Negative photosensitive composition

Abstract

The composition can be used for a negative photosensitive composition, and the composition can exhibit characteristics of at least one advanced material or high-performance material. The compositions may be used in nanotechnology processes to fabricate semiconductor / display devices, such as liquid crystal, quantum dot or OLED displays fabricated on substrates and controlled by semiconductors. A negative-type photosensitive composition comprising (I) a polysiloxane, (II) an acrylic polymer, (III) a compound comprising two or more (meth) acryloyloxy groups, (IV) a polymerization initiator, (V) a thiol compound comprising at least two thiol groups, and (VI) a solvent wherein component (II) has a glass transition temperature of 0 to 60 DEG C.

Description

Technical Field

[0001] This invention relates to a negative photosensitive composition. It also relates to a method for manufacturing a cured film using the negative photosensitive composition, the cured film formed by the method, and an electronic device comprising the cured film. Background Technology

[0002] In recent years, various solutions have been proposed to improve light energy utilization efficiency and save energy for optical devices such as displays, light-emitting diodes, and solar cells. For example, in liquid crystal displays, a method for increasing the aperture ratio of the display device is known. This method involves forming a transparent planarization film on a thin-film transistor (TFT) device to cover the device, and forming pixel electrodes on the planarization film.

[0003] A structure for forming touch panels on organic EL or liquid crystal modules has been proposed. Furthermore, flexible displays using plastic substrates instead of glass substrates have also attracted attention. In any case, thin film formation on the device is preferably performed at a lower temperature to avoid thermal degradation of the device's constituent materials. Moreover, considering environmental factors, coatings formed on materials such as organic semiconductors and organic solar cells also need to be able to cure at lower temperatures.

[0004] A composition for forming a cured film, which is prepared by combining polysiloxane and acrylic polymer, can be cured at low temperature and has transparency, chemical resistance, etc. (e.g., Patent Document 1).

[0005] [Prior art literature]

[0006] [Patent Documents]

[0007] [Patent Document 1] JP2015-18226A Summary of the Invention

[0008] [The problem to be solved by this invention]

[0009] The inventors believe that one or more problems still exist for compositions containing polysilazane, requiring further improvement. These problems include, for example, the following:

[0010] High curing temperature; film shrinkage occurs during heating in the curing process; high residual stress in the cured film; high flexibility but unsuitable hardness in the cured film; undercut may occur during pattern formation.

[0011] [Problem-solving methods]

[0012] The negative photosensitivity combination according to the present invention comprises:

[0013] (I) Polysiloxane,

[0014] (II) Acrylic polymers,

[0015] (III) Compounds containing two or more (meth)acryloyloxy groups,

[0016] (IV) Polymerization initiators,

[0017] (V) Thiol compounds containing at least two thiol groups, and

[0018] (VI) Solvents,

[0019] The glass transition temperature of component (II) is 0 to 60°C.

[0020] The method for preparing a cured film according to the present invention includes: applying the above composition onto a substrate to form a film; exposing the film; and developing the 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] According to the present invention, one or more of the following effects can be provided:

[0025] The curing temperature can be significantly reduced; film shrinkage during heating in the curing process can be suppressed; the residual stress in the cured film is sufficiently low; the cured film has sufficiently high flexibility and appropriate hardness; baking after development can significantly reduce lateral etching during pattern formation. Detailed Implementation

[0026] [Forms for Implementing the Invention]

[0027] The embodiments of the present invention are described in detail below.

[0028] In this specification, unless otherwise stated, symbols, units, abbreviations and terms have the following meanings.

[0029] In this specification, unless otherwise specified, the singular form includes the plural form, and "a" or "the" means "at least one". In this specification, unless otherwise specified, elements in the concept can be expressed as multiple species, and when describing quantities (e.g., mass% or mole%), it refers to the sum of multiple species. "And / or" includes combinations of all elements, as well as the individual use of elements.

[0030] In this specification, when “to / ~” or “-” is used to indicate a numerical range, it includes both endpoints and the units are the same. For example, 5 to 25 mol% means more than 5 mol% and less than 25 mol%.

