Negative photosensitive composition

Abstract

[Problem] The present invention provides a negative photosensitive composition that can be developed even when using a developer at a low concentration. [Solution] A negative photosensitive composition comprising (I) a carboxyl-containing alkali-soluble resin, (II) a polymerization initiator, (III) a compound having two or more (meth)acryloyloxy groups, and (IV) a solvent, wherein the content of the compound having two or more (meth)acryloyloxy groups is 40 to 300% by mass based on the total mass of the alkali-soluble resin.

Description

Technical Field

[0001] The present invention relates to a negative photosensitive composition. In addition, the present invention also relates to a method for manufacturing a cured film using the same, a cured film formed therefrom, and a display device including the cured film Background Art

[0002] In recent years, in optical devices such as displays, light-emitting diodes, and solar cells, various proposals have been made for the purpose of improving light utilization efficiency and energy saving. For example, in a liquid crystal display, a method is known in which a transparent planarization film is formed by coating a film on a thin-film transistor (TFT) device, and a pixel electrode is formed on the planarization film to increase the aperture ratio of the display device

[0003] In addition, a structure for manufacturing a touch panel on an organic EL or liquid crystal module has been proposed. In addition, flexible displays using a plastic substrate instead of a glass substrate have also attracted attention. In any case, it is desired that the film coating on the device be formed at a lower temperature and that the constituent materials of the device do not deteriorate thermally. In addition, when forming a film coating on other organic semiconductors, organic solar cells, etc., it is necessary to be able to cure at a lower temperature

[0004] In addition, in consideration of environmental load, a composition that can be developed with an alkaline developer having a concentration lower than the commonly used 2.38% organic developer is required

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2017 / 140409 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] The present invention has been completed based on the above circumstances, and an object thereof is to provide a negative photosensitive composition that can be developed even when using a low-concentration developer

[0010] Methods for Solving the Problems

[0011] The negative photosensitive composition of the present invention contains:

[0012] (I) A carboxyl group-containing alkali-soluble resin,

[0013] (II) A polymerization initiator,

[0014] (III) A compound having two or more (meth)acryloyloxy groups, and

[0015] (IV) A solvent

[0016] Based on the total mass of the alkali-soluble resin, the content of the compound having two or more (meth)acryloyloxy groups is 40 to 300% by mass.

[0017] The method for producing a cured film of the present invention includes coating the above-described negative photosensitive composition on a substrate to form a coating film, and exposing and developing the coating film.

[0018] The cured film of the present invention is produced by the method described above.

[0019] The display device of the present invention includes the above-described cured film.

[0020] Effects of the Invention

[0021] The negative photosensitive composition of the present invention can be developed even when using a low-concentration alkaline developer, and has excellent environmental resistance. In addition, the negative photosensitive composition according to the present invention can increase the film thickness and can achieve high resolution. Further, a cured film can be formed by low-temperature curing. Detailed Description of the Invention

[0022] Hereinafter, embodiments of the present invention will be described in detail.

[0023] In this specification, unless otherwise specified, symbols, units, abbreviations, and terms have the following meanings.

[0024] In this specification, unless otherwise specified, the singular form includes the plural form, and "a" and "the" mean "at least one". In this specification, unless otherwise specified, the elements of a certain concept can be represented by multiple types, and if the amount thereof (for example, mass% or mol%) is described, the amount is the sum of the amounts of multiple types. "And / or" includes all combinations of elements, or also includes the use of a single element.

[0025] In this specification, when a numerical range is represented by "~" or "to / -", they include both endpoints, and the unit is common. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

[0026] In this specification, hydrocarbons are intended to include carbon and hydrogen, and may contain oxygen or nitrogen as needed. A hydrocarbon group is a hydrocarbon having a valence of 1 or more. In this specification, an aliphatic hydrocarbon means a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon, and an aliphatic hydrocarbon group means an aliphatic hydrocarbon having a valence of 1 or more. An aromatic hydrocarbon means a hydrocarbon containing an aromatic ring, and optionally, it may have an aliphatic hydrocarbon group as a substituent or may be fused with an alicyclic ring. An aromatic hydrocarbon group means an aromatic hydrocarbon having a valence of 1 or more. In addition, an aromatic ring means a hydrocarbon having a conjugated unsaturated ring structure, and an alicyclic ring means a hydrocarbon having a ring structure but not containing a conjugated unsaturated ring structure.

[0027] In this specification, an alkyl group refers to a group obtained by removing any one hydrogen from a straight-chain or branched-chain saturated hydrocarbon, including straight-chain alkyl groups and branched-chain alkyl groups. A cycloalkyl group refers to a group obtained by removing one hydrogen from a saturated hydrocarbon containing a cyclic structure. Optionally, the cyclic structure contains a straight-chain or branched-chain alkyl group as a side chain.

[0028] In this specification, an aryl group refers to a group obtained by removing any one hydrogen from an aromatic hydrocarbon. An alkylene group refers to a group obtained by removing any two hydrogens from a straight-chain or branched-chain saturated hydrocarbon. An arylene group refers to a hydrocarbon group obtained by removing any two hydrogens from an aromatic hydrocarbon.

[0029] In this specification, " x-y C x ~C y " and " x C 1～6 " etc. indicate the number of carbon atoms in a molecule or substituent. For example,

[0030] C

[0031] alkyl group refers to an alkyl group having 1 or more and 6 or less carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). In addition, in this specification, a fluoroalkyl group refers to a group in which one or more hydrogens in an alkyl group are replaced by fluorine, and a fluoroaryl group refers to a group in which one or more hydrogens in an aryl group are replaced by fluorine.

[0032] In this specification, the temperature unit is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0033] <Negative-Type Photosensitive Composition>

[0034] The negative-type photosensitive composition of the present invention (hereinafter, simply referred to as "composition") contains (I) an alkali-soluble resin, (II) a polymerization initiator, (III) a compound having two or more (meth)acryloyloxy groups, and (IV) a solvent. Hereinafter, each component contained in the composition of the present invention will be described in detail.

[0035] The composition of the present invention exhibits the effects of the present invention as long as the film thickness is 100 μm or less. It can also be used as a negative-type photosensitive composition for thick films. Here, in the present invention, a thick film refers to a film having an average film thickness of 5 to 100 μm (preferably 5 to 25 μm, more preferably 8 to 20 μm). In the present invention, the average film thickness is measured at 3 to 5 places with a stylus surface profiler manufactured by ULBAC Co., Ltd. and the average value is taken.

[0036] The viscosity of the composition of the present invention is preferably from 0.1 to 10,000 cP, more preferably from 1.0 to 8,000 cP. Here, the viscosity is measured at 25 °C using a rotational viscometer.

[0037] (I) Alkali-soluble resin

[0038] The composition of the present invention contains a carboxyl group-containing alkali-soluble resin (hereinafter, sometimes simply referred to as "alkali-soluble resin"). Having a carboxyl group can improve the solubility of the alkali-soluble resin in a developer at a low concentration.

[0039] The alkali-soluble resin used in the present invention preferably contains an acryloyl group. In addition, the alkali-soluble resin used in the present invention is not particularly limited, but is preferably selected from polysiloxane having a siloxane bond in the main skeleton and an acrylic resin. Among them, from the viewpoint of heat resistance, polysiloxane is more preferably used.

[0040] (Polysiloxane)

[0041] The alkali-soluble resin preferably contains a siloxane (Si-O-Si) bond as the main skeleton. In the present invention, a polymer containing a siloxane bond as the main skeleton is called polysiloxane. The skeleton structure of polysiloxane is classified into a silicone skeleton (the number of oxygen atoms bonded to a silicon atom is 2), a silsesquioxane skeleton (the number of oxygen atoms bonded to a silicon atom is 3), and a silica skeleton (the number of oxygen atoms bonded to a silicon atom is 4) according to the number of oxygen atoms bonded to the silicon atom. In the present invention, any of these may be used. The polysiloxane molecule may contain various combinations of these skeleton structures. Preferably, the polysiloxane used in the present invention contains a silsesquioxane skeleton.

[0042] Polysiloxane usually has a silanol group or an alkoxysilyl group. Such a silanol group and an alkoxysilyl group refer to a hydroxyl group and an alkoxy group directly bonded to silicon that form a siloxane skeleton. Here, it is considered that the silanol group and the alkoxysilyl group have the effect of promoting the curing reaction when using the composition to form a cured film, and also contribute to the reaction with a silicon-containing compound described later. Therefore, polysiloxane preferably has these groups.

