprising the structural unit (I) further comprises a structural unit having an acidic group.

[ 16 ] A radiation-sensitive composition comprising: a polymer comprising a structural unit having an acidic group (wherein a polymer having a structural unit represented by the formula (1) is excluded);

a quinone diazide compound;

a silanol compound which has a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and which has no alkoxy group;

a basic compound; and

a solvent.

[ 17 ] the radiation-sensitive composition according to [ 16 ], wherein the polymer comprising a structural unit having an acidic group further comprises a structural unit having a crosslinkable group.

[ 18] the radiation-sensitive composition according to [ 17 ], wherein the crosslinkable group is one or more selected from the group consisting of an oxetanyl group and an oxetanyl group.

[ 19 ] the radiation-sensitive composition according to any one of [ 16 ] to [ 18], wherein the quinone diazide compound is a condensate of a phenolic compound or an alcoholic compound with 1, 2-naphthoquinone diazide sulfonyl halide.

[ 20] the radiation-sensitive composition according to any one of [ 16 ] to [ 19 ], wherein the silanol compound has a boiling point of 80 ℃ or higher.

The radiation-sensitive composition according to any one of [ 16 ] to [ 20], wherein the silanol compound is a compound represented by the following formula (2).

(R⁴)_mSi(OH)_4-m…(2)

[ 22 ] the radiation-sensitive composition according to any one of [ 16 ] to [ 21 ], wherein the silanol compound has an aromatic ring.

The radiation-sensitive composition according to any one of [ 16 ] to [ 22 ], wherein the basic compound is an organic base.

[ 24 ] the radiation-sensitive composition according to [ 23 ], wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more.

[ 25 ] the radiation-sensitive composition according to [ 23 ] or [ 24 ], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphorous nitriles.

[ 26 ] A radiation-sensitive composition comprising: a polymer comprising a structural unit having an acidic group;

a polymerizable monomer;

a photopolymerization initiator;

a silanol compound which has a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and which does not have an alkoxy group;

a basic compound; and

a solvent.

The radiation-sensitive composition according to [ 26 ], wherein the polymer comprising a structural unit having an acidic group further comprises a structural unit having a crosslinkable group.

The radiation-sensitive composition according to [ 27], wherein the crosslinkable group is one or more selected from the group consisting of an oxetanyl group and an oxetanyl group.

[ 29] the radiation-sensitive composition according to any one of [ 26 ] to [ 28 ], wherein the silanol compound has a boiling point of 80 ℃ or higher.

[ 30 ] the radiation-sensitive composition according to any one of [ 26 ] to [ 29], wherein the silanol compound is a compound represented by the following formula (2).

(R⁴)_mSi(OH)_4-m…(2)

[ 31 ] the radiation-sensitive composition according to any one of [ 26 ] to [ 30 ], wherein the silanol compound has an aromatic ring.

The radiation-sensitive composition according to any one of [ 26 ] to [ 31 ], wherein the basic compound is an organic base.

[ 33 ] the radiation-sensitive composition according to [ 32 ], wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more.

[ 34 ] the radiation-sensitive composition according to [ 32 ] or [ 33 ], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphorous nitriles.

< hard coating film and method for producing the same >

The hardened film of the present disclosure is formed from the radiation-sensitive composition prepared in the manner described. The radiation-sensitive composition has high radiation sensitivity and excellent storage stability. Further, by using the radiation-sensitive composition, a patterned film which exhibits high adhesion to a substrate even after development, has a low dielectric constant, and is excellent in chemical resistance can be formed. Therefore, the radiation-sensitive composition can be preferably used as a material for forming an interlayer insulating film, a planarizing film, a spacer, a protective film, a coloring pattern film for a color filter, a partition wall, a bank, or the like.

When a cured film is produced, a positive-type cured film can be formed depending on the type of the photosensitive agent by using the radiation-sensitive composition. The cured film can be produced using the radiation-sensitive composition, for example, by a method including the following steps 1 to 4.

(step 1) a step of forming a coating film using the radiation-sensitive composition.

(step 2) exposing at least a part of the coating film.