[0031] In this specification, hydrocarbon compounds refer to compounds containing carbon and hydrogen, and optionally containing oxygen or nitrogen. A hydrocarbon group refers to a hydrocarbon compound with a monovalent, divalent, or higher valence.

[0032] In this specification, hydrocarbon refers to a hydrocarbon containing carbon and hydrogen, and optionally containing oxygen or nitrogen. A hydrocarbon group refers to a hydrocarbon with a monovalent, divalent, or higher valence.

[0033] In this specification, aliphatic hydrocarbons refer to straight-chain, branched, or cyclic aliphatic hydrocarbons, and aliphatic hydrocarbon groups refer to monovalent, divalent, or higher-valent aliphatic hydrocarbons. Aromatic hydrocarbons refer to hydrocarbons containing aromatic rings, which may optionally contain not only aliphatic hydrocarbon groups as substituents but may also be fused with aliphatic rings. Aromatic hydrocarbon groups refer to monovalent, divalent, or higher-valent aromatic hydrocarbons. Furthermore, aromatic rings refer to hydrocarbons containing conjugated unsaturated ring structures, and aliphatic rings refer to hydrocarbons with ring structures but not conjugated unsaturated ring structures.

[0034] In this specification, alkyl refers to a group obtained by removing any one hydrogen atom from a straight-chain or branched saturated hydrocarbon, including straight-chain alkyl and branched alkyl; cycloalkyl refers to a group obtained by removing one hydrogen atom from a saturated hydrocarbon having a cyclic structure, wherein the cyclic structure may optionally contain a straight-chain or branched alkyl as a side chain.

[0035] 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 atoms from a straight-chain or branched saturated hydrocarbon. Arylene refers to a hydrocarbon group obtained by removing any two hydrogen atoms from an aromatic hydrocarbon.

[0036] In this specification, terms such as "C" x-y “C” x -C y "and "C x The descriptions using "" all indicate the number of carbon atoms in the molecule or substituent. For example, C 1-6 Alkyl groups represent alkyl groups having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Additionally, as used herein, fluoroalkyl refers to a group in which one or more hydrogen atoms in the alkyl group are replaced by fluorine, and fluoroaryl refers to a group in which one or more hydrogen atoms in the aryl group are replaced by fluorine.

[0037] In this specification, when the polymer has multiple repeating units, these repeating units copolymerize. These copolymerizations are any one of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or any mixture thereof.

[0038] In this manual, "%" represents mass percentage, and "ratio" represents mass ratio.

[0039] In this manual, degrees Celsius is used as the unit of temperature. For example, 20 degrees means 20 degrees Celsius.

[0040] In this specification, polysiloxane refers to polymers with Si-O-Si bonds (siloxane bonds) as the main chain. Furthermore, in this specification, (RSiO) 1.5 ) n The sesquioxane polymers indicated should also be included as general polysiloxanes.

[0041] <Negative Photosensitive Composition>

[0042] The negative photosensitizing composition according to the present invention (hereinafter referred to as the composition) comprises: (I) a polysiloxane; (II) an acrylic polymer; (III) a compound containing two or more (meth)acryloyloxy groups; (IV) a polymerization initiator; (V) a thiol compound containing at least two mercapto groups; and (VI) a solvent. The components contained in the composition of the present invention will be described in detail below.

[0043] (I) Polysiloxane

[0044] The structure of the polysiloxane (I) used in this invention (hereinafter sometimes referred to as component (I), and the same applies to other components) is not particularly limited and can be freely selected according to the application. Based on the number of oxygen atoms bonded to silicon atoms, the skeletal structure of polysiloxanes can be divided into a silicone skeleton (2 oxygen atoms bonded to silicon atoms), a sesquioxane skeleton (3 oxygen atoms bonded to silicon atoms), and a silica skeleton (4 oxygen atoms bonded to silicon atoms). In this invention, any of the above-mentioned skeletal structures can be used. The polysiloxane molecule can contain various combinations of any of the above-mentioned skeletal structures.