[0043] Preferably, the polysiloxane used in the present invention contains a repeating unit represented by formula (Ia):

[0044]

[0045] (In the formula, R a1 is hydrogen or methyl, ma are each independently an integer of 1 to 6, preferably an integer of 1 to 3, and most preferably 3), and

[0046] an acrylic polymerization unit represented by formula (a):

[0047]

[0048] (In the formula, R a2 is independently hydrogen or methyl, and R a3 is hydrogen or a hydrocarbon group having a valence of 1 to 6 of C 1～50 , and one or more methylene groups in the hydrocarbon group may be replaced by an oxy group, an imino group, and / or a carbonyl group. When R a3 has a valence of 2 or more, R a3 connects the carbonyloxy group in formula (a) to the carbonyloxy group contained in other repeating units represented by formula (a), and na is an integer of 0 or more)

[0049] The * of at least one repeating unit in formula (Ia) is directly bonded to the * of other repeating units represented by formula (Ia), or bonded via the acrylic polymer unit represented by the above formula (a), and

[0050] there is at least one acrylic polymer unit in which R a3 in formula (a) is hydrogen.

[0051] In the acrylic polymer unit represented by formula (a), formula (a) can be bonded to other formula (a) to form a block. However, if there are many acrylic polymer units, the heat resistance tends to decrease. Therefore, in one molecule of polysiloxane, it is preferable that the total of na / ((the number of repeating units represented by (Ia)) + the total of na) = 0.15 or less, and more preferably 0.05 or less.

[0052] na is not particularly limited as long as it satisfies the above conditions, and is preferably 0 to 6, more preferably 1 to 4, and further preferably 1 to 2. It should be noted that when there are multiple (a), each na may be the same or different.

[0053] Since the heat resistance tends to decrease when the number of carbon atoms is large, R a3 is preferably hydrogen or a hydrocarbon group of C 1～30 , and more preferably hydrogen or a hydrocarbon group of C 1～20 .

[0054] As R a3 , the following can be exemplified, for example.

[0055]

[0056] Among the above, hydrogen, tris-(2-acryloyloxyethyl) isocyanurate, and dipentaerythritol hexaacrylate are preferred.

[0057] It should be noted that when the repeating unit represented by formula (a) is a group derived from an acrylic compound containing multiple double bonds, it is preferable that some double bonds remain unbroken.

[0058] In the polymer unit represented by formula (a), R a3It may also be a group obtained by removing a plurality, preferably 2 or 3 hydrogens, from a nitrogen- and / or oxygen-containing cycloaliphatic hydrocarbon compound having a hydrocarbon group substituted with an amino group, an imino group, and / or a carbonyl group (preferably a group obtained by removing 2 or 3 hydrogens from a nitrogen-containing aliphatic hydrocarbon ring having an imino group and / or a carbonyl group, more preferably a 5- or 6-membered ring containing nitrogen in the members, and most preferably a group obtained by removing 2 or 3 hydrogens from a piperidine derivative, a pyrrolidine derivative, or an isocyanurate derivative) of an acrylic acid polymerization unit.

[0059] The polysiloxane used in the present invention may also contain a repeating unit represented by formula (Ia'):

[0060]

[0061] (In the formula, R a1’ is hydrogen or methyl, and ma' are each independently an integer of 1 to 6, preferably an integer of 1 to 3, and most preferably 3).

[0062] As will be described later, the polysiloxane containing the repeating unit represented by formula (Ia) can be obtained by (1) reacting a silane monomer having an acryloyl group to obtain an acryloyl group-containing polysiloxane, and (2) breaking and polymerizing the carbon-carbon double bond in the obtained acryloyl group-containing polysiloxane. In this step (2), if unreacted acryloyl groups remain, a polysiloxane having a repeating unit represented by formula (Ia') is formed. A mode of the present invention is also a polysiloxane that does not perform step (2) and is obtained only by step (1).

[0063] If the ratio of the repeating units represented by formula (Ia) and (Ia') is high, the heat resistance decreases, and thus it is preferably 10 to 100 mol% relative to the total number of repeating units of the polysiloxane.

[0064] In the present specification, "relative to the total number of repeating units of the polysiloxane" means the total number of repeating units of the siloxane of the polysiloxane. For example, the acrylic acid polymerization unit represented by formula (a) is not included in this total number.

[0065] The polysiloxane of the present invention preferably contains a repeating unit represented by formula (Ib).

[0066]

[0067] (In the formula, R b1 represents hydrogen, a linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group of C 1～30 , or an aromatic hydrocarbon group,

[0068] The above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic hydrocarbon group may each be substituted with fluorine, a hydroxyl group, an alkoxy group, an aldehyde (-CHO), a carboxyl group, or -COOR' (wherein R' is an alkyl group having 1 to 8 carbon atoms), and in the above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic hydrocarbon group, one or more methylene groups may be replaced with an oxygen group or an imino group, provided that R b1 is neither a hydroxyl group nor an alkoxy group)

[0069] It should be noted that here, the above-mentioned methylene group also includes the terminal methyl group.

[0070] In addition, the above-mentioned "substituted with fluorine, a hydroxyl group, an alkoxy group, an aldehyde, a carboxyl group, or -COOR'" means that the hydrogen atom directly bonded to the carbon atom in the aliphatic hydrocarbon group and the aromatic hydrocarbon group can be replaced with fluorine, a hydroxyl group, an alkoxy group, an aldehyde, a carboxyl group, or -COOR'. The same applies to other similar descriptions in this specification.

[0071] In the repeating unit represented by formula (Ib), as R b1 , for example, there may be mentioned (i) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl, (ii) aryl groups such as phenyl, tolyl, and benzyl, (iii) fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl, (iv) fluoroaryl groups, (v) cycloalkyl groups such as cyclohexyl, (vi) nitrogen-containing groups having an amino or imide structure such as isocyanate and amino, (vii) oxygen-containing groups having an epoxy structure such as glycidyl, (viii) carboxyl-containing groups such as carboxymethyl and dicarboxyl. Preferred are methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl, isocyanate, and carboxyl. As the fluoroalkyl group, a perfluoroalkyl group is preferred, especially trifluoromethyl and pentafluoroethyl. When R b1 is methyl, the raw material is easily obtained, the cured film has high hardness, and has high chemical resistance, so it is preferred. In addition, when R b1 is phenyl, the solubility of the polysiloxane in the solvent is increased, and the cured film is not easily broken, so it is preferred. In addition, when R b1 has a hydroxyl group, a glycidyl group, an isocyanate group or an amino group, the adhesion to the substrate is improved, so it is preferred.

[0072] As the polysiloxane used in the present invention, for example, polysiloxanes containing the following structures can be mentioned.

[0073]

[0074] If the ratio of the repeating unit represented by formula (Ib) is high, the strength and heat resistance of the formed cured film are improved, but the adhesion is reduced. Therefore, it is preferably 0 to 90 mol% relative to the total number of repeating units of the polysiloxane.

[0075] The polysiloxane used in the present invention preferably contains repeating units represented by formula (Ic).

[0076]

[0077] The polysiloxane used in the present invention may also contain repeating units represented by formula (Id).

[0078]

[0079] In the formula, R d1 is a group obtained by removing a plurality of hydrogens from a nitrogen- and / or oxygen-containing alicyclic hydrocarbon compound containing an amino group, an imino group, and / or a carbonyl group. Here, the alicyclic hydrocarbon compound has a cyclic structure and may also contain a linear or branched structure as needed.

[0080] In formula (Id), as R d1 , it is preferably a group obtained by removing a plurality of, more preferably 2 or 3 hydrogens from a nitrogen-containing alicyclic hydrocarbon ring containing an imino group and / or a carbonyl group, and more preferably a 5-membered or 6-membered ring containing nitrogen in its constituent members. For example, groups obtained by removing 2 or 3 hydrogens from piperidine, pyrrolidine, and isocyanurate can be cited. The group not bonded to oxygen in formula (Id) connects the Si atoms contained in a plurality of repeating units.

[0081] When the ratio of the repeating units represented by formula (Id) and formula (Ic) is high, the sensitivity of the composition decreases, the compatibility with solvents or additives decreases, and the film stress increases, so cracks are likely to occur. Therefore, it is preferably 40 mol% or less, more preferably 20 mol% or less, based on the total number of repeating units of the polysiloxane.

[0082] The polysiloxane used in the present invention may also contain repeating units represented by formula (Ie).