(step 3) a step of developing the exposed coating film.

(step 4) a step of heating the developed coating film.

Hereinafter, each step will be described in detail.

[ Process 1: coating Process)

In this step, the radiation-sensitive composition is applied to a film-forming surface (hereinafter, also referred to as a "film-forming surface"), and preferably a solvent is removed by heat treatment (prebaking) to form a coating film on the film-forming surface. The material of the film formation surface is not particularly limited. For example, in the case of forming an interlayer insulating film, the radiation-sensitive composition is applied to a substrate provided with a switching element such as a Thin Film Transistor (TFT) to form a coating film. Examples of the substrate include a glass substrate, a silicon substrate, and a resin substrate. A metal thin film may be formed on the surface of the substrate on which the coating film is formed, depending on the application, and various surface treatments such as Hexamethyldisilazane (HMDS) treatment may be performed.

Examples of the method for applying the radiation-sensitive composition include: spray method, roll coating method, spin coating method, slit die coating method, bar coating method, ink jet method, and the like. Among these coating methods, it is preferable to perform the coating by a spin coating method, a slit die coating method, or a bar coating method. The prebaking conditions vary depending on the kind and content ratio of each component of the radiation-sensitive composition, and are, for example, 0.5 to 10 minutes at 60 to 130 ℃. The film thickness of the formed coating film (i.e., the film thickness after the pre-baking) is preferably 0.1 to 12 μm. The radiation-sensitive composition applied to the film formation surface may be dried under reduced pressure (Vacuum Dry, VCD)) before prebaking.

[ step 2: exposure Process

In this step, at least a part of the coating film formed in the step 1 is irradiated with radiation. At this time, a cured film having a pattern can be formed by irradiating the coating film with radiation through a mask having a predetermined pattern. Examples of the radiation include ultraviolet rays, far ultraviolet rays, and ultraviolet rays,Charged particle beams such as visible rays, X-rays, and electron beams. Of these, ultraviolet rays are preferable, and examples thereof include g-rays (wavelength: 436 nm) and i-rays (wavelength: 365 nm). The exposure dose of radiation is preferably 0.1J/m²～20,000J/m²。

[ step 3: development Process

In this step, the coating film irradiated with the radiation in the step 2 is developed. Specifically, the coating film irradiated with radiation in step 2 is subjected to positive development in which the irradiated portion of the radiation is removed by development with a developer. As the developer, for example, an aqueous solution of an alkali (alkaline compound) is exemplified. Examples of the base include sodium hydroxide, tetramethylammonium hydroxide, and bases exemplified in paragraph [0127] of Japanese patent application laid-open No. 2016-145913. The alkali concentration of the aqueous alkali solution is preferably 0.1 to 5% by mass from the viewpoint of obtaining appropriate developability. The developing method includes a suitable method such as a liquid coating method, a dipping method, a shaking dipping method, and a shower method. The development time also varies depending on the composition of the composition, and is, for example, 30 seconds to 120 seconds. After the development step, the patterned coating film is preferably subjected to rinsing treatment by running water cleaning.

[ step 4: heating procedure

In this step, a treatment (post-baking) of heating the coating film developed in the above-mentioned step 3 is performed. The post baking can be performed using a heating device such as an oven or a hot plate. The post-baking conditions are, for example, heating temperatures of 120 to 250 ℃. For example, when the heat treatment is performed on a hot plate, the heating time is 5 to 40 minutes, and when the heat treatment is performed in an oven, the heating time is 10 to 80 minutes. In the manner described above, a cured film having a target pattern can be formed on a substrate. The shape of the pattern of the cured film is not particularly limited, and examples thereof include a line-and-space pattern, a dot pattern, a hole pattern, and a lattice pattern.

< semiconductor element >

The semiconductor element of the present disclosure includes a hardened film formed using the radiation-sensitive composition. The cured film is preferably an interlayer insulating film for insulating between wirings in the semiconductor element. The semiconductor element of the present disclosure can be manufactured using a known method.

