Low temperature curable negative photosensitive composition

Abstract

This invention provides a negative photosensitive composition with excellent chemical resistance and capable of low-temperature curing. The negative photosensitive composition comprises (I) a polysiloxane having a specific structure, (II) a polymerization initiator, (III) a compound containing two or more (meth)acryloyloxy groups, and (IV) a solvent.

Description

Technical Field

[0001] This invention relates to a negative photosensitive composition. Furthermore, this invention also relates to a method for manufacturing a cured film using the same, a cured film formed therefrom, and an electronic device having the cured film. Background Technology

[0002] In recent years, various proposals have been put forward in the fields of optical devices such as displays, light-emitting diodes, and solar cells, with the aim of improving light utilization efficiency and energy saving. For example, in the field of liquid crystal displays, a method is known to improve the aperture ratio of a display device by coating a transparent planarization film on a thin-film transistor (TFT) device and forming pixel electrodes on the planarization film.

[0003] Furthermore, structures for fabricating touch panels on organic EL or liquid crystal modules have been proposed. Additionally, flexible displays using plastic substrates instead of glass substrates have attracted attention. In either case, it is desirable to perform coating formation on the device at lower temperatures to prevent thermal degradation of the device's constituent materials. Furthermore, in the case of coating formation on organic semiconductors, organic solar cells, etc., there is a desire to consider environmental factors and cure at even lower temperatures. However, it is well known, for example, in the field of touch panels, that as a reliability test for panels, the ability to function normally under high temperature and high humidity conditions, even with a constant voltage applied continuously for a certain period, is a passing condition. Therefore, while conventional acrylic polymers can be cured at low temperatures, they generally do not possess the durability and properties required by customers.

[0004] Polysiloxanes are known to be heat-resistant. When forming and curing a coating from a polysiloxane-containing composition, the curing temperature needs to be lowered depending on the constituent materials of the device. Typically, to obtain a coating resistant to high temperatures and humidity, the coating needs to be heated at high temperatures to rapidly complete the condensation reaction of the silanol groups in the polysiloxane or the reaction of polymers with unsaturated bonds. If unreacted reactive groups remain, they may react with chemical reagents used in the device manufacturing process. Furthermore, adhesion to the substrate may deteriorate. Various polysiloxane compositions that maintain chemical resistance and can be cured at low temperatures have been proposed (e.g., Patent Document 1). It is desirable to develop a polysiloxane-containing composition that can be cured at low temperatures while maintaining chemical resistance.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2013-173809 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] The present invention is based on the above circumstances, and its purpose is to provide a negative photosensitive composition with excellent chemical resistance and low-temperature curability.

[0010] Solution for solving the problem

[0011] The negative photosensitizing composition according to the present invention comprises:

[0012] (I) Polysiloxane A containing repeating units as shown in formula (Ia),

[0013]

[0014] (In formula (Ia),

[0015] R Ia1 It is an alkylene group having 1 to 5 carbon atoms. Here, the -CH2- in the aforementioned alkylene group can be replaced by -O-.

[0016] R Ia2 Each is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms. Here, the -CH2- in the aforementioned alkyl group and the aforementioned alkylene group can also be replaced by -O-. Here, R Ia2 When it is an alkylene group, there are no nitrogen-bonded terminals bonded to the Si contained in the repeating unit shown in formula (Ia).

[0017] (II) Polymerization initiator,

[0018] (III) Compounds containing two or more (meth)acryloyloxy groups, and

[0019] (IV) Solvent.

[0020] The method for manufacturing a cured film according to the present invention includes: coating the aforementioned negative photosensitive composition onto a substrate to form a coating film, and exposing and developing the coating film.

[0021] The cured film according to the present invention is manufactured by the method described above.

[0022] The electronic device according to the present invention comprises the above-described cured film.

[0023] The effects of the invention

[0024] The negative photosensitive composition of the present invention can be cured at a temperature lower than that used in typical thermosetting photosensitive compositions, forming a cured film with high chemical resistance. Furthermore, the cured film or pattern can be manufactured more cheaply without the need for a post-exposure heating process. Moreover, since the resulting cured film possesses excellent flatness and electrical insulation properties, it can be used as a planarization film for thin-film transistor (TFT) substrates used in the backplanes of displays such as liquid crystal displays and organic EL displays, or as an interlayer insulating film for semiconductor devices; as an insulating film or transparent protective film in solid-state imaging devices, anti-reflective films, anti-reflective plates, filters, high-intensity light-emitting diodes, touch panels, solar cells, etc.; and is also suitable for use in optical devices such as optical waveguides. Detailed Implementation

[0025] The embodiments of the present invention will now be described in detail.

[0026] In this specification, unless otherwise stated, symbols, units, abbreviations and terms have the following meanings.

[0027] In this specification, unless otherwise stated, the singular form includes the plural form, and "a" or "that" means "at least one". In this specification, unless otherwise stated, elements of a concept may be represented by multiple kinds, and where their quantity (e.g., mass % or mole %) is stated, the quantity means the sum of multiple kinds. "And / or" includes all combinations of elements, as well as individual uses.

[0028] In this specification, when numerical ranges are indicated by “~” or “to / -”, they include both endpoints and the units are common. For example, 5 to 25 mol% means more than 5 mol% and less than 25 mol%.

[0029] In this specification, hydrocarbons contain carbon and hydrogen, and may contain oxygen or nitrogen as needed. A hydrocarbon group means a hydrocarbon with a valence of 1 or higher. In this specification, aliphatic hydrocarbons refer to straight-chain, branched, or cyclic aliphatic hydrocarbons, and an aliphatic hydrocarbon group refers to an aliphatic hydrocarbon with a valence of 1 or higher. Aromatic hydrocarbons refer to hydrocarbons containing an aromatic ring, which may have an aliphatic hydrocarbon group as a substituent or may be fused with an aliphatic ring if desired. An aromatic hydrocarbon group refers to an aromatic hydrocarbon with a valence of 1 or higher. Furthermore, an aromatic ring refers to a hydrocarbon with a conjugated unsaturated ring structure, and an aliphatic ring refers to a hydrocarbon with a ring structure but without a conjugated unsaturated ring structure.

[0030] In this specification, alkyl refers to a group obtained by removing any one hydrogen from a straight-chain or branched saturated hydrocarbon, including straight-chain alkyl and branched alkyl. Cycloalkyl is a group obtained by removing one hydrogen from a saturated hydrocarbon containing a cyclic structure. As needed, a straight-chain or branched alkyl may be included as a side chain in the cyclic structure.

[0031] In this specification, aryl refers to a group obtained by removing any one hydrogen atom from an aromatic hydrocarbon. Alkylene refers to a group obtained by removing any two hydrogen atom from a straight-chain or branched saturated hydrocarbon. Arylene refers to a hydrocarbon group obtained by removing any two hydrogen atom from an aromatic hydrocarbon.

[0032] In this specification, "C" x-y “C” x -C y "and "C x The term "etc." refers to the number of carbon atoms in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl group having 1 or more but less than 6 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). Furthermore, in this specification, fluoroalkyl refers to an alkyl group in which one or more hydrogen atoms are replaced by fluorine, while fluoroaryl refers to an aryl group in which one or more hydrogen atoms are replaced by fluorine.

[0033] In this specification, when the polymer has multiple types of repeating units, these repeating units are copolymerized. These copolymerizations are alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof.

[0034] In this manual, "%" represents mass percentage, and "ratio" represents mass ratio.