[0083]

[0084] In the formula, R e1 are each independently hydrogen, a linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group of C 1～30 , or an aromatic hydrocarbon group,

[0085] the aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group may be further substituted with fluorine, a hydroxyl group, or an alkoxy group, and in the aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group, a methylene group may be replaced by an oxygen group or an imino group, provided that R e1 is not a hydroxyl group nor an alkoxy group.

[0086] It should be noted that here, the aforementioned methylene group also includes the terminal methyl group.

[0087] In the repeating unit represented by formula (Ie), as R e1 , for example, the following can be enumerated: (i) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; (ii) aryl groups such as phenyl, tolyl, and benzyl; (iii) fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl; (iv) fluoroaryl groups; (v) cycloalkyl groups such as cyclohexyl; (vi) nitrogen-containing groups having an amino or imide structure such as isocyanate and amino; (vii) oxygen-containing groups having an epoxy structure such as glycidyl. Methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl, and isocyanate are preferred. As the fluoroalkyl group, a perfluoroalkyl group is preferred, particularly trifluoromethyl and pentafluoroethyl. When R e1 is methyl, the raw material is easily obtained, the cured film has high hardness, and has high chemical resistance, so it is preferred. In addition, when R e1 is phenyl, the solubility of the polysiloxane in the solvent is increased, and the cured film is not easily broken, so it is preferred. Further, when R e1 has a hydroxyl group, glycidyl group, isocyanate group or amino group, the adhesion to the substrate is improved, so it is preferred.

[0088] By having the repeating unit represented by the above formula (Ie), the polysiloxane used in the present invention can have a partially linear structure. However, since the heat resistance is reduced, a small amount of the linear structure portion is preferred. Specifically, relative to the total number of repeating units of the polysiloxane, the repeating unit represented by formula (Ie) is preferably 30 mol% or less.

[0089] The polysiloxane used in the present invention has a structure formed by block-bonding the above-described repeating units, but preferably has a silanol group at the terminal. Such a silanol group is a group formed by bonding the bonding end of the foregoing repeating unit or block to -O 0.5 H.

[0090] The weight-average molecular weight of the polysiloxane used in the present invention is not particularly limited. However, the higher the molecular weight, the more likely the coating property is to be improved. On the other hand, the lower the molecular weight, the fewer the restrictions on the synthesis conditions, the easier the synthesis, and the synthesis of a polysiloxane with a very high molecular weight is difficult. For such reasons, the weight-average molecular weight of the polysiloxane is usually 1,500 to 20,000, and preferably 2,000 to 15,000 in consideration of the solubility in an organic solvent and the solubility in an alkaline developer. Here, the weight-average molecular weight is the weight-average molecular weight in terms of polystyrene and can be measured by gel permeation chromatography based on polystyrene.

[0091] The polysiloxane used in the present invention may also be a mixture composed of a polysiloxane containing the repeating unit shown in (Ia) and a polysiloxane containing any of the repeating units shown in (Ia'), (Ib) to (Ie) and not containing the repeating unit shown in (Ia).

[0092] The polysiloxane containing (Ia) is obtained through the following steps, for example:

[0093] (1) Hydrolyzing and polymerizing the silane monomer or its mixture shown in formula (ia), if necessary, in the presence of an acidic catalyst or a basic catalyst, to obtain an acryloyl group-containing polysiloxane:

[0094]

[0095] (In the formula, R a1” is hydrogen or methyl, ma” is an integer from 1 to 6, preferably an integer from 1 to 3, most preferably 3, and R ia is a linear or branched C 1～6 alkyl), and

[0096] (2) Breaking the carbon-carbon double bond in the obtained acryloyl group-containing polysiloxane and polymerizing it.

[0097] Here, the above mixture may also be a mixture of the silane monomer shown in formula (ia) and other silane monomers shown in formula (ia), or a mixture with the silane monomers shown in the following (ib) to (ie), or a mixture with compounds other than silane monomers.

[0098] The polysiloxane obtained by the above process can provide a composition with excellent properties. The obtained structure includes, for example, the structures exemplified above, but various structures can be obtained according to the type and ratio of the monomers, etc. Therefore, it is considered that structures other than those exemplified above can also be obtained.

[0099] [Step (1)]

[0100] In formula (ia), preferred R ia include methyl, ethyl, n-propyl, isopropyl, and n-butyl, etc. In formula (ia), there are multiple R ia , but each R ia can be the same or different.

[0101] It is preferred to further combine the silane monomer shown in formula (ib) in the silane monomer shown in formula (ia):

[0102] R b1’ -Si-(OR ib ) 3 (ib)

[0103] (In the formula, Rb1’ represents hydrogen, C 1～30 a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with fluorine, a hydroxyl group, an alkoxy group, an aldehyde (-CHO), a carboxyl group, or -COOR' (where R' is an alkyl group having 1 to 8 carbon atoms), and in the aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group, a methylene group may be replaced with an oxygen atom or an imino group, provided that R b1’ is not a hydroxyl group nor an alkoxy group, and R ib is a linear or branched C 1～6 alkyl group).

[0104] In formula (ib), the preferred R b1’ is the same as the above-mentioned preferred R b1 . Preferred R ib include methyl, ethyl, n-propyl, isopropyl, and n-butyl, etc.

[0105] As specific examples of the silane monomer represented by formula (ib), for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane can be cited. Among them, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and phenyltrimethoxysilane are preferred. The silane monomers represented by formula (ib) can also be combined in two or more kinds.

[0106] An acrylic polymerized polysiloxane can also be obtained by further combining the silane monomers represented by the following formula (ic) and / or (id) in the silane monomers represented by the above formula (ia) and / or (ib). When using the silane monomers represented by formula (ic) and / or formula (id) in this way, a polysiloxane containing repeating units (Ic) and / or (Id) can be obtained.

[0107] Si(OR ic ) 4 (ic)

[0108] R d1’ -Si-(OR id ) 3 (id)

[0109] In the formula, R ic and R idEach is independently a linear or branched C 1～6 alkyl group, and examples thereof include methyl, ethyl, n-propyl, isopropyl, and n-butyl. A plurality of R ic and R id are included in one monomer, but each R ic and R id may be the same or different,

[0110] R d1’ is a group obtained by removing a plurality of hydrogens from a nitrogen- and / or oxygen-containing cycloaliphatic hydrocarbon compound containing an amino group, an imino group, and / or a carbonyl group. Preferred R d1’ is the same as the above-mentioned preferred R d1 .

[0111] Specific examples of the silane monomer represented by the formula (ic) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and the like.

[0112] Specific examples of the silane monomer represented by the formula (id) include tris(3-trimethoxysilylpropyl) isocyanurate, tris(3-triethoxysilylpropyl) isocyanurate, tris(3-trimethoxysilylethyl) isocyanurate, and the like.

[0113] Furthermore, the following silane monomer represented by the formula (ie) can also be combined. When the silane monomer represented by the formula (ie) is used, a polysiloxane containing a repeating unit (Ie) can be obtained.

[0114] (R e1’ ) 2 -Si-(OR ie ) 2 (ie)

[0115] In the formula, R ie are each independently a linear or branched C 1～6 alkyl group, and examples thereof include methyl, ethyl, n-propyl, isopropyl, and n-butyl. A plurality of R ie are contained in one monomer, but each R ie may be the same or different,

[0116] R e1’ are each independently hydrogen, a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group of C 1～30 , or an aromatic hydrocarbon group,

[0117] The aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group may each be substituted with fluorine, a hydroxyl group or an alkoxy group, and in the aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group, a methylene group may be replaced with an oxygen group or an imino group, but R e1’ is not a hydroxyl group nor an alkoxy group. Preferred Re1’ is the same as the above-preferred R e1 identical.

[0118] As specific examples of the silane monomer represented by the formula (ie), dimethyldiethoxysilane, diphenyldimethoxysilane, etc. can be cited.

[0119] [Process (2)]

[0120] In process (2), the carbon-carbon double bond of the acryloyl group in the obtained acryloyl group-containing polysiloxane is cleaved and polymerized. In this reaction, as the polymerization initiator, azo initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropionic acid) dimethyl, etc., and peroxide initiators such as benzoyl peroxide, tert-butyl hydroperoxide (70% aqueous solution), α,α-dimethylbenzyl hydroperoxide, tert-butyl peroxide, bis(1-methyl-1-phenylethyl) peroxide, etc. are preferably used. The carbon-carbon double bond of the acryloyl group is cleaved and polymerized, but a part of it can remain without cleavage and polymerization.

[0121] The content of the polymerization initiator is not particularly limited, and is preferably 0.1 to 500 mol% relative to the number of acrylic acid functional groups.