< display element >

The display element of the present disclosure includes a hardened film formed using the radiation-sensitive composition. In addition, the display element of the present disclosure includes a hardened film formed using the radiation-sensitive composition by including the semiconductor element of the present disclosure. Further, the display element of the present disclosure may further include a planarization film formed on the TFT substrate as a cured film formed using the radiation-sensitive composition. Examples of the display element include a liquid crystal display element and an organic Electroluminescence (EL) display element.

[ examples ]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples and comparative examples, "part(s)" and "%" are based on mass unless otherwise specified. In the present example, the weight average molecular weight (Mw) and the number average molecular weight of the polymer were measured by the following methods.

[ weight average molecular weight (Mw) and number average molecular weight (Mn) ]

The Mw and Mn of the polymer were measured by the following methods.

The measurement method: gel Permeation Chromatography (GPC) method

An apparatus: GPC-101 of Showa electrician

GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 of Shimadzu GLC corporation were combined

The mobile phase: tetrahydrofuran (THF)

Column temperature: 40 deg.C

Flow rate: 1.0 mL/min

Sample concentration: 1.0% by mass

Sample injection amount: 100 μ L

The detector: differential refractometer

Standard substance: monodisperse polystyrene

[ monomer ]

The monomers used in the synthesis of the polymer are abbreviated as follows.

Monomer for providing structural Unit (I)

A monomer having a group represented by the formula (1)

MPTMS: 3-methacryloxypropyltrimethoxysilane

MPTES: 3-methacryloxypropyltriethoxysilane

STMS: p-styryl trimethoxy silane

And (3) SDMS: p-styryl dimethoxy hydroxyl silane

STES: p-styryl triethoxy silane

Monomers having acid-dissociable groups

MATHF: 2-tetrahydrofuryl methacrylate

Other monomers

AA: acrylic Acid (AA)

MA: methacrylic acid (MAA)

MI: maleimide

And (3) OXMA: OXE-30 (manufactured by Osaka organic chemical industries, ltd.) methyl methacrylate (3-Ethyl oxetan-3-yl)

GMA: glycidyl methacrylate

ECHMA: 3, 4-epoxycyclohexylmethyl methacrylate

EDCPMA: methacrylic acid [3, 4-epoxy tricyclic ring (5.2.1.0)^2,6) Decan-9-yl]Esters of salicylic acid

MMA: methacrylic acid methyl ester

ST: styrene (meth) acrylic acid ester

< Synthesis of Polymer (A) >

Synthesis example 1 Synthesis of Polymer (A-1)

A flask equipped with a cooling tube and a stirrer was charged with 24 parts of propylene glycol monomethyl ether, 39 parts of methyltrimethoxysilane and 18 parts of 3-methacryloxypropyltrimethoxysilane, and the mixture was heated to a solution temperature of 60 ℃. After the solution temperature reached 60 ℃, 0.1 part of formic acid and 19 parts of water were charged, and the temperature of the solution was raised to 75 ℃ while stirring slowly, and the temperature was maintained for 2 hours. After cooling to 45 ℃, 28 parts by mass of trimethyl orthoformate was added as a dehydrating agent, and stirred for 1 hour. Further, the solution temperature was adjusted to 40 ℃ and evaporation was carried out while keeping the temperature, whereby water and methanol produced in the hydrolytic condensation were removed, thereby obtaining a polymer solution containing the polymer (A-1). The polymer solution had a solid content concentration of 35% by mass, a weight-average molecular weight (Mw) of the polymer (A-1) was 1,800, and a molecular weight distribution (Mw/Mn) was 2.2.

Synthesis example 2 Synthesis of Polymer (A-2)

Polymer (A-2) having the same solid content concentration, weight average molecular weight and molecular weight distribution as polymer (A-1) was obtained in the same manner as in Synthesis example 1, except that the monomers used were changed to phenyltrimethoxysilane 39 parts and 3-methacryloxypropyltrimethoxysilane 18 parts.