[0035] In this manual, the temperature unit is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0036] In this specification, polysiloxane refers to polymers having Si-O-Si bonds (siloxane bonds) as the main chain. Furthermore, in this specification, general polysiloxanes should also include those with the formula (RSiO... 1.5 ) n The term represents a sesquioxane polymer.

[0037] <Negative Photosensitive Composition>

[0038] The negative photosensitizing composition of the present invention (hereinafter referred to as the "composition") comprises (I) a polysiloxane having a specific structure, (II) a polymerization initiator, (III) a compound containing two or more (meth)acryloyl groups, and (IV) a solvent. The components contained in the composition of the present invention will be described in detail below.

[0039] (I) Polysiloxane A

[0040] The polysiloxane A used in this invention contains repeating units represented by formula (Ia).

[0041]

[0042] In equation (Ia),

[0043] R Ia1 It is an alkylene group having 1 to 5 carbon atoms. Here, the -CH2- in the aforementioned alkylene group can be replaced by -O-, but preferably not by -O-.

[0044] R Ia2 Each is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms. Here, the -CH2- in the aforementioned alkyl group and the aforementioned alkylene group can be replaced by -O-, but preferably not by -O-. Here, R Ia2 When it is an alkylene group, there are no nitrogen-bonded ends bonded to the Si contained in the other repeating units shown by formula (Ia).

[0045] It should be noted that when the aforementioned alkyl or alkylene contains -O-, the total number of carbon atoms and oxygen atoms is 1 to 5.

[0046] As R Ia1 Examples of such compounds include methylene, ethylene, and propylene, with propylene being the preferred option.

[0047] As R Ia2 Examples of such compounds include hydrogen, methyl, ethyl, propyl, methylene, ethylidene, and propylidene, with propyl and propylidene being preferred.

[0048] Two Rs contained in a repeating unit Ia2 The components can be the same or different, but at least one is preferably alkylene. In other words, the isocyanurate ring preferably has a structure that crosslinks the two polysiloxane chains. More preferably, both R... Ia2 Both are alkylene groups, and more preferably two R groups. Ia2 It is also propylidene.

[0049] Polysiloxane A preferably further contains repeating units represented by formula (Ib).

[0050]

[0051] In equation (Ib),

[0052] R Ib Indicates hydrogen, C 1-30 Straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon groups, or aromatic hydrocarbon groups.

[0053] The aforementioned aliphatic and aromatic hydrocarbon groups may be substituted with fluorine, hydroxyl, or alkoxy groups, respectively, and the -CH2- in the aforementioned aliphatic and aromatic hydrocarbon groups may be replaced by -O- or -CO-. However, R Ib It is neither hydroxyl nor alkoxy.

[0054] It should be noted that, here, -CH2-(methylene) also includes the terminal methyl group.

[0055] Furthermore, the phrase "can be replaced by fluorine, hydroxyl, or alkoxy groups" means that the hydrogen atom directly bonded to the carbon atom in aliphatic and aromatic hydrocarbon groups can be replaced by fluorine, hydroxyl, or alkoxy groups. The same applies to other similar descriptions in this specification.

[0056] As R Ib Examples of alkyl groups include (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; and (vi) epoxy groups such as glycidyl, or groups containing oxygen groups having an acryloyl or methacryloyl structure. Methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl, and isocyanates are preferred. As fluoroalkyl groups, perfluoroalkyl groups are preferred, particularly trifluoromethyl or pentafluoroethyl. Ib When the methyl group is used, the raw materials are readily available, the cured film has high hardness and high chemical resistance, making it a preferred choice. Additionally, when R... Ib When the polysiloxane is phenyl, its solubility in the solvent is increased, and the cured film is less likely to break, therefore it is preferred.

[0057] The polysiloxane A used in this invention may contain repeating units represented by formula (Ic).

[0058]

[0059] When the proportion of repeating units represented by formula (Ic) is high, the sensitivity of the composition decreases, the compatibility with solvents or additives decreases, the film stress increases, and cracks are easily generated. Therefore, the content of repeating units relative to the total number of repeating units of polysiloxane A is preferably 40 mol% or less, more preferably 20 mol% or less.

[0060] The polysiloxane A used in this invention may also contain repeating units represented by formula (Id).

[0061]

[0062] In formula (Id),

[0063] R Id Hydrogen and C are represented independently, respectively. 1～30 Straight-chain, branched, or cyclic saturated or unsaturated aliphatic or aromatic hydrocarbon groups.

[0064] The aforementioned aliphatic and aromatic hydrocarbon groups may be substituted with fluorine, hydroxyl, or alkoxy groups, and the -CH2- in the aforementioned aliphatic and aromatic hydrocarbon groups may also be replaced by -O- or -CO-, but R Id It is neither hydroxyl nor alkoxy.

[0065] As R Id Examples of alkyl groups include (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; and (vi) epoxy groups such as glycidyl, or groups containing oxygen groups having an acryloyl or methacryloyl structure. Methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl, and isocyanates are preferred. As fluoroalkyl groups, perfluoroalkyl groups are preferred, particularly trifluoromethyl or pentafluoroethyl. Id When the methyl group is used, the raw materials are readily available, the cured film has high hardness and high chemical resistance, making it a preferred choice. Additionally, when R... Id When the polysiloxane is phenyl, its solubility in the solvent is increased, and the cured film is less likely to break, therefore it is preferred.

[0066] By having repeating units represented by the above formula (Id), the polysiloxane used in this invention can have a partially linear structure. However, due to reduced heat resistance, a smaller linear structure portion is preferred. Specifically, the repeating units represented by formula (Id) are preferably 30 mol% or less, more preferably 10 mol% or less, relative to the total number of repeating units in the polysiloxane. Complete absence of repeating units represented by formula (Id) is also one of the preferred embodiments of this invention.

[0067] The polysiloxane A used in this invention has a structure formed by repeating units or block bonds as described above, but preferably has a silanol group at the end. This silanol group is formed by the bonding end of the aforementioned repeating unit or block and -O. 0.5 Groups formed by H bonds.

[0068] To improve adhesion to the substrate, the polysiloxane A preferably contains a large number of repeating units represented by formula (Ia). Furthermore, to control solubility in the developer, a small number is preferable. Specifically, the total number of Si atoms in formula (Ia) contained in the polysiloxane A is preferably 1 to 15% based on the total number of Si atoms in the polysiloxane, more preferably 2 to 5%.

[0069] There are no particular limitations on the mass-average molecular weight of the polysiloxane A used in this invention.

[0070] On the one hand, the lower the molecular weight, the fewer restrictions there are on the synthesis conditions, and the easier the synthesis. The synthesis of polysiloxanes with very high molecular weights is more difficult. Therefore, the mass-average molecular weight of polysiloxanes is typically 1,500–20,000, and preferably 2,000–15,000 considering their solubility in organic solvents and alkaline developing solutions. Here, the mass-average molecular weight is the mass-average molecular weight converted from polystyrene, which can be determined using gel permeation chromatography with polystyrene as a reference.

[0071] <Synthesis Method of Polysiloxane A>

[0072] The synthesis method of polysiloxane A used in this invention is not particularly limited. For example, it can be obtained by hydrolyzing and polymerizing the silane monomer shown in formula (ia) in the presence of an acidic or basic catalyst, as needed:

[0073]

[0074] (in formula (ia), R) ia2 Each is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or -R ia1 -Si-(OR ia’ )3, Here, the -CH2- in the aforementioned alkyl group can also be replaced by -O-, R ia1 It is an alkylene group having 1 to 5 carbon atoms. Here, the -CH2- in the aforementioned alkylene group can also be replaced by -O-, and R ia’ C can be either a straight chain or a branched chain, respectively. 1-6 alkyl).