[0122] In process (2),

[0123] the polymerization reaction can also be carried out in the coexistence of the acrylate monomer represented by the formula (a'):

[0124]

[0125] (In the formula, R a2’ is hydrogen or methyl, R a3’ is hydrogen, a hydrocarbon group of C 1～50 One or more methylenes in the aforementioned hydrocarbon group can also be replaced by an oxy group, an imino group, and / or a carbonyl group. The preferred R a3’ is the same as the above-preferred R a3 identical, and x is an integer of 1 to 6, preferably an integer of 3 to 6)

[0126] The above-mentioned methylene also includes the terminal methyl.

[0127] In addition, the acrylic monomer represented by formula (a') may have multiple acrylate groups in the molecule, and may be a nitrogen- and / or oxygen-containing cycloaliphatic hydrocarbon compound containing an amino group, an imino group and / or a carbonyl group (preferably a nitrogen-containing aliphatic hydrocarbon ring containing an imino group and / or a carbonyl group, more preferably a 5-membered or 6-membered ring containing nitrogen in the constituent members, and most preferably a piperidine derivative, a pyrrolidine derivative or an isocyanurate derivative).

[0128] Examples of the acrylate monomer represented by formula (a') include methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, phenoxypolyethylene glycol acrylate, isostearyl acrylate, polyethylene glycol diacrylate, propoxylated bisphenol A diacrylate, tricyclodecane dimethanol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated glycerol triacrylate, trimethylolpropane triacrylate, bis-trimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate. Methoxypolyethylene glycol acrylate, tricyclodecane dimethanol diacrylate, and ethoxylated isocyanuric acid triacrylate are preferred.

[0129] In addition, during the radical polymerization reaction, well-known chain transfer agents, polymerization inhibitors, molecular weight regulators, etc. can be appropriately used to control the molecular weight. Furthermore, the polymerization reaction can be carried out in one step or in two or more steps. The temperature of the polymerization reaction is not particularly limited, but typically it is in the range of 50°C to 200°C, preferably in the range of 80°C to 150°C.

[0130] Since the polysiloxane polymerized with acrylic acid in step (2) has a complex three-dimensional structure due to the polymerization of acrylic acid, it is considered to contribute to improving the heat resistance and the adhesion to the substrate.

[0131] The weight-average molecular weight of the polysiloxane polymerized with acrylic acid obtained in step (2) is preferably 1.4 to 5 times, more preferably 1.4 to 3 times, the weight-average molecular weight of the acryloyl group-containing polysiloxane obtained in step (1).

[0132] The polysiloxane without the repeating unit represented by (Ia) is obtained in the same manner as in the above step (1).

[0133] (Acrylic resin)

[0134] The alkali-soluble resin used in the present invention may be a carboxyl group-containing acrylic resin (hereinafter, simply referred to as "acrylic resin" or "acrylic polymer"). Commonly used acrylic resins may be selected from, for example, polyacrylic acid, polymethacrylic acid, polyalkyl acrylate, polyalkyl methacrylate, etc. The acrylic resin used in the present invention preferably further contains an acryloyl group-containing repeating unit, and in addition, preferably further contains an alkoxysilyl group-containing repeating unit.

[0135] The acrylic resin used in the present invention is not particularly limited as long as it is an acrylic resin containing a repeating unit having a carboxyl group in the side chain, and preferably a repeating unit derived from an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof.

[0136] The alkoxysilyl group only needs to be contained as a repeating unit having an alkoxysilyl group in the side chain, and preferably a repeating unit derived from a monomer represented by the following formula (B).

[0137] X B -(CH 2 ) a -Si(OR B ) b (CH 3 ) 3-b (B)

[0138] In the formula, X B is vinyl, styryl or (meth)acryloyloxy, R B is methyl or ethyl, a is an integer of 0 to 3, and b is an integer of 1 to 3.

[0139] In addition, the acrylic resin used in the present invention preferably contains a hydroxyl group-containing repeating unit derived from a hydroxyl group-containing unsaturated monomer.

[0140] The weight-average molecular weight of the alkali-soluble resin of the present invention is not particularly limited, and is preferably 1,000 to 40,000, more preferably 2,000 to 30,000. Here, the weight-average molecular weight is the weight-average molecular weight in terms of polystyrene obtained by gel permeation chromatography. In addition, from the viewpoint of being able to be developed with a low-concentration alkaline developer and taking into account reactivity and storage stability, in terms of the number of acid groups, the acid value of the solid content is usually 40 to 190 mg KOH / g, more preferably 60 to 150 mg KOH / g.

[0141] Since the polysiloxane containing the repeating unit represented by (Ia) can form a thick film even when used alone, it is preferable to use a polysiloxane containing the repeating unit represented by (Ia) as the alkali-soluble resin.

[0142] When using a polysiloxane that does not contain the repeating unit shown in (Ia), a mixture of the polysiloxane and an acrylic resin can be used as the alkali-soluble resin. In this case, the ratio of the acrylic resin to the polysiloxane is not particularly limited. However, when the coating film is made into a thick film, it is preferable that the ratio of the acrylic resin is large. On the other hand, when applied to high-temperature processing, or from the viewpoints of transparency and chemical resistance after curing, it is preferable that the ratio of the polysiloxane is large. For these reasons, the ratio of the polysiloxane to the acrylic resin is preferably 90:10 to 10:90, more preferably 85:15 to 25:75.

[0143] In addition, the composition of the present invention is coated on a substrate, and after imagewise exposure and development, a cured film is formed. At this time, it is necessary to have a difference in solubility between the exposed part and the unexposed part, and the coating film of the unexposed part should have a solubility of a certain level or more in the developer. For example, as long as the dissolution rate (hereinafter simply referred to as the alkali dissolution rate or ADR; details will be described later) of the coating film after pre-baking in the developer used is / second or more, it is considered that a pattern can be formed by exposure-development. However, since the required solubility varies depending on the average film thickness of the cured film formed or the development conditions, the alkali-soluble resin should be appropriately selected according to the development conditions. Although it varies depending on the types and addition amounts of the photosensitizer and the silanol group condensation catalyst contained in the composition, for example, as long as the average film thickness is 0.1 to 100 μm (1,000 to ), the dissolution rate in the developer used is preferably 50 to / second, and more preferably 100 to / second.

[0144] [Method for measuring and calculating alkali dissolution rate (ADR)]

[0145] The alkali dissolution rate of the alkali-soluble resin is measured and calculated as follows using the developer, i.e., the alkali solution.

[0146] The alkali-soluble resin is diluted to 35% by mass in propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) and dissolved with a stirrer for 1 hour at room temperature. In a dust-free room with a temperature of 23.0 ± 0.5 °C and a humidity of 50 ± 5.0%, 1 cc of the prepared alkali-soluble resin solution is dropped onto the central part of a 4-inch silicon wafer with a thickness of 525 μm with a pipette, spin-coated to a thickness of 2 ± 0.1 μm, and then heated on a hot plate at 100 °C for 90 seconds to remove the solvent. The film thickness of the coating film is measured with a spectroscopic ellipsometer (JA Woollam Co., Ltd.).

[0147] Next, the silicon wafer with the film is gently immersed in a 6-inch diameter glass petri dish containing 100 ml of a developer with a specified concentration adjusted to 23.0 ± 0.1 °C, and then left standing. The time until the film coating disappears is measured. The dissolution rate is obtained by dividing the time it takes for the film to disappear in the inner part 10 mm from the wafer edge. In the case where the dissolution rate is very slow, the wafer is immersed in the developer for a certain period of time, and then heated on a hot plate at 200 °C for 5 minutes to remove the moisture mixed into the film during the dissolution rate measurement. Then, the film thickness is measured, and the dissolution rate is calculated by dividing the change in film thickness before and after immersion by the immersion time. The above measurement method is performed 5 times, and the average value of the obtained values is taken as the dissolution rate of the alkali-soluble resin.

[0148] (II) Polymerization initiator

[0149] The composition of the present invention contains a polymerization initiator. The polymerization initiator includes a polymerization initiator that generates an acid, a base, or a free radical by radiation and a polymerization initiator that generates an acid, a base, or a free radical by heat. In the present invention, since the reaction starts immediately after radiation, the process of reheating after radiation and before the development process can be omitted. Therefore, the former is preferred in terms of shortening the process and cost, and a photo radical generator is more preferred.

[0150] The photo radical generator can improve the resolution by enhancing the shape of the pattern or increasing the contrast of development. The photo radical generator used in the present invention is a photo radical generator that emits free radicals when irradiated with radiation. Here, examples of the radiation include visible light, ultraviolet light, infrared light, X-rays, electron beams, α-rays, γ-rays, etc.