Synthesis example 3 Synthesis of Polymer (A-3)

A flask equipped with a cooling tube and a stirrer was charged with 10 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile) and 200 parts of diethylene glycol methyl ethyl ether. Then, 15 parts of 3-methacryloxypropyltrimethoxysilane, 10 parts of methacrylic acid, 20 parts of (3-ethyloxetan-3-yl) methyl methacrylate, 30 parts of glycidyl methacrylate and 25 parts of methyl methacrylate were charged, and after nitrogen substitution, the temperature of the solution was increased to 70 ℃ with gentle stirring, and the temperature was maintained for 5 hours, thereby obtaining a polymer solution containing the polymer (A-3). The polymer solution had a solid content concentration of 34.0% by mass, the Mw of the polymer (A-3) was 10,500, and the molecular weight distribution (Mw/Mn) was 2.2.

Synthesis examples 4 to 12, 19 and 20 polymers (A-4) to (A-12), polymer (CA-1) and Polymer (CA-2)

Polymer solutions each containing polymers (A-4) to (A-12), polymer (CA-1) and polymer (CA-2) having the same solid content concentration, weight average molecular weight and molecular weight distribution as those of polymer (A-3) were obtained in the same manner as in Synthesis example 3, except that the components were used in the same types and amounts (parts by mass) as shown in Table 1.

Synthesis examples 13 to 18 Synthesis of polymers (A-13) to (A-18)

Polymer solutions each containing polymers (A-13) to (A-18) having the same solid content concentration, weight average molecular weight, and molecular weight distribution as those of polymer (A-3) were obtained in the same manner as in Synthesis example 3, except that the components were used in the types and amounts (parts by mass) shown in Table 1.

Preparation of < radiation-sensitive composition (1) >

The polymer (a), the silanol compound (B), the photoacid generator (C), the additive (X), and the solvent (G) used for preparing the radiation-sensitive composition are shown below.

Polymer (A)

A-1 to A-12: polymers (A-1) to (A-12) synthesized in Synthesis examples 1 to 12

CA-1 to CA-2: synthesis examples 19 and 20 Polymer (CA-1) and Polymer (CA-2)

Silanol compound (B)

B-1: trimethylsilanol

B-2: triethylsilanol

B-3: methylsilanetriols

B-4: diphenylsilanediols

B-5: phenyl silanetriol

B-6: triphenylsilicol

B-7: tris (4-tolyl) silanol

Photoacid Generator (C)

C-1: brilliant good solid (Irgacure) PAG121 (manufactured by BASF corporation)

C-2: OS-17 described in International publication No. 2016/124493

C-3: OS-25 described in International publication No. 2016/124493

Additives (X)

Sealing assistants

X-1: 3-glycidoxypropyltrimethoxysilane

X-2:2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane

Acid diffusion controlling agent

X-3: 2-phenylbenzimidazoles

X-4: n- (tert-butoxycarbonyl) -2-phenylbenzimidazoles

X-5: 4-methyl-2-phenylbenzimidazoles

Solvent (G)

G-1: diethylene glycol ethyl methyl ether

G-2: propylene glycol monomethyl ether

G-3: propylene glycol monomethyl ether acetate

[ example 1]

In the polymer solution containing the polymer (A-1) obtained in Synthesis example 1,5 parts of the silanol compound (B-1), 1 part of the photoacid generator (C-2) and 5 parts of the additive (x-1) were mixed in an amount corresponding to 100 parts (solid content) of the polymer (A-1), and the mixture was heated at a temperature of 1: diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether were added in a mass ratio of 1. Then, the mixture was filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive composition.

Examples 2 to 20 and comparative examples 1 to 5

Radiation-sensitive compositions of examples 2 to 20 and comparative examples 1 to 5 were prepared in the same manner as in example 1, except that the components were used in the types and amounts (parts by mass) shown in Table 2. In table 2, as for the solvent (G), in the examples using two kinds of organic solvents (example 1, example 2, example 4 to example 14, example 18 to example 20, and comparative example 5), the solvent 1 and the solvent 2 were mixed in the following ratio of the solvent 1: vehicle 2=1:1 in a mass ratio. In examples using three organic solvents (example 3, example 15 to example 17, comparative example 1 to comparative example 4), the solvent 1, the solvent 2 and the solvent 3 were mixed in the ratio of the solvent 1: solvent 2: vehicle 3=5:4:1 in a mass ratio.