[0075] Preferred R ia1 With the above R Ia1 The same is listed in the middle.

[0076] Preferred R ia’ Examples include methyl, ethyl, n-propyl, isopropyl, and n-butyl. Formula (ia) contains multiple R... ia’ However, each R ia’ They can be the same or different.

[0077] Preferred R ia2 It can be selected from the above R Ia2 The preferred ones listed above and the R mentioned above ia1 The middle section is the preferred option.

[0078] Specific examples of silane monomers represented by formula (ia) include, for example, tri-(3-trimethoxysilylpropyl)isocyanurate, tri-(3-triethoxysilylpropyl)isocyanurate, tri-(3-tripropoxysilylpropyl)isocyanurate, tri-(3-trimethoxysilylethyl)isocyanurate, tri-(3-triethoxysilylethyl)isocyanurate, tri-(3-tripropoxysilylethyl)isocyanurate, tri-(3-trimethoxysilyl) methyl isocyanurate, tri-(3-triethoxysilylmethyl) isocyanurate, tri-(3-tripropoxysilylmethyl) isocyanurate, bis-(3-trimethoxysilylpropyl)methyl isocyanurate, bis-(3-triethoxysilylpropyl)methyl isocyanurate, bis-(3-tripropoxysilylpropyl)methyl isocyanurate, bis-(3-trimethoxysilylethyl)methyl isocyanurate, bis-(3-triethoxysilylethyl)methyl isocyanurate Urea esters, bis-(3-tripropoxysilylethyl)methyl isocyanurate, bis-(3-trimethoxysilylmethyl)methyl isocyanurate, bis-(3-triethoxysilylmethyl)methyl isocyanurate, bis-(3-tripropoxysilylmethyl)methyl isocyanurate, 3-trimethoxysilylpropyl dimethyl isocyanurate, 3-triethoxysilylpropyl dimethyl isocyanurate, 3-tripropoxysilylpropyl dimethyl isocyanurate, 3-trimethoxy Silyl ethyl dimethyl isocyanurate, 3-triethoxysilyl ethyl dimethyl isocyanurate, 3-tripropoxysilyl ethyl dimethyl isocyanurate, 3-trimethoxysilyl methyl dimethyl isocyanurate, 3-triethoxysilyl methyl dimethyl isocyanurate, 3-tripropoxysilyl methyl dimethyl isocyanurate, wherein tri-(3-trimethoxysilylpropyl) isocyanurate and tri-(3-triethoxysilylpropyl) isocyanurate are preferred.

[0079] Furthermore, it is preferable to combine it with the silane monomer shown by formula (ib).

[0080] R ib -Si-(OR ib’ )3 (ib)

[0081] In formula (ib),

[0082] R ib Indicates hydrogen, C 1-30 Straight-chain, branched, or cyclic saturated or unsaturated aliphatic or aromatic hydrocarbon groups.

[0083] The aforementioned aliphatic and aromatic hydrocarbon groups may be substituted with fluorine, hydroxyl, or alkoxy groups, and the -CH2- in the aforementioned aliphatic and aromatic hydrocarbon groups may also be replaced by -O- or -CO-, but R ib It is neither hydroxyl nor alkoxy.

[0084] R ib’ C can be either a straight chain or a branched chain, respectively. 1-6 alkyl.

[0085] It is also preferred to combine two or more silane monomers represented by formula (ib).

[0086] Preferred R ib With the above R Ib The same is listed as the preferred option.

[0087] Preferred R ib’ Examples include methyl, ethyl, n-propyl, isopropyl, and ethyl-n-butyl. Formula (ib) contains multiple R... ib’ However, each R ib’ They can be the same or different.

[0088] Furthermore, it can also be combined with a silane monomer represented by the following formula (ic). When using a silane monomer represented by formula (ic), a polysiloxane containing a repeating unit (Ic) can be obtained.

[0089] Si(OR ic’ )4 (ic)

[0090] In formula (ic), R ic’ C is a straight chain or a branched chain 1-6 Alkyl group. In formula (ic), R is preferred. ic’ Examples include methyl, ethyl, n-propyl, isopropyl, and n-butyl. The formula (ic) contains multiple R... ic’ However, each R ic’ They can be the same or different.

[0091] Specific examples of silane monomers represented by formula (ic) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetran-butoxysilane.

[0092] Furthermore, it can be combined with a silane monomer represented by the following formula (id). When using a silane monomer represented by formula (id), a polysiloxane containing repeating units (Id) can be obtained.

[0093] (R id )2-Si-(OR id’ )2 (id)

[0094] In formula (id),

[0095] R id’ C can be either a straight chain or a branched chain, respectively. 1-6 Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, and n-butyl, are examples. A monomer may contain multiple R groups. id’ Each R id’ They can be the same or different.

[0096] R id Hydrogen and C are represented independently, respectively. 1-30 Straight-chain, branched, or cyclic saturated or unsaturated aliphatic or aromatic hydrocarbon groups.

[0097] The aforementioned aliphatic and aromatic hydrocarbon groups may also be substituted with fluorine, hydroxyl, or alkoxy groups, and the -CH2- in the aforementioned aliphatic and aromatic hydrocarbon groups may also be replaced by -O- or -CO-, but R id It is neither hydroxyl nor alkoxy.

[0098] Preferred R id The above R Id The best examples are listed below.

[0099] The compositions of the present invention may further comprise polymers different from polysiloxane A. Preferably, they comprise acrylic resin and / or polysiloxane B without the repeating unit of formula (Ia). Hereinafter, polysiloxane A, acrylic resin, and polysiloxane B may be collectively referred to as alkali-soluble resins.

[0100] (Acrylic resin)

[0101] The acrylic resin used in this invention may be selected from commonly used acrylic resins, such as polyacrylic acid, polymethacrylic acid, polyalkyl polyacrylate, polyalkyl methacrylate, etc., but preferably an acrylic resin containing at least one of repeating units containing acryloyl groups, repeating units containing carboxyl groups, and repeating units containing alkoxysilyl groups as substituents, and more preferably an acrylic resin containing repeating units containing acryloyl groups, repeating units containing carboxyl groups, and repeating units containing alkoxysilyl groups.

[0102] There are no particular restrictions on repeating units containing carboxyl groups, as long as the repeating unit has a carboxyl group in its side chain. It is preferred to repeating units derived from unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof.

[0103] The repeating unit containing alkoxysilyl is any repeating unit with a side chain containing alkoxysilyl, preferably a repeating unit derived from a monomer represented by the following formula (B).

[0104] X B -(CH2) a -Si(OR B )b (CH3) 3-b (B)

[0105] In formula (B), X B For vinyl, styrene, or (meth)acryloyloxy, R B It is either methyl or ethyl, a is an integer from 0 to 3, and b is an integer from 1 to 3.

[0106] In addition, the aforementioned polymer preferably contains hydroxyl-containing repeating units derived from hydroxyl-containing unsaturated monomers.

[0107] The mass-average molecular weight of the acrylic resin of the present invention is not particularly limited, but is preferably 1,000 to 40,000, more preferably 2,000 to 30,000. Here, the mass-average molecular weight is the mass-average molecular weight converted from polystyrene obtained by gel permeation chromatography. From the viewpoint of being able to be developed with a low-concentration alkaline developer and taking into account both reactivity and preservation, in terms of acid number, the acid value of the solid component is generally 40 to 190 mg KOH / g, more preferably 60 to 150 mg KOH / g.