[0151] The optimal addition amount of the photo radical generator varies depending on the type and amount of the active substance generated by the decomposition of the photo radical generator, the required sensitivity, and the dissolution contrast between the exposed part and the unexposed part. However, based on the total mass of the alkali-soluble resin, it is preferably 0.001 to 50% by mass, and more preferably 0.01 to 30% by mass. When the addition amount is less than 0.001% by mass, the dissolution contrast between the exposed part and the unexposed part is too low, and sometimes the addition effect is not achieved. On the other hand, when the addition amount of the photo radical generator exceeds 50% by mass, cracks may occur in the formed coating film, or coloring due to the decomposition of the photo radical generator may become obvious, resulting in a decrease in the colorless transparency of the coating film. In addition, if the addition amount is large, due to the thermal decomposition of the photo radical generator, the electrical insulation of the cured product deteriorates and gas evolution occurs, causing problems in subsequent processes. Furthermore, the resistance of the coating film to a photoresist stripper using monoethanolamine or the like as a main reagent sometimes decreases.

[0152] Examples of the photo radical generator include azo compounds, peroxides, acylphosphine oxides, alkyl phenyl ketones, oxime esters, titanocene initiators. Among them, alkyl phenyl ketones, acylphosphine oxides, and oxime esters are preferred initiators, and examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], acetophenone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetoxime), and the like.

[0153] (V) A compound having two or more (meth)acryloyloxy groups

[0154] The composition of the present invention contains a compound having two or more (meth)acryloyloxy groups (hereinafter, sometimes simply referred to as a compound having a (meth)acryloyloxy group). Here, the (meth)acryloyloxy group is a general term for an acryloyloxy group and a methacryloyloxy group. This compound is a compound that can react with the aforementioned polysiloxane and the aforementioned alkali-soluble resin to form a crosslinked structure. Here, in order to form a crosslinked structure, a compound having two or more acryloyloxy groups or methacryloyloxy groups as reactive groups is required, and in order to form a higher-order crosslinked structure, a compound having three or more acryloyloxy groups or methacryloyloxy groups is preferred.

[0155] As such a compound having two or more (meth)acryloyloxy groups, esters obtained by reacting (α) a polyol compound having two or more hydroxyl groups with (β) two or more (meth)acrylic acids are preferably used. As the polyol compound (α), compounds having a saturated or unsaturated aliphatic hydrocarbon, aromatic hydrocarbon, heterocyclic hydrocarbon, primary amine, secondary amine or tertiary amine, ether, etc. as a basic skeleton and having two or more hydroxyl groups as substituents can be cited. Within the range not damaging the effects of the present invention, the polyol compound may further contain other substituents such as a carboxyl group, a carbonyl group, an amino group, an ether bond, a thiol group, a thioether bond, and the like.

[0156] As preferred polyol compounds, alkyl polyols, aryl polyols, polyalkanolamines, cyanuric acid, dipentaerythritol, etc. can be cited. Here, when the polyol compound (α) has three or more hydroxyl groups, it is not necessary for all hydroxyl groups to react with (meth)acrylic acid, and some can be esterified. That is, this ester can have unreacted hydroxyl groups. As such esters, tris(2-acryloyloxyethyl) isocyanurate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, polybutylene glycol dimethacrylate, trimethylolpropane trimethacrylate, bis(trimethylolpropane) tetraacrylate, tricyclodecane dimethanol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, etc. can be cited. Among them, from the viewpoints of reactivity and the number of crosslinkable groups, tris(2-acryloyloxyethyl) isocyanurate and dipentaerythritol hexaacrylate are preferred. In addition, in order to adjust the shape of the formed pattern, two or more of these compounds can be combined. Specifically, it is preferred to combine a compound containing three (meth)acryloyloxy groups and a compound containing two (meth)acryloyloxy groups.

[0157] From the viewpoint of reactivity, such a compound is preferably a molecule relatively smaller than the alkali-soluble resin. Therefore, the molecular weight is preferably 2,000 or less, and more preferably 1,500 or less.

[0158] Based on the total mass of the alkali-soluble resin, the content of the (meth)acryloyloxy group-containing compound is 40 to 300% by mass, preferably 50 to 100% by mass. In addition, these (meth)acryloyloxy group-containing compounds can be used alone or in combination of two or more.

[0159] (IV) Solvent

[0160] The composition of the present invention contains a solvent. The solvent is not particularly limited as long as it can uniformly dissolve or disperse the aforementioned alkali-soluble resin, black colorant, polymerization initiator, and additives added as needed. Examples of solvents that can be used in the present invention include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; propylene glycol alkyl ether acetates such as PGMEA, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters such as ethyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone, etc. Among these, from the viewpoints of easy availability, easy handling, and solubility of the polymer, propylene glycol alkyl ether acetates or esters, and straight-chain or branched-chain alcohols having 4 or 5 carbon atoms in the alkyl group are preferably used. From the viewpoints of coatability and storage stability, the solvent ratio of the alcohol is preferably 5 to 80%.

[0161] The solvent content rate of the composition of the present invention can be arbitrarily adjusted according to methods such as the method of coating the composition. For example, in the case of coating the composition by spraying, the proportion of the solvent in the composition can be 90% by mass or more. In addition, in the case of slit coating for coating a large substrate, it is usually 60% by mass or more, preferably 70% by mass or more. The characteristics of the composition of the present invention do not change significantly with the amount of the solvent.

[0162] The composition of the present invention requires the aforementioned (I) to (IV), but further compounds can be combined as needed. The materials that can be combined are described below.

[0163] (V) Sugar

[0164] The composition of the present invention may further contain sugar. The sugar can be any of monosaccharides, oligosaccharides, or polysaccharides, but oligosaccharides are preferred. Here, the oligosaccharides in this specification refer to sugars formed by dehydration condensation of 2 to 10 molecules of monosaccharides, and also include cyclic oligosaccharides (such as cyclodextrin). Among these sugars, disaccharides formed by condensation of 2 molecules of cyclodextrin or monosaccharides are preferred, and disaccharides formed by condensation of 2 molecules of monosaccharides are more preferred. In addition, the sugar is preferably an alkylene oxide having 1 to 6 carbon atoms, more preferably an alkylene oxide having 2 to 5 carbon atoms, and further preferably an ethylene oxide or propylene oxide adduct. That is, it is preferred that the hydroxyl group (-OH) contained in the sugar is replaced by -(C x H 2x -O-)y -H substitution. Here, x is an integer from 2 to 6, preferably an integer from 2 to 5, more preferably 2 or 3, and y is an integer from 1 to 8, more preferably an integer from 2 to 5.

[0165] According to the research of the present inventors, it was found that these sugars have a dissolution promoting effect in the developer. Since sugars have hydrophilicity and hydrophobicity, they dissolve in the solvent of the composition and also dissolve in the developer, and are considered to have a dissolution promoting effect. When the composition of the present invention is developed with a low-concentration developer, this effect is particularly beneficial.

[0166] Based on the total mass of the alkali-soluble resin, the content of the sugar used in the present invention is preferably 1 to 80% by mass, more preferably 10 to 50% by mass, and further preferably 30 to 50% by mass.

[0167] Based on the total mass of the composition, the content of the components other than (I) to (V) in the whole composition is preferably 30% or less, more preferably 20% or less, and further preferably 10% or less.

[0168] (VI) Other additives

[0169] The composition of the present invention may further contain other additives as needed.

[0170] Examples of such additives include developer dissolution promoters, scum removers, thickeners, polymerization inhibitors, defoamers, surfactants, sensitizers, crosslinking agents, curing agents, etc.

[0171] The developer dissolution promoter or scum remover has the function of adjusting the solubility of the formed coating film in the developer or preventing scum from remaining on the substrate after development. As such an additive, crown ether can be used. As the crown ether, the crown ether having the simplest structure is represented by the general formula (-CH 2 -CH 2 -O-) nrepresentation. Among these, crown ethers with n being 4 to 7 are preferred in the present invention. Crown ethers can be referred to as x-crown-y-ethers, where x is the total number of atoms constituting the ring and y is the number of oxygen atoms contained therein. In the present invention, crown ethers with x = 12, 15, 18 or 21 and y = x / 3, and crown ethers selected from the group consisting of these benzocondensates and cyclohexyl condensates are preferred. Specific examples of more preferred crown ethers are 21-crown-7-ether, 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, dibenzo-21-crown-7-ether, dibenzo-18-crown-6-ether, dibenzo-15-crown-5-ether, dibenzo-12-crown-4-ether, dicyclohexyl-21-crown-7-ether, dicyclohexyl-18-crown-6-ether, dicyclohexyl-15-crown-5-ether and dicyclohexyl-12-crown-4-ether. In the present invention, crown ethers selected from 18-crown-6-ether and 15-crown-5-ether are most preferred among these. Based on the total mass of the alkali-soluble resin, its content is preferably 0.05 to 15% by mass, and more preferably 0.1 to 10% by mass.