< evaluation >

The radiation-sensitive compositions of examples 1 to 20 and comparative examples 1 to 5 were used to evaluate the following items by the methods described below. The evaluation results are shown in table 3.

[ radiation sensitivity ]

The radiation-sensitive composition was applied to a silicon substrate subjected to HMDS treatment at 60 ℃ for 60 seconds using a spinner, and then prebaked at 90 ℃ for 2 minutes on a hot plate to form a coating film having an average thickness of 3.0 μm. The coating film was irradiated with a predetermined amount of ultraviolet light by a mercury lamp through a pattern mask having a line and space pattern with a width of 10 μm. Subsequently, a developing treatment was performed at 25 ℃ for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide as a developer, and then, rinsing was performed with ultrapure water for 1 minute. At this time, the minimum exposure amount capable of forming a line and space pattern having a width of 10 μm was measured. The measured value at the minimum exposure amount is less than 300J/m²The radiation sensitivity was evaluated as good at 300J/m²In the above case, it can be evaluated that the radiation sensitivity is poor.

[ evaluation of chemical resistance of cured film ]

The chemical resistance of the cured film was evaluated based on the degree of swelling caused by the stripping solution. After the radiation-sensitive composition was coated on a silicon substrate using a spinner, it was prebaked on a hot plate at 90 ℃ for 2 minutes to form a coating film having an average thickness of 3.0 μm. Subsequently, the entire surface of the substrate was irradiated with 3000J/m using a proximity exposure apparatus ("MA-1200" (ghi ray mix) from Canon corporation²After the light treatment, the resultant was calcined (post-baked) for 30 minutes in an oven heated to 230 ℃. The resulting cured film was immersed in an N-methyl-2-pyrrolidone solvent heated to 40 ℃ for 6 minutes to determine the rate of change in film thickness before and after immersion(%). The film thickness change rate was evaluated as an index of chemical resistance according to the following criteria.

AA: the change rate of the film thickness is less than 2 percent

A: the film thickness change rate is more than 2 percent and less than 5 percent

B: the film thickness change rate is more than 5% and less than 10%

C: the film thickness change rate is more than 10% and less than 15%

D: the film thickness change rate is more than 15%

In the case of AA, A or B, the chemical resistance can be evaluated as good, and in the case of C or D, the chemical resistance can be evaluated as poor. The film thickness was measured at 25 ℃ using an optical interference film thickness measuring apparatus (Lambda Ace VM-1010).

[ evaluation of storage stability ]

The prepared radiation-sensitive composition was sealed in a light-shielding, airtight container. After 7 days at 25 ℃, the container was opened, measurement was performed in accordance with the above-mentioned [ radiation sensitivity ] evaluation, and the increase rate of radiation sensitivity (minimum exposure amount) before and after 7 days of storage was calculated. The case where the value is less than 5% is determined as "AA", the case where the value is 5% or more and less than 10% is determined as "a", the case where the value is 10% or more and less than 20% is determined as "B", the case where the value is 20% or more and less than 30% is determined as "C", and the case where the value is 30% or more is determined as "D". Good storage stability can be evaluated in the case of AA, A or B, and poor storage stability can be evaluated in the case of C or D.

[ evaluation of substrate adhesion (development adhesion) ]

The radiation-sensitive composition was coated on a silicon substrate which was not subjected to HMDS treatment using a spinner, and then prebaked on a hot plate at 90 ℃ for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Exposing the coating film to a mercury lamp at an exposure of 400J/m at 365nm through a pattern mask having a line-and-space pattern with a width of 1-50 μm²Ultraviolet rays of (4). Next, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was used as a developer, and after development treatment was performed at 25 ℃ for 60 seconds, the treatment was performed with ultrapure waterWashing with running water for 1 minute. In this case, a case where a measured value of the minimum width obtained by measuring the minimum width of the line-and-space pattern remaining without peeling off the substrate is 2 μm or less is determined as "AA", a case where the measured value is greater than 2 μm and 5 μm or less is determined as "a", a case where the measured value is greater than 5 μm and 10 μm or less is determined as "B", a case where the measured value is greater than 10 μm and 30 μm or less is determined as "C", and a case where the measured value is greater than 30 μm is determined as "D". In the case of AA, a or B, the development adhesion was good, and in the case of C or D, the development adhesion was poor.