[0108] (Polysiloxane B)

[0109] Polysiloxane B is a polysiloxane that does not contain the repeating unit represented by formula (Ia) above. Polysiloxane B preferably contains the repeating unit represented by formula (Ib) above, and more preferably contains the repeating unit represented by formula (Ic). Furthermore, it may also contain other repeating units.

[0110] There are no particular limitations on the mass-average molecular weight of polysiloxane B. However, higher molecular weight tends to improve coatability. On the other hand, lower molecular weights have fewer restrictions on synthesis conditions and are easier to synthesize; the synthesis of polysiloxanes with very high molecular weights is more difficult. Therefore, the mass-average molecular weight of polysiloxanes is typically 1,500 to 20,000, and preferably 2,000 to 15,000, considering solubility in organic solvents and alkaline developing solutions. Here, the mass-average molecular weight is the mass-average molecular weight converted from polystyrene and can be determined using gel permeation chromatography with polystyrene as a reference.

[0111] The content of polysiloxane A is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of all polymers contained in the composition.

[0112] Furthermore, the composition containing the alkali-soluble resin used in this invention is coated onto a substrate, and then subjected to image exposure and development to form a cured film. At this time, a difference in solubility between the exposed and unexposed areas is required; the coating on the unexposed areas should have a certain degree of solubility in the developer. For example, the solubility rate (hereinafter referred to as alkali dissolution rate or ADR; details below) of the pre-baked coating in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution is acceptable. If the exposure speed is above 100 μm, it is considered that a pattern can be formed through exposure-development. However, since the required solubility varies depending on the thickness of the cured film to be formed or the development conditions, an alkali-soluble resin should be appropriately selected according to the development conditions. For example, if the film thickness is 0.1–100 μm... The preferred dissolution rate in a 2.38% TMAH aqueous solution is... / second, further optimized / Second.

[0113] The alkali-soluble resin used in this invention can be selected from alkali-soluble resins containing any ADR within the above-mentioned range, depending on the application or required characteristics. Alternatively, polysiloxanes or acrylic resins with different ADRs can be combined to form mixtures having the desired ADR.

[0114] By changing the catalyst, reaction temperature, reaction time, or polymer, alkali-soluble resins with different alkali dissolution rates and mass-average molecular weights can be prepared. Combining polysiloxanes and acrylic resins with different alkali dissolution rates can reduce insoluble residues after development, decrease pattern collapse, and improve pattern stability.

[0115] Examples of such alkali-soluble resins include: (M) pre-baked films are soluble in 2.38% by mass TMAH aqueous solutions, and their dissolution rate is... / second of polysiloxane.

[0116] Additionally, the pre-baked film (L) can be dissolved in a 5% (w / w) TMAH aqueous solution as needed, and its dissolution rate is... The dissolution rate of polysiloxanes or (H) pre-baked films in 2.38% TMAH aqueous solution is less than / second. Polysiloxanes are mixed at a rate of more than 1 / second to obtain a composition with the desired dissolution rate.

[0117] [Methods for determining and calculating alkaline dissolution rate (ADR)]

[0118] The alkali dissolution rate of alkali-soluble resins was determined and calculated using TMAH aqueous solution as the alkali solution, as follows.

[0119] The alkali-soluble resin was diluted to 35% by mass in propylene glycol monomethyl ether acetate (PGMEA) and dissolved while stirring with a stirrer for 1 hour at room temperature. In a cleanroom environment with an atmosphere of 23.0 ± 0.5 °C and 50 ± 5.0% humidity, 1 cc of the prepared alkali-soluble resin solution was dropwise onto the center of a 4-inch (525 μm) thick silicon wafer using a pipette, and spin-coated to a thickness of 2 ± 0.1 μm. The coating was then heated on a hot plate at 100 °C for 90 seconds to remove the solvent. The film thickness was measured using a spectroscopic ellipsometry (JA Woollam).

[0120] Next, the silicon wafer with the coating was gently immersed in a 6-inch diameter glass petri dish containing 100 ml of a TMAH aqueous solution of a specified concentration, adjusted to 23.0 ± 0.1 °C. The dish was then left to stand, and the time until the coating disappeared was measured. The dissolution rate was determined by dividing the time it took for the coating to disappear from the portion 10 mm inside the wafer tip. In cases of very slow dissolution, the wafer was immersed in the TMAH aqueous solution for a certain time, then heated on a hot plate at 200 °C for 5 minutes to remove any moisture introduced into the coating during the dissolution rate measurement. The coating thickness was then measured, and the dissolution rate was calculated by dividing the change in coating thickness before and after immersion by the immersion time. This measurement method was performed five times, and the average value was taken as the dissolution rate of the alkali-soluble resin.

[0121] (II) Polymerization Initiator

[0122] The compositions according to the invention comprise a polymerization initiator. This polymerization initiator includes polymerization initiators that generate acids, bases, or free radicals via radiation and polymerization initiators that generate acids, bases, or free radicals via heat. In this invention, since the reaction begins immediately after radiation irradiation, the reheating process after radiation irradiation and before the development process can be eliminated. Therefore, the former is preferred in terms of shortening the process and reducing costs, and a photoradical generator is more preferred.

[0123] Photoradical generators can improve resolution by enhancing the shape of a pattern or increasing the contrast of the development. The photoradical generator used in this invention is one that emits free radicals when irradiated with radiation. Examples of radiation include visible light, ultraviolet light, infrared light, X-rays, electron beams, alpha rays, and gamma rays.

[0124] The optimal amount of photoradical generator varies depending on the type and amount of active substances produced by the decomposition of the photoradical generator, the required photosensitivity, and the solubility contrast between the exposed and unexposed areas. However, based on the total mass of the alkali-soluble resin, it is preferably 0.001 to 30% by mass, more preferably 0.01 to 10% by mass. When the amount added is less than 0.001% by mass, the solubility contrast between the exposed and unexposed areas is too low, and sometimes the additive effect is negligible. On the other hand, when the amount of photoradical generator added exceeds 30% by mass, the formed coating may develop cracks, or the coloring caused by the decomposition of the photoradical generator may become more pronounced, thereby reducing the colorless transparency of the coating. In addition, if the amount added is too large, it may lead to thermal decomposition, resulting in poor electrical insulation of the cured product and gas release, causing problems for subsequent processes. Furthermore, the coating's resistance to photoresist stripping solutions with monoethanolamine or similar main reagents may sometimes decrease.

[0125] Examples of photoradical generators include azo, peroxide, phosphine oxide, alkyl phenyl ketone, oxime ester, and titanocene initiators. Among these, alkyl phenyl ketone, phosphine oxide, and oxime ester initiators are preferred, including 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)benzyl]phenyl}-2-methylpropane-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one. 2-Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-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-benzoyl oxime)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), etc.

[0126] (III) Compounds containing two or more (meth)acryloyloxy groups

[0127] The compositions of the present invention comprise compounds containing two or more (meth)acryloyloxy groups (hereinafter, for simplicity, sometimes referred to as compounds containing (meth)acryloyloxy groups). Here, (meth)acryloyloxy is a general term for acryloyloxy and methacryloyloxy. The compound is one that can react with alkali-soluble resins, etc., to form a cross-linked structure. Here, in order to form a cross-linked structure, it is necessary to be a compound containing two or more acryloyloxy or methacryloyloxy groups as reactive groups; for forming a more advanced cross-linked structure, it is preferable to contain three or more acryloyloxy or methacryloyloxy groups.