[0172] When using the composition of the present invention to form a cured film, the tackifier has the effect of preventing the pattern from peeling off due to the stress applied after firing. As the tackifier, imidazoles, silane coupling agents, etc. are preferred. Among imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole and 2-aminoimidazole are preferred, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole and imidazole are particularly preferably used.

[0173] As the silane coupling agent, known ones are preferably used, and examples thereof include epoxy group-containing silane coupling agents, amino group-containing silane coupling agents, mercapto group-containing silane coupling agents, etc. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. are preferred. They can be used alone or in combination of multiple kinds. Based on the total mass of the alkali-soluble resin, its addition amount is preferably 0.05 to 15% by mass.

[0174] In addition, as the silane coupling agent, silane compounds having acid groups, siloxane compounds, etc. can also be used. As the acid group, carboxyl group, acid anhydride group, phenolic hydroxyl group, etc. can be cited. When containing monobasic acid groups such as carboxyl group and phenolic hydroxyl group, it is preferred that a single silicon-containing compound has multiple acid groups.

[0175] As a specific example of such a silane coupling agent, the compound represented by the formula (C) can be cited:

[0176] X n Si(OR 3 ) 4-n (C)

[0177] or a polymer having it as a repeating unit. At this time, X or R 3 different repeating units can also be used in combination.

[0178] In formula (C), as R 3 , hydrocarbon groups such as alkyl groups such as methyl, ethyl, n-propyl, isopropyl, and n-butyl can be cited. In general formula (C), there are a plurality of R 3 , but each R 3 can be the same or different.

[0179] As X, groups having acid groups such as phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, sulfo, and alcohol groups can be cited, and groups in which these acid groups are protected by acetyl, aryl, pentyl, benzyl, methoxymethyl, methanesulfonyl, tolyl, trimethoxysilyl, triethoxysilyl, triisopropylsilyl, or triphenylmethyl, etc., and acid anhydride groups.

[0180] Among these, substances having methyl as R 3 and having a carboxylic anhydride group as X are preferred, such as silicone containing an acid anhydride group. More specifically, a polymer containing a compound represented by the following formula (X-12-967C (trade name, Shin-Etsu Chemical Co., Ltd.)) or a structure similar thereto at the end or side chain of a silicone-containing polymer such as silicone is preferred.

[0181]

[0182] In addition, compounds in which acid groups such as thiol, phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, and sulfo are added to the end portion of dimethyl silicone are also preferred. As such compounds, compounds represented by the following formulas (X-22-2290AS and X-22-1821 (both are trade names, Shin-Etsu Chemical Co., Ltd.)) can be cited.

[0183]

[0184] When the silane coupling agent contains a silicone structure, if the molecular weight is too large, the compatibility with the polysiloxane contained in the composition deteriorates, the solubility in the developer does not increase, and the reactive groups remain in the film, which may cause adverse effects such as the inability to maintain chemical resistance that can withstand subsequent processes. Therefore, the weight average molecular weight of the silane coupling agent is preferably 5000 or less, more preferably 4000 or less. The content of the silane coupling agent is preferably 0.01 to 15% by mass based on the total mass of the alkali-soluble resin.

[0185] As polymerization inhibitors, in addition to nitronium nitrate, nitroxyl radicals, hydroquinone, catechol, phenothiazine, phenoxazine, hindered amines and their derivatives, ultraviolet absorbers can also be added. Among them, methyl hydroquinone, catechol, 4-tert-butylcatechol, 3-methoxycatechol, phenothiazine, chlorpromazine, phenoxazine, TINUVIN 144, 292, 5100 (manufactured by BASF) as hindered amines, and TINUVIN 326, 328, 384-2, 400, 477 (manufactured by BASF) as ultraviolet absorbers are preferred. They can be used alone or in combination of multiple types. Based on the total mass of the alkali-soluble resin, their content is preferably 0.01 to 20% by mass.

[0186] As defoaming agents, alcohols (C 1～18 ), higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glycerol monolaurate, polyethers such as polyethylene glycol (PEG) (Mn 200 to 10,000) and polypropylene glycol (PPG) (Mn 200 to 10,000), silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil, and fluorosilicone oil, and silicone surfactant described in detail below can be cited. They can be used alone or in combination of multiple types. Based on the total mass of the alkali-soluble resin, their content is preferably 0.1 to 3% by mass.

[0187] In addition, as needed, the composition of the present invention may further contain a surfactant. The purpose of adding the surfactant is to improve coating characteristics, developability, etc. As the surfactant that can be used in the present invention, for example, nonionic surfactants, anionic surfactants, amphoteric surfactants, etc. can be cited.

[0188] As nonionic surfactants, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether, polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters, polyoxyethylene-polyoxypropylene block polymers, acetylenic alcohols, acetylenic diols, polyethoxylates of acetylenic alcohols, polyethoxylates of acetylenic diols and other acetylenic diol derivatives, fluorosurfactants such as Fluorad (trade name, Sumitomo 3M Limited), Megafac (trade name, DIC Corporation), Surflon (trade name, Asahi Glass Co., Ltd.), or silicone surfactants such as KP341 (trade name, Shin-Etsu Chemical Co., Ltd.) can be cited. As the aforementioned acetylenic diols, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyn-3,6-diol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, 2,5-dimethyl-2,5-hexanediol, etc. can be cited.

[0189] In addition, examples of the anionic surfactant include ammonium salts or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyl diphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkyl benzene sulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfate, ammonium salts or organic amine salts of alkyl sulfate, and the like.

[0190] Furthermore, examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolium betaine, lauramidopropyl hydroxysulfobetaine, and the like.

[0191] These surfactants can be used alone or in combination of two or more. Based on the total mass of the composition, their content is preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass.

[0192] In addition, a sensitizer can be added to the composition of the present invention as needed.

[0193] As the sensitizer preferably used in the composition of the present invention, coumarin, coumarinone and their derivatives, thiopyrylium salts, acetophenones, etc. can be mentioned. Specifically, bis(o-methylstyryl)benzene, 7-dimethylamino-4-methylquinolone-2, 7-amino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 2-(p-dimethylaminostyryl)-pyridylmethyl iodide, 7-diethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 2,3,5,6-1H,4H-tetrahydro-8-methylquinazino-<9,9a,1-gh>coumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-dimethylamino-4-trifluoromethylcoumarin, 7-amino-4-trifluoromethylcoumarin, 2,3,5,6-1H,4H-tetrahydroquinazino-<9,9a,1-gh>coumarin, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, 2,3,5,6-1H,4H-tetrahydro-9-ethoxycarbonylquinazino-<9,9a,1-gh>coumarin, 3-(2'-N-methylbenzimidazolyl)-7-N,N-diethylaminocoumarin, N-methyl-4-trifluoromethylpiperidino-<3,2-g>coumarin, 2-(p-dimethylaminostyryl)-benzothiazolylethyl iodide, 3-(2'-benzimidazolyl)-7-N,N-diethylaminocoumarin, 3-(2'-benzothiazolyl)-7-N,N-diethylaminocoumarin, and sensitizing dyes such as pyrrylium salts and thiopyrylium salts represented by the following chemical formulas can be mentioned. By adding the sensitizing dye, patterning using an inexpensive light source such as a high-pressure mercury lamp (360 to 430 nm) becomes possible. Based on the total mass of the alkali-soluble resin, its content is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass.

[0194]

[0195] X <![CDATA[R 21 > <![CDATA[R 22 > <![CDATA[R 23 > Y S <![CDATA[OC 4 H 9 > H H <![CDATA[BF 4 > S <![CDATA[OC 4 H 9 > <![CDATA[OCH 3 > <![CDATA[OCH 3 > <![CDATA[BF 4 > S H <![CDATA[OCH 3 > <![CDATA[OCH 3 > <![CDATA[BF 4 > S <![CDATA[N(CH 3 ) 2 > H H <![CDATA[ClO 2 > O <![CDATA[OC 4 H 9 > H H <![CDATA[SbF 6 >

[0196] In addition, as the sensitizer, a compound containing an anthracene skeleton can be used. Specifically, the compounds represented by the following formulas can be mentioned.