[ evaluation of relative dielectric constant ]

After the radiation-sensitive composition was applied onto a glass substrate using a spinner, the resultant was prebaked on a hot plate at 90 ℃ for 2 minutes to form a coating film having an average thickness of 3.0 μm. Subsequently, the entire surface of the substrate was irradiated with 3000J/m using a proximity exposure apparatus ("MA-1200" (ghi ray mix) from Canon corporation²After the light irradiation, the resultant was calcined (post-baked) in an oven heated to 230 ℃ for 30 minutes to form a cured film. The relative dielectric constant of the obtained cured film at a frequency of 10kHz was measured. The reduction rate of the relative permittivity was calculated with the relative permittivity of example 5 as a reference, and the reduction rate was evaluated according to the following reference.

AA: the reduction rate of the relative dielectric constant is more than 20%

A: the reduction rate of the relative dielectric constant is more than 15 percent and less than 20 percent

B: the reduction rate of the relative dielectric constant is more than 10 percent and less than 15 percent

C: the reduction rate of the relative dielectric constant is more than 5% and less than 10%

D: the reduction rate of the relative dielectric constant is less than 5 percent

The dielectric constant can be evaluated as good in the case of AA, a, or B, as good in the case of C, and as poor in the case of D.

[ Table 3]

In table 3, "-" indicates that it was not analyzed in the sensitivity evaluation and thus could not be evaluated.

As shown in table 3: the radiation-sensitive compositions of examples 1 to 20 were good in radiation sensitivity, chemical resistance, storage stability, development adhesion, and relative permittivity as practical characteristics, and the balance of the characteristics was obtained. In contrast, comparative examples 1 to 3 were not resolved by exposure, and were low in chemical resistance and relative dielectric constant. In the radiation-sensitive compositions of comparative examples 4 and 5, the evaluation of radiation sensitivity, chemical resistance and storage stability were the same as in examples 1 to 20, but the development adhesion and relative dielectric constant were lower than in examples 1 to 20.

Preparation of < radiation-sensitive composition (2) >

Compounds used for the preparation of the radiation-sensitive composition are shown below. The polymer (a), the silanol compound (B), the photoacid generator (C), the additive (X), and the solvent (G) are the same as those used for the preparation of the radiation-sensitive composition (1), and therefore, the description thereof is omitted.

Alkali Compound (E)

E-1:1, 8-diazabicyclo [5.4.0] -7-undecene

E-2:1,5, 7-triazabicyclo [4.4.0] dec-5-ene

[ examples 21 to 29]

Radiation-sensitive compositions of examples 21 to 29 were prepared in the same manner as in example 1, except that the components were used in the types and amounts (parts by mass) shown in table 4. In table 4, as for the solvent (G), in the case of using two organic solvents, the solvent 1 and the solvent 2 were mixed in the ratio of the solvent 1: vehicle 2=1:1 in a mass ratio. In the case of using three organic solvents, solvent 1, solvent 2 and solvent 3 are mixed in a ratio of solvent 1: solvent 2: vehicle 3=5:4:1 was mixed and used (the same applies to table 6).

< evaluation >

The radiation-sensitive compositions of examples 21 to 29 were used to evaluate the respective items by the same methods as in example 1. The evaluation results are shown in table 5. The radiation-sensitive compositions of examples 21 to 29 had the same compositions as those of examples 2,5, 7, 8, 10, 13, 14, 16 and 19 except that the basic compound (E) was added.