[0128] As compounds containing 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 preferred. Examples of such polyol compounds (α) include compounds with a basic skeleton of saturated or unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, primary amines, secondary or tertiary amines, ethers, etc., and having two or more hydroxyl groups as substituents. Without impairing the effects of the present invention, the polyol compound may also contain other substituents such as carboxyl groups, carbonyl groups, amino groups, ether bonds, thiol groups, thioether bonds, etc.

[0129] Preferred polyol compounds include alkyl polyols, aryl polyols, polyalkanolamines, cyanuric acid, and dipentaerythritol. Here, when the polyol compound (α) has three or more hydroxyl groups, not all hydroxyl groups need to react with (meth)acrylic acid; they can be partially esterified. That is, these esters can have unreacted hydroxyl groups. Examples of such esters include 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, tricyclodecanediol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, and 1,10-decanediol diacrylate. From the viewpoint of reactivity and the number of crosslinkable groups, tris(2-acryloyloxyethyl) isocyanurate and dipentaerythritol hexaacrylate are preferred. Furthermore, to adjust the shape of the formed pattern, two or more of these compounds can be combined. Specifically, compounds containing three (meth)acryloyloxy groups and compounds containing two (meth)acryloyloxy groups can be combined.

[0130] From a reactivity point of view, such compounds are preferably molecules that are relatively smaller than those of alkali-soluble resins. Therefore, a molecular weight of 2,000 or less is preferred, and more preferably 1,500 or less is even more desirable.

[0131] The content of the (meth)acryloxy group-containing compound can be adjusted according to the polymer used and the type of (meth)acryloxy group-containing compound, but from the viewpoint of compatibility with the resin, it is preferably 3 to 50% by mass based on the total mass of the alkali-soluble resin. Furthermore, from the viewpoint of suppressing film loss, it is more preferably 20 to 50% by mass. In addition, these (meth)acryloxy group-containing compounds can be used alone or in combination of two or more.

[0132] (IV) Solvents

[0133] The compositions of the present invention comprise a solvent. The solvent is not particularly limited, as long as it can uniformly dissolve or disperse the alkali-soluble resin, polymerization initiator, (meth)acryloyloxy compound, and additives 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; and propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether. Alkyl ethers, 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 pentanone, 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; and cyclic esters such as γ-butyrolactone. Among these, considering ease of availability, ease of handling, and polymer solubility, propylene glycol alkyl ether acetates or esters, and straight-chain or branched alcohols having 4 or 5 carbon atoms in the alkyl group are preferred. From the viewpoint of coatability and storage stability, a solvent ratio of 5% to 80% for the alcohol is preferred.

[0134] The solvent content of the compositions of the present invention can be adjusted arbitrarily according to the coating method, etc. For example, when coating the composition by spraying, the proportion of solvent in the composition can be 90% by mass or more. Furthermore, in the case of slot coating for coating large substrates, it is generally 60% by mass or more, preferably 70% by mass or more. The properties of the compositions of the present invention do not change significantly with the amount of solvent.

[0135] The compositions of the present invention require the aforementioned (I) to (IV), but other compounds may be combined as needed. These combinable materials are described below. It should be noted that, based on the total mass of the composition, the amount of components other than (I) to (IV) in the overall composition is preferably 50% by mass or less, more preferably 30% by mass or less, and preferably 30% by mass or less, more preferably 20% by mass or less, when a colorant is added, and when no colorant is added.

[0136] The compositions of the present invention may also contain other additives as needed.

[0137] Examples of such additives include developer dissolution promoters, descumming agents, thickeners, polymerization inhibitors, defoamers, surfactants, and sensitizers.

[0138] Developer dissolution enhancers or descum removers regulate the solubility of the formed coating in the developer or prevent scum residue from remaining on the substrate after development. Crown ethers can be used as such additives. The crown ether with the simplest structure is of the general formula (-CH2-CH2-O-). n This indicates that, among these, crown ethers with n being 4 to 7 are preferred in this invention. Crown ethers may 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 this invention, crown ethers with x = 12, 15, 18, or 21 and y = x / 3 are preferred, as are crown ethers selected from the group consisting of these benzo[a] condensates and cyclohexyl condensates. More preferred examples of 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 this invention, the crown ethers most preferably selected from 18-crown-6-ether and 15-crown-5-ether are preferred. Based on the total mass of the alkali-soluble resin, the content is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass.

[0139] When a cured film is formed using the composition of the present invention, the tackifier has the effect of preventing the pattern from peeling off due to stress applied after firing. As a 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 preferred.

[0140] The silane coupling agent preferably uses well-known ones, such as epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, etc. Specifically, 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane are preferred. Ethoxysilanes, 3-ureopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-isocyanopropyltriethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, etc. These can be used alone or in combination, and the preferred addition amount is 0.05–15% by mass, based on the total mass of the alkali-soluble resin.

[0141] In addition, silane compounds and siloxane compounds containing acid groups can also be used as silane coupling agents. Examples of acid groups include carboxyl groups, anhydride groups, and phenolic hydroxyl groups. When containing monobasic acid groups such as carboxyl groups and phenolic hydroxyl groups, it is preferable that a single silicon-containing compound has multiple acid groups.

[0142] As a specific example of such a silane coupling agent, the compound represented by formula (C) can be listed:

[0143] X n Si(OR 3 ) 4-n (C)

[0144] Or polymers that use it as a repeating unit. In this case, X or R can be... 3 Different combinations of repetitive units are used.

[0145] In equation (C), R is used as 3 Examples of alkyl groups include hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, and n-butyl. In the general formula (C), there are multiple R groups. 3 However, each R 3 They can be the same or different.

[0146] As X, groups having acid groups such as phosphonium, borates, carboxyl, phenol, peroxide, nitro, cyano, sulfonyl, and alcohol, as well as groups and anhydride groups that have these acid groups protected by acetyl, aryl, pentyl, benzyl, methoxymethyl, methanesulfonyl, toluene, trimethoxysilyl, triethoxysilyl, triisopropylsilyl, or triphenylmethyl.

[0147] Among these, those with methyl as R are preferred.3 Substances having a carboxylic anhydride group as X, such as silicones containing an anhydride group. More specifically, it is preferable that the ends or side chains of silicones or other silicone-containing polymers contain a compound represented by the following formula (X-12-967C (trade name, Shin-Etsu Chemical Co., Ltd.)) or a polymer with a similar structure.

[0148]

[0149] Furthermore, compounds with an acid group such as a thiol, phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, or sulfonyl added to the terminal portion of dimethylsiloxane are preferred. Examples of such compounds include those represented by the formulas X-22-2290AS and X-22-1821 (both trade names, Shin-Etsu Chemical Co., Ltd.)

[0150]

[0151] 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 is not improved, and reactive groups remain in the film, which may lead to adverse effects such as the inability to maintain chemical resistance to subsequent processes. Therefore, the mass-average molecular weight of the silane coupling agent is preferably 5000 or less, more preferably 4000 or less.

[0152] In addition to nitroglycerin, nitroxide radicals, hydroquinone, catechol, phenothiazine, phenothiazine, hindered amines and their derivatives, ultraviolet absorbers can also be added as polymerization inhibitors. Among these, methylhydroquinone, catechol, 4-tert-butylcatechol, 3-methoxycatechol, phenothiazine, chlorpromazine, phenothiazine, TINUVIN 144, 292, 5100 (BASF) as hindered amines, and TINUVIN 326, 328, 384-2, 400, 477 (BASF) as ultraviolet absorbers are preferred. These can be used alone or in combination, and their content is preferably 0.01 to 20% by mass based on the total mass of the alkali-soluble resin.