[0197]

[0198] In the formula, R 31 each independently represents a substituent selected from the group consisting of an alkyl group, an aralkyl group, an allyl group, a hydroxyalkyl group, an alkoxyalkyl group, a glycidyl group, and a haloalkyl group,

[0199] R 32Each independently represents a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group, and a carboalkoxy group.

[0200] k is each independently an integer selected from 0, 1 to 4.

[0201] When using such a sensitizer having an anthracene skeleton, based on the total mass of the alkali-soluble resin, its content is preferably 0.01 to 5% by mass.

[0202] <Method for forming a cured film>

[0203] The method for forming the cured film of the present invention includes: coating the aforementioned composition on a substrate to form a coating film, and exposing and developing the coating film. The method for forming the cured film will be described below in the order of processes.

[0204] (1) Coating process

[0205] First, coat the aforementioned composition on a substrate. The coating film of the composition of the present invention can be formed by any method known as a coating method for photosensitive compositions in the past. Specifically, it can be arbitrarily selected from dip coating, roll coating, bar coating, brush coating, spray coating, knife coating, flow coating, spin coating, and slit coating, etc. In addition, as the substrate for coating the composition, appropriate substrates such as a silicon substrate, a glass substrate, and a resin film can be used. According to needs, various semiconductor devices, etc. can be formed on these substrates. If the substrate is a thin film, gravure coating can also be used. Optionally, a drying process can be additionally provided after the coating film. In addition, the coating process can be repeated once or more than twice as needed to obtain the desired film thickness of the coating film to be formed.

[0206] (2) Pre-baking process

[0207] After forming a coating film by coating the composition, in order to dry the coating film and reduce the solvent residue amount in the coating film, it is preferable to perform pre-baking (pre-heat treatment) on the coating film. The pre-baking process is usually carried out at a temperature of 50 to 150 °C, preferably 90 to 120 °C, for 10 to 300 seconds, preferably 30 to 120 seconds when using a hot plate, and for 1 to 30 minutes when using a clean oven.

[0208] (3) Exposure process

[0209] After forming the coating film, light irradiation is performed on the surface of the coating film. As the light source for light irradiation, any light source commonly used in the pattern forming method can be used. Examples of such light sources include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, lamps such as xenon, laser diodes, LEDs, etc. As the irradiation light, ultraviolet rays such as g-line, h-line, and i-line are usually used. Except for ultra-fine processing such as semiconductors, light with a wavelength of 360 to 430 nm (high-pressure mercury lamp) is usually used for patterning with a size of several μm to several tens of μm. The energy of the irradiation light also depends on the light source and the film thickness of the coating film, but is usually 5 to 2,000 mJ / cm 2 , preferably 10 to 1,000 mJ / cm 2 . If the energy of the irradiation light is less than 10 mJ / cm 2 , sufficient resolution may not be obtained. On the contrary, if it is higher than 2,000 mJ / cm 2 , overexposure may occur, resulting in halation.

[0210] In order to irradiate light in accordance with the pattern shape, a usual photomask can be used. Such a photomask can be arbitrarily selected from known photomasks. The environment during irradiation is not particularly limited, and usually, an ambient atmosphere (in the air) or a nitrogen atmosphere is sufficient. In addition, when forming a film on the entire surface of the substrate, it is only necessary to irradiate light on the entire surface of the substrate. In the present invention, the pattern film also includes the case where a film is formed on the entire surface of the substrate.

[0211] (4) Post-exposure baking process

[0212] After exposure, the reaction between polymers in the film is promoted by a polymerization initiator, so post-exposure baking can be performed as needed. This heat treatment is different from the baking process (6) described later. It is not performed to completely cure the coating film, but to leave only the required pattern on the substrate after development, and the other parts are removed by development. Therefore, it is not essential in the present application.

[0213] When performing post-exposure heating, a hot plate, an oven, a furnace, etc. can be used. The heating temperature should not be too high because it is not preferable for the acid, base, or free radicals in the exposed area generated by light irradiation to diffuse into the unexposed area. From this perspective, the post-exposure heating temperature range is preferably 40°C to 150°C, more preferably 60°C to 120°C. If necessary, stepwise heating can also be applied to control the curing rate of the composition. In addition, the atmosphere during heating is not particularly limited, and for the purpose of controlling the curing rate of the composition, it can be selected from inert gases such as nitrogen, under vacuum, under reduced pressure, in oxygen, etc. In addition, the heating time is preferably a certain amount or more to maintain the uniformity of the temperature profile inside the wafer surface more highly. In addition, in order to suppress the diffusion of the generated acid, base, or free radicals, the heating time is preferably not too long. From such a perspective, the heating time is preferably 20 seconds to 500 seconds, more preferably 40 seconds to 300 seconds.

[0214] (5) Development process

[0215] After exposure, post-exposure heating is performed as needed, and then the coated film is developed. As the developer used during development, any developer used in the development of conventional photosensitive compositions can be used. As preferred developers, aqueous solutions of basic compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilicates (hydrates), alkali metal phosphates (hydrates), aqueous sodium carbonate solution, ammonia, alkylamines, alkanolamines, heterocyclic amines, etc., i.e., alkaline developers, are exemplified. Particularly preferred alkaline developers are aqueous solutions of tetramethylammonium hydroxide, aqueous potassium hydroxide solution or aqueous sodium hydroxide solution, and aqueous sodium carbonate solution. These alkaline developers can further contain water-soluble organic solvents such as methanol and ethanol, or surfactants as needed. In the present invention, development can be performed using a developer with a lower concentration than the 2.38 mass% TMAH developer usually used as a developer. As such a developer, for example, 0.05 to 1.5 mass% TMAH aqueous solution, 0.1 to 2.5 mass% aqueous sodium carbonate solution, 0.01 to 1.5 mass% aqueous potassium hydroxide solution, etc. can be exemplified. The development time is usually 10 to 300 seconds, preferably 30 to 180 seconds.

[0216] The development method can also be arbitrarily selected from conventionally known methods. Specifically, methods such as dipping in a developer, spin coating immersion, spraying, slit coating, curtain coating, and spraying can be exemplified. A pattern can be obtained through this development, and it is preferable to perform water washing after development with a developer.

[0217] (6) Heating process

[0218] After development, the obtained pattern film is cured by heating. As the heating device used in the heating step, the same heating device as that used in the post-exposure heating described above can be used. As the heating temperature in this heating step, there is no particular limitation as long as it is a temperature capable of curing the coating film, and it can be arbitrarily set. However, if the silanol group of the polysiloxane remains, the chemical resistance of the cured film becomes insufficient or the dielectric constant of the cured film becomes high. From this point of view, the heating temperature can be selected to be relatively high compared to normal. However, the composition of the present invention can be cured at a relatively low temperature. Specifically, it is preferably cured by heating at 350 °C or lower. In order to maintain a high residual film rate after curing, the curing temperature is more preferably 300 °C or lower, and particularly preferably 250 °C or lower. On the other hand, in order to promote the curing reaction and obtain a sufficient cured film, the curing temperature is preferably 70 °C or higher, and more preferably 100 °C or higher. In addition, the heating time is not particularly limited, and is usually 10 minutes to 24 hours, preferably 30 minutes to 3 hours. It should be noted that this heating time is the time after the temperature of the pattern film reaches the desired heating temperature. Usually, it takes several minutes to several hours for the temperature of the pattern film to reach the desired temperature from the temperature before heating.

[0219] The cured film thus obtained can achieve excellent transparency. For example, the light transmittance of a film cured at 100 °C can be 95% or more, and the relative dielectric constant is also 4 or less. In addition, since it can be developed with a low-concentration developer, the environmental performance is excellent. It is preferably used in various fields such as flat panel displays (FPDs), planarization films for the above-mentioned various devices, interlayer insulating films for low-temperature polysilicon, buffer coating films for IC chips, transparent protective films, etc.

[0220] Examples and comparative examples are listed below to further specifically illustrate the present invention, but the present invention is not limited by any of these examples and comparative examples.

[0221] Gel permeation chromatography (GPC) was measured using an HLC-8220GPC type high-speed GPC system (trade name, Tosoh Corporation) and two Super Multipore HZ-N type GPC columns (trade name, Tosoh Corporation). The measurement was carried out under the analysis conditions of using monodisperse polystyrene as the standard sample, tetrahydrofuran as the eluent, a flow rate of 0.6 ml / min, and a column temperature of 40 °C.