[ Table 5]

As shown in table 5: the radiation-sensitive compositions of examples 21 to 29 had the same compositions as those of examples 2,5, 7, 8, 10, 13, 14, 16 and 19 except that the basic compound (E) was not contained, and thus the radiation sensitivity, chemical resistance and storage stability were highly maintained, and the development adhesion was further improved. In addition, it was confirmed that: by blending the basic compound (E), the relative dielectric constant of the cured film is improved.

Preparation of a radiation-sensitive composition (3) >

Compounds used for the preparation of the radiation-sensitive composition are shown below. The details of the compound (E) and the basic compound (E) which are the same as those in the preparation (1) of the radiation-sensitive composition among the polymer (a), the silanol compound (B), the photoacid generator (C), the additive (X) and the solvent (G) are as described above, and are omitted from the description.

Polymer (A)

A-13 to A-18: synthesis examples 13 to 18 Polymer (A-13) to Polymer (A-18)

Radioactive-sensitive Compound (D)

D-1: condensate of 4,4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol (1.0 mol) and 1, 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

D-2: condensate of 4,4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol (1.0 mol) and 1, 2-naphthoquinonediazide-5-sulfonyl chloride (1.0 mol)

D-3: condensate of 1, 1-tris (p-hydroxyphenyl) ethane (1.0 mol) with 1, 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

D-4: condensate of 1, 1-tris (p-hydroxyphenyl) ethane (1.0 mol) with 1, 2-naphthoquinonediazide-5-sulfonyl chloride (1.0 mol)

D-5: irgacure OXE02 (manufactured by BASF corporation)

Polymerizable monomer (M)

M-1: kayalrad (KAYARAD) DPHA (manufactured by Japan Chemicals, inc.)

Examples 30 to 35 and comparative examples 6 to 14

Radiation-sensitive compositions of examples 30 to 35 and comparative examples 6 to 14 were prepared in the same manner as in example 1, except that the components were used in the types and amounts (parts by mass) shown in Table 6. The radiation-sensitive compositions of examples 30 and 31 correspond to the first composition, the radiation-sensitive compositions of examples 32 to 34 correspond to the second composition, and the radiation-sensitive composition of example 35 corresponds to the third composition.

< evaluation >

The radiation-sensitive compositions of examples 30 to 35 and comparative examples 6 to 14 were used to evaluate the respective items by the same method as in example 1. The evaluation results are shown in table 7.

[ Table 7]

The radiation-sensitive compositions of examples 30 and 31, which were the first compositions, were good in radiation sensitivity, chemical resistance, storage stability, development adhesion, and relative permittivity as practical characteristics, and had a balanced relationship between the characteristics. In particular, in the radiation-sensitive composition of example 31 containing the basic compound (E), development adhesion can be improved while maintaining high radiation sensitivity, chemical resistance, storage stability and relative permittivity.

The radiation-sensitive compositions of examples 32 to 34 as the second composition can highly maintain radiation sensitivity, chemical resistance and storage stability and improve development adhesion as compared with comparative examples 6, 9 and 12, which have almost the same composition except that they do not contain the basic compound (E).

The radiation-sensitive composition of example 35 as the third composition can highly maintain the radiation sensitivity, storage stability and relative permittivity, and at the same time can improve the chemical resistance and development adhesion, as compared with comparative example 14 containing no basic compound (E).

Claims

1. A radiation-sensitive composition comprising: a polymer which is at least one selected from the group consisting of a polymer containing a structural unit (I) having a group represented by the following formula (1) or an acid-dissociable group, and a siloxane polymer;

a photoacid generator; and

a silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group,

in the formula (1), R¹、R²And R³Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms,An alkyl group or phenyl group having 1 to 10 carbon atoms; wherein R is¹、R²And R³At least one of them is an alkoxy group having 1 to 6 carbon atoms; "" indicates a bond.

2. The radiation-sensitive composition according to claim 1, wherein the silanol compound has a boiling point of 80 ℃ or higher.

3. The radiation-sensitive composition according to claim 1 or 2, wherein the silanol compound is a compound represented by the following formula (2),

(R⁴)_mSi(OH)_4-m…(2)

in the formula (2), R⁴Is a monovalent hydrocarbon group; m is an integer of 1 to 3.