[0153] Alcohols (C) can be listed as defoamers. 1-18 The following are included: higher fatty acids such as oleic acid and stearic acid; higher fatty acid esters such as glyceryl monolaurate; polyethers such as polyethylene glycol (PEG) (Mn200 to 10,000) and polypropylene glycol (PPG) (Mn200 to 10,000); organosilicon compounds such as dimethyl silicone oil, alkyl-modified silicone oil, and fluorosilicone oil; and organosiloxane surfactants described in detail below. These can be used alone or in combination, and their content is preferably 0.1 to 3% by mass, based on the total mass of the alkali-soluble resin.

[0154] Furthermore, the compositions of the present invention may also contain surfactants as needed. The purpose of adding surfactants is to improve coating properties, developability, etc. Examples of surfactants that can be used in the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0155] Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oil-based ether, and polyoxyethylene hexadecyl ether; acetylenic diol derivatives such as polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers, alkynyl alcohols, alkynyldiols, polyethoxylated compounds of alkynyl alcohols, and polyethoxylated compounds of alkynyldiols; fluorinated surfactants such as Fluorad (trade name, Sumitomo 3M Corporation), Megafac (trade name, DIC Corporation), and Surflon (trade name, Asahi Glass Corporation); and organosiloxane surfactants such as KP341 (trade name, Shin-Etsu Chemical Co., Ltd.). Examples of the aforementioned ynylene diols include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyyn-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, and 2,5-dimethyl-2,5-hexanediol.

[0156] As anionic surfactants, examples 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 alkylbenzene sulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfuric acid, and ammonium salts or organic amine salts of alkyl sulfuric acid.

[0157] Furthermore, examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and lauramidopropyl hydroxysulfonyl betaine.

[0158] These surfactants can be used alone or in combination of two or more, and their content is preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on the total mass of the composition.

[0159] In addition, sensitizers may be added to the compositions of the present invention as needed.

[0160] Preferred sensitizers used in the compositions of the present invention include coumarin, coumarinone and their derivatives, and thiopyrylium salts. Salts), acetophenones, etc., 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, 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-trifluoromethylpiperidinyl-<3,2-g>coumarin, 2-(p-dimethylaminostyryl)-benzothiazolyl ethyl iodide, 3-(2'-benzimidazolyl)-7-N,N-diethylaminocoumarin, 3-(2'-benzothiazolyl)-7-N,N-diethylaminocoumarin, and sensitizing pigments such as pyranonium salts and thiopyranonium salts represented by the following chemical formulas. By adding sensitized pigments, patterning using inexpensive light sources such as high-pressure mercury lamps (360–430 nm) becomes possible. Based on the total mass of the alkali-soluble resin, its content is preferably 0.05–15% by mass, more preferably 0.1–10% by mass.

[0161]

[0162] X <![CDATA[R 21 ]]> <![CDATA[R 22 ]]> <![CDATA[R 23 ]]> Y S <![CDATA[OC4H9]]> H H <![CDATA[BF4]]> S <![CDATA[OC4H9]]> <![CDATA[OCH3]]> <![CDATA[OCH3]]> <![CDATA[BF4]]> S H <![CDATA[OCH3]]> <![CDATA[OCH3]]> <![CDATA[BF4]]> S <![CDATA[N(CH3)2]]> H H <![CDATA[ClO2]]> O <![CDATA[OC4H9]]> H H <![CDATA[SbF6]]>

[0163] Alternatively, compounds containing an anthracene skeleton can be used as sensitizers. Specifically, compounds represented by the following formulas can be listed.

[0164]

[0165] In the formula, R 31 Each of these groups independently represents a substituent selected from the group consisting of alkyl, aralkyl, allyl, hydroxyalkyl, alkoxyalkyl, glycidyl, and haloalkyl groups.

[0166] R 32Each of these groups independently represents a substituent selected from the group consisting of hydrogen, alkyl, alkoxy, halogen, nitro, sulfonic acid, hydroxyl, amino, and carboalkoxy groups.

[0167] k can be an integer selected independently from 0, 1 to 4.

[0168] When using this sensitizer with an anthracene skeleton, its content is preferably 0.01 to 5% by mass, based on the total mass of the alkali-soluble resin.

[0169] Furthermore, a curing agent may be added to the composition of the present invention as needed.

[0170] Curing agents can improve resolution by enhancing the shape of the pattern or increasing the contrast of the development. Examples of curing agents used in this invention include photoacid-generating agents that release acid and photoalkali-generating agents that release alkali, wherein the acid is an active substance that decomposes upon irradiation with radiation and photocures the composition. Examples of radiation include visible light, ultraviolet light, infrared light, X-rays, electron beams, alpha rays, and gamma rays.

[0171] The optimal amount of curing agent varies depending on the type and amount of active substances produced by the decomposition of the curing agent, the required photosensitivity, and the dissolution contrast between the exposed and unexposed areas. Based on the total mass of the alkali-soluble resin, it is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

[0172] <Methods for forming cured films>

[0173] The method for forming the cured film of the present invention includes coating the aforementioned composition onto a substrate to form a coating film, exposing the coating film to light, and developing it. Hereinafter, the method for forming the cured film will be described in the order of the steps.

[0174] (1) Coating process

[0175] First, the aforementioned composition is coated onto a substrate. The coating film of the composition of the present invention can be formed using any method known conventionally for coating photosensitive compositions. Specifically, dipping, roller coating, rod coating, brush coating, spraying, blade coating, flow coating, spin coating, slot coating, etc., can be selected. Furthermore, suitable substrates such as silicon substrates, glass substrates, and resin films can be used as the substrate for coating the composition. Various semiconductor devices can be formed on these substrates as needed. If the substrate is a thin film, gravure coating can also be used. A drying step can be performed separately after coating, depending on preference. Moreover, the coating process can be repeated once or more as needed to obtain the desired film thickness.

[0176] (2) Pre-baking process

[0177] After the coating film is formed by applying the coating composition, it is preferable to pre-bake (pre-heat treatment) the coating film in order to dry the film and reduce the amount of solvent residue in the 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.

[0178] (3) Exposure process

[0179] After the coating is formed, the surface of the coating is irradiated with light. Any light source commonly used in pattern forming methods can be used as the light source for irradiation. Examples of such light sources include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, laser diodes, and LEDs. Ultraviolet light such as g-rays, h-rays, and i-rays is typically used as the irradiation light. Except for ultra-fine processing such as semiconductors, light of 360–430 nm (high-pressure mercury lamps) is typically used for patterning from a few μm to tens of μm. In the case of liquid crystal display devices, 430 nm light is often used. In this case, it is advantageous to incorporate sensitized pigments into the composition of the present invention, as described above. The energy of the irradiation light also depends on the light source and the thickness of the coating, but is typically 5–2,000 mJ / cm². 2 Preferably, it is 10–1,000 mJ / cm². 2 If the energy of the irradiated light is less than 5 mJ / cm 2 If the resolution is too high, sufficient resolution may not be achieved; conversely, if it exceeds 2,000 mJ / cm², it may not be possible to obtain sufficient resolution. 2 If this happens, overexposure may occur, resulting in a halo effect.

[0180] To ensure that light irradiates the patterned area, a conventional photomask can be used. This photomask can be arbitrarily selected from known photomasks. The irradiation environment is not particularly limited; generally, an ambient atmosphere (atmosphere) or a nitrogen atmosphere is sufficient. Furthermore, when forming a film on the entire surface of a substrate, irradiation of the entire substrate surface is sufficient. In this invention, patterned films also include cases where a film is formed on the entire surface of a substrate.