[0222] <Synthesis Example 1: Synthesis of Polysiloxane A>

[0223] In a 2 L flask equipped with a stirrer, a thermometer, and a condenser tube, 36.7 g of a 25 wt% TMAH solution, 600 mL of IPA, and 3.0 g of water were charged. Then, a mixed solution of 17 g of methyltrimethoxysilane, 29.7 g of phenyltrimethoxysilane, 7.6 g of tetramethoxysilane, and 43.4 g of 3-(methacryloyloxy)propyltrimethoxysilane was prepared in a dropping funnel. The mixed solution was added dropwise at 40 °C and stirred at the same temperature for 2 hours, and then neutralized with 10% aqueous HCl solution. 400 mL of toluene and 600 mL of water were added to the neutralized solution, and the mixture was separated into two layers, and the aqueous layer was removed. The organic layer was washed three times with 300 mL of water, and the solvent was removed by concentration under reduced pressure. PGMEA was added to the concentrate to make the solid content concentration 30 wt%, and a polysiloxane solution was obtained. The polysiloxane obtained at this stage had Mw = 3722.

[0224] 14.7 g of the polysiloxane solution, 0.35 g of methacrylic acid, and 0.63 g of azobisisobutyronitrile were added to a 100 mL flask equipped with a stirrer, a thermometer, and a condenser tube, and the mixture was stirred at 80 °C for 4 hours to obtain a polysiloxane A solution. The Mw of the obtained polysiloxane A was 5,966.

[0225] <Synthesis Example 2: Synthesis of Acrylic Polymer A>

[0226] 500 g of PGMEA was added to a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, and the temperature was raised to 95 °C. Then, 160 g of methacrylic acid, 100 g of methyl methacrylate, and 16.6 g of tert-butyl peroxy-2-ethylhexanoate (Perbutyl O; NOF Corporation) were added dropwise over 3 hours. After the addition, the mixture was stirred at room temperature for 4 hours to synthesize a polymer solution. 160 g of 3,4-epoxycyclohexyl methacrylate, 1.5 g of triphenylphosphine, and 1.0 g of methylhydroquinone were added to the polymer solution, and the reaction was carried out at 110 °C for 6 hours under a nitrogen atmosphere. After the reaction, the solid content was diluted with PGMEA to 35 wt% to obtain acrylic polymer A with Mw of 11,000.

[0227] <Synthesis Example 3: Synthesis of Acrylic Polymer B>

[0228] In a 2 L flask equipped with a stirrer, a thermometer, and a cooling tube, 500 g of bisphenol F type epoxy resin (Nippon Steel Chemical & Material Co., Ltd. "YDF2001 (trade name)"), 80 g of acrylic acid, 0.5 g of methylhydroquinone, and 150 g of ethylene glycol monoethyl ether acetate were mixed and stirred while heating to 90°C. Then, after cooling to 60°C, 2 g of trioctylmethylammonium chloride was mixed and heated to 110°C to react. Then, 230 g of tetrahydrophthalic anhydride and 85 g of ethylene glycol monoethyl ether acetate were mixed, heated to 80°C, and stirred for 6 hours to obtain a reaction mixture. The resulting acrylic polymer B had an Mw of 12,300.

[0229] <Example 1>

[0230] To a solution containing 100 parts by mass of the polysiloxane A obtained in Synthesis Example 1, 3.0 parts by mass of "Irgacure OXE-02" (manufactured by BASF) as a polymerization initiator, 50 parts by mass of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "A-DPH") as a compound containing (meth)acryloyloxy group, and 0.01 part by mass of "AKS-10" (manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant were added, and PGMEA was added to prepare a 35% solution, obtaining the composition of Example 1.

[0231] <Examples 2 to 8, Comparative Examples 1 to 5>

[0232] With respect to Example 1, the compositions were prepared by changing the composition as shown in Tables 1 and 2.

[0233] [Table 1]

[0234]

[0235] [Table 2]

[0236]

[0237] In the table,

[0238] Acrylic polymer A: "RN-081F" (manufactured by Natoco Co., Ltd.)

[0239] Compound A: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "A-DPH").

[0240] Compound B: Polyethylene glycol #600 diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "A-600").

[0241] Compound C: Ethoxylated isocyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "A-9300").

[0242] Sugar A: Ethylene oxide adduct of sucrose

[0243] Surfactant A: "AKS-10" (Shin-Etsu Chemical Co., Ltd.).

[0244] (Pattern formation at 2 μm or 10 μm)

[0245] Each of the obtained compositions was coated on a silicon wafer by spin coating. After coating, it was pre-baked on a hot plate at 100 °C for 90 seconds to prepare an average film thickness of 2 μm or 10 μm. It was exposed with an i-line exposure machine, developed with 0.025% KOH, and washed with pure water for 30 seconds. As a result, it was confirmed whether a 10-μm contact hole (C / H) pattern was formed. The obtained results are shown in Tables 1 and 2. It was confirmed that patterns were formed (OK) in all the examples. In all the comparative examples, no patterns were formed (NG).

[0246] (Transmittance)

[0247] The transmittance % at a wavelength of 400 nm of the cured film prepared with an average film thickness of 2 μm was measured using a Multi Spec-1500 manufactured by Shimadzu Corporation. The obtained results are as described in Tables 1 and 2.

[0248] (Pattern shape)

[0249] Each of the obtained compounds was coated on a silicon wafer by spin coating. After coating, it was pre-baked on a hot plate at 100 °C for 90 seconds, and the average film thickness was adjusted to 10 μm. When exposed with an i-line exposure machine and using 0.1 mass% KOH or 0.01 mass% KOH as the developer to form a 10-μm contact hole-shaped pattern size, the cross-section of the pattern was observed by SEM and compared, and the evaluation was carried out as follows. The obtained results are as described in Tables 1 and 2.

[0250] A: No residues were found in both the hole part and the pattern part.

[0251] B: No residues were found in the hole part, but a small amount of residues were found on the wall part of the pattern part.

[0252] C: More than half of the hole part was dissolved, but residues were confirmed and no pattern was formed.

[0253] D: More than half of the hole part was not dissolved

[0254] (Resolution)

[0255] When the above average film thickness was adjusted to 10 μm and 0.1 mass% KOH or 0.01 mass% KOH was used as the developer, the minimum mask size for forming contact holes under an optical microscope (MX61A-F, OLYMPUS Corporation) was taken as the resolution. The obtained results are shown in Table 1.

Claims

1. A negative photosensitive composition comprising: (I) a carboxyl group-containing alkali-soluble resin, (II) a polymerization initiator, (III) a compound having two or more (meth)acryloyloxy groups, and (IV) a solvent, wherein, based on the total mass of the alkali-soluble resin, the content of the compound having two or more (meth)acryloyloxy groups is 40 to 300% by mass, wherein, the alkali-soluble resin is a polysiloxane, the polysiloxane contains a silsesquioxane skeleton, and the polysiloxane includes a repeating unit represented by formula (Ia) and an acrylic polymerization unit represented by formula (a): In formula (Ia), R a1 is hydrogen or methyl, and ma are each independently an integer from 1 to 6, In formula (a), R a2 is independently hydrogen or methyl, and R a3 is hydrogen or a C 1～50 hydrocarbyl group having a valence of 1 to 6, and one or more methylene groups in the foregoing hydrocarbyl group may be replaced by an oxy group, an imino group, and / or a carbonyl group. When R a3 has a valence of 2 or more, R a3 connects the carbonyloxy group in formula (a) to the carbonyloxy group contained in other repeating units represented by formula (a), and na is an integer of 0 or more. * of at least one repeating unit in formula (Ia) is bonded directly or via the acrylic polymerization unit represented by formula (a) to * of other repeating units represented by formula (Ia), and There is at least one R represented by formula (a). a3 An acrylic acid polymerization unit that is hydrogen.

2. The composition according to claim 1, further comprising (V) sugar.

3. A method for manufacturing a cured film, comprising coating the composition according to claim 1 or 2 on a substrate to form a coating film, and exposing and developing the coating film.

4. The method according to claim 3, wherein, the developing is carried out using an aqueous solution of 0.05 to 1.5% by mass of TMAH, an aqueous solution of 0.1 to 2.5% by mass of sodium carbonate, or an aqueous solution of 0.01 to 1.5% by mass of potassium hydroxide as a developer.

5. A cured film manufactured by the method according to claim 3 or 4.

6. A display device including the cured film according to claim 5.

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