4. The radiation-sensitive composition of claim 1 or 2, wherein the silanol compound has an aromatic ring.

5. The radiation-sensitive composition according to claim 1 or 2, wherein the group represented by formula (1) is bonded to an aromatic ring group or a chain hydrocarbon group.

6. The radiation-sensitive composition according to claim 1 or 2, wherein the structural unit (I) has at least one selected from the group consisting of a group represented by the following formula (3-1), a group represented by the following formula (3-2), and a group represented by the following formula (3-3),

in the formulae (3-1), (3-2) and (3-3), A¹And A²Independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; n1 is an integer of 0 to 4; n2 is an integer of 0 to 6; wherein, when n1 is 2 or more, a plurality of A¹Are the same or different from each other; when n2 is 2 or more, a plurality of A²Are the same or different from each other; r is⁶Is alkanediyl; r¹、R²And R³The same as the formula (1); "" indicates a bond.

7. The radiation-sensitive composition according to claim 1 or 2, wherein the photoacid generator comprises at least one selected from the group consisting of an oxime sulfonate compound and a sulfonimide compound.

8. The radiation-sensitive composition according to claim 1 or 2, further comprising an acid diffusion controlling agent.

9. The radiation-sensitive composition according to claim 8, wherein the acid diffusion controller is at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines.

10. The radiation-sensitive composition according to claim 8, further comprising a basic compound excluding the acid diffusion controller.

11. The radiation-sensitive composition of claim 10, wherein the basic compound is an organic base.

12. The radiation-sensitive composition according to claim 11, wherein the basic compound is an organic base having an acid dissociation constant pKa of 9 or more.

13. The radiation-sensitive composition according to claim 11 or 12, wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphorous nitriles.

14. The radiation-sensitive composition according to claim 1 or 2, wherein the polymer comprising the structural unit (I) further comprises a structural unit having one or more selected from the group consisting of an oxetanyl group and an oxetanyl group.

15. The radiation-sensitive composition according to claim 1 or 2, wherein the polymer comprising the structural unit (I) further comprises a structural unit having an acidic group.

16. A radiation-sensitive composition comprising: a polymer comprising a structural unit having an acidic group, with the exception of a polymer having a structural unit represented by the following formula (1);

a quinone diazide compound;

a basic compound; and

a solvent, a water-soluble organic solvent,

in the formula (1), R¹、R²And R³Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms or a phenyl group; wherein R is¹、R²And R³At least one of them is an alkoxy group having 1 to 6 carbon atoms; "" indicates a bond.

17. The radiation-sensitive composition according to claim 16, wherein the polymer comprising a structural unit having an acidic group further comprises a structural unit having a crosslinkable group.

18. The radiation-sensitive composition according to claim 17, wherein the crosslinkable group is one or more selected from the group consisting of an oxetanyl group and an oxetanyl group.

19. The radiation-sensitive composition according to any one of claims 16 to 18, wherein the quinone diazide compound is a condensate of a phenolic compound or an alcoholic compound with 1, 2-naphthoquinone diazide sulfonyl halide.

20. A radiation-sensitive composition comprising: a polymer comprising a structural unit having an acidic group;

a polymerizable monomer;

a photopolymerization initiator;

a silanol compound which has a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and which has no alkoxy group,

a basic compound; and

and (3) a solvent.

21. The radiation-sensitive composition according to claim 20, wherein the polymer comprising a structural unit having an acidic group further comprises a structural unit having a crosslinkable group.

22. The radiation-sensitive composition according to claim 21, wherein the crosslinkable group is one or more selected from the group consisting of an oxetanyl group and an oxetanyl group.

23. A method of manufacturing a hardened film, comprising: a step of forming a coating film using the radiation-sensitive composition according to any one of claims 1 to 22;

irradiating at least a part of the coating film with radiation;

developing the coating film irradiated with the radiation; and

and heating the developed coating film.

24. A hardened film formed using the radiation-sensitive composition according to any one of claims 1 to 22.

25. A semiconductor element comprising the cured film according to claim 24.

26. A display element comprising the cured film according to claim 24.