[0181] (4) Post-exposure heating process

[0182] After exposure, a polymerization initiator is used to promote the reaction between polymers within the film, so post-exposure heating can be performed as needed. This heating treatment differs from the heating step (6) described later; it is not performed to completely cure the coating, but rather to leave only the desired pattern on the substrate after development, with the rest removed by development. Therefore, it is not necessary in this invention.

[0183] When heating after exposure, a hot plate, oven, or furnace can be used. The heating temperature should not be too high, as it is undesirable for acids, alkalis, or free radicals generated by light irradiation to diffuse into unexposed areas. From this perspective, the post-exposure heating temperature range is preferably 40°C to 150°C, more preferably 60°C to 120°C. Staged heating can also be used to control the curing speed of the composition, as needed. Furthermore, the heating atmosphere is not particularly limited; for the purpose of controlling the curing speed of the composition, it can be selected from inert gases such as nitrogen, under vacuum, under reduced pressure, or oxygen. In addition, the heating time is preferably a certain duration to better maintain the uniformity of the temperature path within the wafer surface, and to suppress the diffusion of generated acids, alkalis, or free radicals, the heating time is preferably not too long. From this perspective, the heating time is preferably 20 seconds to 500 seconds, more preferably 40 seconds to 300 seconds.

[0184] (5) Developing process

[0185] After exposure, post-exposure heating is performed as needed, followed by development of the coating. Any developer used in the development of conventional photosensitive compositions can be used as the developing solution. In this invention, an aqueous solution of TMAH is used to determine the dissolution rate of the alkali-soluble resin, but the developing solution used to form the cured film is not limited to this. Preferred developing solutions include aqueous solutions of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilicates (hydrates), alkali metal phosphates (hydrates), ammonia, alkylamines, alkanolamines, and heterocyclic amines, i.e., alkaline developing solutions. Particularly preferred alkaline developing solutions are aqueous solutions of TMAH, potassium hydroxide, or sodium hydroxide. These alkaline developing agents may further include water-soluble organic solvents such as methanol and ethanol, or surfactants, as needed. The developing method can also be any method known in the art. Specifically, methods such as immersion in the developing solution, spin-dip, spraying, slit coating, cap coat, and spraying can be included. A pattern can be obtained through this development process, preferably by washing with water after development with a developing solution.

[0186] (6) Heating process

[0187] After development, the resulting patterned film is cured by heating. The same heating apparatus used in the heating process as that used in the post-exposure heating described above can be used. The heating temperature in this process is not particularly limited, as long as it is sufficient to cure the coating, and can be set arbitrarily. However, if residual silanol groups remain, the chemical resistance of the cured film becomes insufficient, or the dielectric constant of the cured film becomes high. From this viewpoint, a relatively high heating temperature can be selected. Generally, to maintain a high residual film yield after curing, a curing temperature of 350°C or lower is more preferred, and particularly 250°C or lower is especially preferred. On the other hand, to promote the curing reaction and obtain a fully cured film, a curing temperature of 70°C or higher is preferred, more preferably 80°C or higher, and particularly preferably 90°C or higher is especially preferred. However, the composition of the present invention can maintain sufficient chemical resistance even when cured at low temperatures of 70–130°C, particularly below 100°C. Furthermore, the heating time is not particularly limited, generally ranging from 10 minutes to 24 hours, preferably from 30 minutes to 3 hours. It should be noted that this heating time is the time after the temperature of the patterned film reaches the desired heating temperature. Typically, it takes several minutes to several hours for the patterned film to reach the desired temperature from its initial temperature before heating.

[0188] The cured film obtained in this way achieves excellent transparency, chemical resistance, and environmental resistance. For example, the light transmittance of the film cured at 100°C can reach over 95%, and the relative permittivity can reach below 4. Even after 1000 hours at 65°C and 90% humidity, the relative permittivity remains unchanged. Therefore, it possesses light transmittance, relative permittivity, chemical resistance, and environmental resistance not found in conventional acrylic materials, making it suitable for various applications such as planarization films for flat panel displays (FPDs), interlayer insulating films for low-temperature polycrystalline silicon, buffer coatings for IC chips, and transparent protective films.

[0189] The following examples and comparative examples are provided to further illustrate the present invention, but the present invention is not limited by these examples and comparative examples.

[0190] Gel permeation chromatography (GPC) was performed using an HLC-8220GPC high-speed GPC system (trade name, Tosoh Corporation) and two Super Multipore HZ-N GPC columns (trade name, Tosoh Corporation). The determination was conducted using monodisperse polystyrene as the standard sample, tetrahydrofuran as the developing solvent, and under analytical conditions of a flow rate of 0.6 mL / min and a column temperature of 40 °C.

[0191] <Synthesis Example 1: Synthesis of Polysiloxane A: PSA-1: Me:Ph:KBM-9659:H = 50:40:9.5:5>

[0192] In a 3L flask equipped with a stirrer, thermometer, and cooling tube, a mixed solution of 204g methyltrimethoxysilane, 237g phenyltrimethoxysilane, 185g KBM-9695 (Shin-Etsu Silicone), 1200g PGMEA, and 1.8g trimethoxyhydrosilane was prepared. 6.6g of 35% HCl aqueous solution was added to this mixed solution, and the mixture was stirred at 25°C for 3 hours. 400ml toluene and 600ml water were added to the neutralized solution to separate it into two layers; the aqueous layer was removed. The solution was then washed three times with 300ml of water, and the resulting organic layer was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to bring the solids concentration to 35% by mass, yielding polysiloxane PSA-1. The Mw of the obtained polysiloxane PSA-1 was 12,000.

[0193] <Synthesis Example 2: Synthesis of Polysiloxane A: PSA-2>

[0194] Except for changing the ratio to Me:Ph:KBM-9659:H = 50:20:19.5:5, a polysiloxane PSA-2 solution was obtained in the same manner as in Synthesis Example 1. The resulting polysiloxane PSA-2 had a Mw of 16,400.

[0195] <Synthesis Example 3: Synthesis of Polysiloxane A: PSA-3>

[0196] Except for changing the ratio of Me:Ph:KBM-9659:H to 50:45:4.5:5, a polysiloxane PSA-3 solution was obtained in the same manner as in Synthesis Example 1. The resulting polysiloxane PSA-3 had an Mw of 8,200.

[0197] <Synthesis Example 4: Synthesis of Polysiloxane B:PSB-1>

[0198] In a 2L flask equipped with a stirrer, thermometer, and cooling tube, 49.0 g of 25% TMAH aqueous solution, 600 ml of isopropanol (IPA), and 4.0 g of water were added. Then, a mixed solution of 68.0 g of methyltrimethoxysilane, 79.2 g of phenyltrimethoxysilane, and 15.2 g of tetramethoxysilane was prepared in a dropping funnel. This mixed solution was added dropwise at 40°C, and the mixture was stirred at the same temperature for 2 hours. Then, 10% HCl aqueous solution was added for neutralization. 400 ml of toluene and 600 ml of water were added to the neutralized solution to separate it into two layers; the aqueous layer was removed. The solution was washed three times with 300 ml of water. The resulting organic layer was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to bring the solids concentration to 35% by mass, yielding a polysiloxane PSB-1 ​​solution. The Mw of the obtained polysiloxane PSB-1 ​​was 1700.