[0045] The polysiloxane (I) preferably contains repeating units represented by formula (Ia):

[0046]

[0047] Where R Ia Represents hydrogen, C 1-30 (C is preferred) 1-10 (a) Straight-chain, branched or cyclic saturated aliphatic hydrocarbon group, aromatic hydrocarbon group or (meth)acryloyloxy group; and any -CH2- in the aliphatic hydrocarbon group or aromatic hydrocarbon group may be replaced by -O- or -CO-.

[0048] In the repeating unit represented by equation (Ia), except for hydrogen, R IaExamples also 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; (vi) nitrogen-containing groups having an amino or imide structure, such as isocyanates and amino groups; and (vii) oxygen-containing groups having an epoxy structure (e.g., glycidyl), acryloyl, or methacryloyl). Preferably, R Ia It can be methyl, ethyl, propyl, butyl, pentyl, hexyl, or phenyl. R is preferred. Ia Methyl groups are preferred because the raw materials are readily available, and the cured film exhibits high hardness and good chemical resistance. Furthermore, R is preferred. Ia The phenyl group is used because the polysiloxane has increased solubility in solvents, making the cured film less prone to cracking.

[0049] The polysiloxane used in this invention may also contain repeating units represented by the following formula (Ib):

[0050]

[0051] Where R Ib It is a group obtained by removing multiple hydrogens from a cyclic aliphatic hydrocarbon compound containing nitrogen and / or oxygen (including amino, imino and / or carbonyl groups).

[0052] In equation (Ib), R Ib Preferably, the group is obtained by removing multiple hydrogen atoms (preferably two or three hydrogen atoms) from a nitrogen-containing cyclic aliphatic hydrocarbon compound (containing an imino group and / or a carbonyl group), more preferably a five- or six-membered ring containing nitrogen as a ring member. Examples of such groups include piperidine, pyrrolidine, and groups obtained by removing two or three hydrogen atoms from isocyanurates. Ib The Si atoms in multiple repeating units are connected to each other.

[0053] Component (I) may also contain repeating units represented by the following formula (Ic):

[0054]

[0055] When the mixing ratio of the repeating units represented by formulas (Ib) and (Ic) is high, cracks are more likely to occur due to decreased sensitivity of the composition, reduced compatibility with solvents and additives, and increased film stress. Therefore, based on the total number of polysiloxane repeating units, the amount is preferably 40 mol% or lower, more preferably 20 mol% or lower.

[0056] Component (I) may also contain repeating units represented by the following formula (Id):

[0057]

[0058] Where R Id Each independently represents hydrogen and C. 1-30 (C is preferred) 1-10 Straight-chain, branched, or cyclic, saturated or unsaturated aliphatic or aromatic hydrocarbon groups:

[0059] Both aliphatic and aromatic hydrocarbon groups may be unsubstituted or replaced by fluorine, hydroxyl, or C. 1-8 Alkoxy substitution, and

[0060] In aliphatic and aromatic hydrocarbon groups, the methylene group is not substituted, or one or more methylene groups are substituted by oxygen, imino, or carbonyl groups; however, R Id It is neither hydroxyl nor alkoxy.

[0061] In the repeating unit represented by equation (Id), R Id Examples 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; (vi) nitrogen-containing groups having an amino or imide structure, such as isocyanates and amino groups; and (vii) oxygen-containing groups having an epoxy structure (e.g., glycidyl), acryloyl, or methacryloyl). Preferably, R Id It can be methyl, ethyl, propyl, butyl, pentyl, hexyl, or phenyl. R is preferred. Id Methyl groups are preferred because the raw materials are readily available, and the cured film exhibits high hardness and good chemical resistance. Furthermore, R is preferred. Id The phenyl group is used because the polysiloxane has increased solubility in solvents, making the cured film less prone to cracking.

[0062] The polysiloxane according to the invention can have a partially linear structure by having repeating units represented by formula (Id). However, to prevent a decrease in heat resistance, a smaller linear structure portion is preferred. Specifically, based on the total number of repeating units in the polysiloxane, the repeating units represented by formula (Id) are preferably 30 mol% or less, more preferably 5 mol% or less. One embodiment of the invention may also omit the repeating units represented by formula (Id) (0 mol%).