[0199] <Synthesis Example 5: Synthesis of Acrylic Resin: AC-1>

[0200] In a 2L flask equipped with a stirrer, thermometer, cooling tube, and nitrogen inlet, n-butanol and PGMEA solvent were added. Under a nitrogen atmosphere, the temperature was raised to a suitable level, referencing the 10-hour half-life temperature of the initiator. Separately, acrylic acid, γ-methacryloyloxypropyltrimethoxysilane, 2-hydroxyethyl methacrylate, and methyl methacrylate were mixed in a ratio of 10:20:20:50. AIBN:azobisisobutyronitrile and PGMEA were then mixed to prepare a mixed solution. This mixed solution was added dropwise to the aforementioned solvent over a period of 4 hours. The mixture was then allowed to react for 3 hours to obtain acrylic resin AC-1. The Mw of the obtained acrylic resin AC-1 was 8,700.

[0201] <Synthesis Example 6: Synthesis of Acrylic Resin: AC-2>

[0202] 500 g of PGMEA was added to a 2 L separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet. The mixture was heated to 95 °C, and then 160 g of methacrylic acid, 100 g of methyl methacrylate, and 16.6 g of tert-butyl peroxide-2-ethylhexanoate (Perbutyl O; Nippon Oil Co., Ltd.) were added dropwise over 3 hours. The mixture was stirred at room temperature for 4 hours after the addition 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 this polymer solution, and the reaction was carried out at 110 °C for 6 hours under a nitrogen atmosphere. After the reaction, the mixture was diluted with PGMEA to a solid content of 35% by weight to obtain an acrylic resin with a Mw of 11,000.

[0203] <Synthetic Example 7: Other Polymers: Synthesis of P-1>

[0204] In a 2L four-necked flask, 235g of bisphenol fluorene-type epoxy resin (epoxy equivalent 235), 110mg of tetramethylammonium chloride, 100mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0g of acrylic acid were added and heated at 120°C for 12 hours to dissolve. Then, while the solution remained turbid, the temperature was gradually increased to 120°C to ensure complete dissolution. The resulting bisphenol fluorene-type epoxy acrylate, acrylic acid, 2-hydroxyethyl methacrylate, and methyl methacrylate were mixed in a ratio of 10:20:20:50. AIBN:azobisisobutyronitrile and PGMEA were also mixed to prepare a mixed solution. This mixed solution was added dropwise to the aforementioned solvent over 4 hours. The reaction was then allowed to proceed for 3 hours to obtain polymer P-1. The Mw of the obtained polymer P-1 was 16,100.

[0205] <Example 1>

[0206] In a solution containing 100 parts by mass of polysiloxane PSA-1 obtained in Synthesis Example 1, 3.5 parts by mass of BASF's "Irgacure OXE-02" as a polymerization initiator, 16 parts by mass of dipentaerythritol hexaacrylate (Ninakamura Chemical Industry Co., Ltd. "A-DPH") as a (meth)acryloyloxy compound, 8.5 parts by mass of ε-caprolactone-modified tri-(2-acryloyloxyethyl) isocyanurate (Ninakamura Chemical Industry Co., Ltd. "A-9300-1CL"), and 0.01 parts by mass of Shin-Etsu Chemical Industry Co., Ltd. "AKS-10" as a surfactant were added to prepare a 35% solution.

[0207] <Examples 2-19, Comparative Examples 1-8>

[0208] The compositions were prepared with changes to the composition as shown in Tables 1 and 2, relative to Example 1. The values ​​in the tables represent parts by mass.

[0209]

[0210] [Table 2]

[0211]

[0212] In the table,

[0213] Polymerization initiator A: BASF's "Irgacure OXE-02".

[0214] AM-1: Dipentaerythritol hexaacrylate (Shin-Nakamura Chemical Industry Co., Ltd. "A-DPH").

[0215] AM-2: ε-caprolactone-modified tri-(2-acryloyloxyethyl)isocyanurate (Shinnakamura Chemical Industry Co., Ltd. "A-9300-1CL").

[0216] AM-3: Polyethylene glycol #200 diacrylate (Shin-Nakamura Chemical Industry Co., Ltd. "A-200").

[0217] AM-4: Polyethylene glycol #1000 diacrylate (Shin-Nakamura Chemical Industry Co., Ltd. "A-1000").

[0218] AM-5: Tricyclodecylmethane diacrylate (Shin-Nakamura Chemical Industry Co., Ltd. "A-DCP").

[0219] AM-6: 2,2-bis(4-(acryloyloxydiethoxy)phenyl)propane (EO: 4mol) (Shinnakamura Chemical Industry Co., Ltd. "A-BPE-4").

[0220] Silane coupling agent A: Tri-(trimethoxysilylpropyl)isocyanurate.

[0221] Silane coupling agent B: 3-methacryloyloxypropyltrimethoxysilane.

[0222] Surfactant A: Shin-Etsu Chemical Industry Co., Ltd. "AKS-10".

[0223] The obtained compositions were spin-coated onto ITO or silicon wafers, and then pre-baked at 100°C for 90 seconds on a hot plate. At this point, the average film thickness was 2–3 μm. Exposure was performed using an i-line exposure machine, followed by development with a 2.38% TMAH aqueous solution and rinsing with pure water for 30 seconds. After rinsing, the wafers were heated at 100°C or 120°C for 1 hour. Then, the wafers were immersed in a stripping solution TOK106 (Tokyo Ohka Kogyo Co., Ltd.) for 3 minutes, and the changes in the pattern shape after immersion were measured.

[0224] A: The thinning of the film before and after impregnation is within ±10%.

[0225] B: The amount of film thinning before and after impregnation exceeds 10% but is within ±20%.

[0226] C: The film thinning exceeds 20%, or pattern peeling is confirmed.

Claims

1. A negative photosensitizing composition comprising: (I) Polysiloxane A containing repeating units as shown in formula (Ia), In equation (Ia), R Ia1 is an alkylene group having 1 to 5 carbon atoms, and in the aforementioned alkylene group, -CH2- can be replaced by -O-, R Ia2 Each is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms. Here, the -CH2- in the aforementioned alkyl group and the aforementioned alkylene group can also be replaced by -O-. Here, R Ia2 When it is an alkylene group, there are no nitrogen-bonded terminals bonded to the Si contained in other repeating units represented by formula (Ia). (II) Polymerization initiator, (III) Compounds containing two or more (meth)acryloyloxy groups, and (IV) Solvent, in, The content of polysiloxane A is 60 to 100% by mass, based on the total mass of all polymers contained in the aforementioned composition.

2. The composition according to claim 1, wherein, The aforementioned polysiloxane A further contains repeating units represented by formula (Ib), In equation (Ib), R Ib Indicates hydrogen, C 1-30 Straight-chain, branched, or cyclic saturated or unsaturated aliphatic or aromatic hydrocarbon groups. The aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group may be substituted with fluorine, hydroxyl, or alkoxy groups, respectively, and The -CH2- in the aforementioned aliphatic and aromatic hydrocarbon groups can also be replaced by -O- or -CO-, where R Ib It is neither hydroxyl nor alkoxy.

3. The composition according to claim 1 or 2, wherein, The total number of Si atoms in formula (Ia) contained in the aforementioned polysiloxane A is 1 to 15% based on the total number of Si atoms in the aforementioned polysiloxane.

4. The composition according to any one of claims 1 to 3, further comprising an acrylic resin and / or a polysiloxane B without repeating units of formula (Ia).

5. A method for manufacturing a cured film, comprising coating the composition of any one of claims 1 to 4 onto a substrate to form a coating film, and exposing and developing the coating film.

6. The method according to claim 5, further comprising a step of heating at a temperature of 70 to 130°C after development.

7. A cured film formed by the method of claim 5 or 6.

8. An electronic device having the cured film of claim 7.

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