[0063] Component (I) may contain two or more types of repeating units. For example, it may contain three types of repeating units, including the repeating unit represented by equation (Ia) (where R... Ia All are methyl or phenyl), and repeating units represented by formula (Ic).

[0064] Component (I) preferably contains silanol. Here, silanol refers to a structure in which the hydroxyl group (OH) is directly bonded to the silicon backbone of the polysiloxane, or the hydroxyl group is directly bonded to the silicon atoms in the polysiloxane composed of repeating units of formulas (Ia) to (Id). That is, silanol is formed by the -O group in formulas (Ia) to (Id). 0.5 H and -O 0.5 The structure is formed by phase bonding. The silanol content in polysiloxanes depends on the synthesis conditions of the polysiloxane, such as the monomer mixing ratio and the type of reaction catalyst.

[0065] There are no particular limitations on the mass-average molecular weight of the polysiloxanes used in this invention. However, higher molecular weights are often beneficial for improving coating performance. On the other hand, lower molecular weights have fewer restrictions on synthesis conditions and are easier to synthesize, while synthesizing high molecular weight polysiloxanes is more difficult. For these reasons, considering their solubility in organic solvents, the mass-average molecular weight of the polysiloxanes is typically from 500 to 25,000, preferably from 1,000 to 20,000. The mass-average molecular weight referred to herein is based on polystyrene and can be determined by polystyrene-based gel permeation chromatography.

[0066] Component (I) can be a single type or two or more types. Based on the total mass of components (I) and (II), the content of component (I) is preferably 8.0 to 35.0% by mass, more preferably 8.0 to 30.0% by mass.

[0067] (II) Acrylic polymers

[0068] The acrylic polymer (II) used in this invention may be selected from commonly used acrylic polymers, such as polyacrylic acid, polymethacrylic acid, polyalkyl polyacrylate, and polyalkyl polymethacrylate. The acrylic polymer used in this invention preferably comprises repeating units having acryloyl groups, and more preferably also comprises repeating units having carboxyl groups and / or repeating units having alkoxysilyl groups.

[0069] There are no particular restrictions on repeating units having a carboxyl group, as long as their side chains contain a carboxyl group, but repeating units derived from unsaturated carboxylic acids, unsaturated carboxylic anhydrides or mixtures thereof are preferred.

[0070] The repeating unit having an alkoxysilyl group can be a repeating unit containing an alkoxysilyl group on its side chain. Preferably, the repeating unit is derived from the monomer shown in formula (B).

[0071] X B -(CH2) a -Si(OR B ) b (CH3) 3-b (B)

[0072] Where 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.

[0073] Furthermore, the polymer preferably contains repeating units having hydroxyl groups, which are derived from hydroxyl-containing unsaturated monomers.

[0074] The glass transition temperature of component (II) is 0–60°C, preferably 10–60°C. When the glass transition temperature meets the above range, the residual stress of the cured film can be reduced. Although not theoretically limited, it can be considered that this is because acrylic polymers with lower glass transition temperatures can alleviate the stress generated by the dehydration condensation of polysiloxanes during the curing process.

[0075] There is no particular limitation on the mass-average molecular weight of component (II), but it is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. Here, mass-average molecular weight refers to the mass-average molecular weight based on polystyrene as determined by gel permeation chromatography.

[0076] Based on the total mass of components (I) and (II), the content of component (II) is preferably 65.0 to 92.0% by mass, more preferably 70.0 to 92.0% by mass.

[0077] (III) Compounds containing two or more (meth)acryloyloxy groups

[0078] The composition according to the invention comprises a compound containing two or more (meth)acryloyloxy groups (for simplicity, it is sometimes referred to hereinafter as a compound containing (meth)acryloyloxy groups). Here, (meth)acryloyloxy is a collective term for acryloyloxy and methacryloyloxy. This compound is capable of reacting with substances such as alkali-soluble resins to form a cross-linked structure. Here, in order to form a cross-linked structure, a compound containing two or more acryloyloxy or methacryloyloxy groups (both active groups) is required; for forming a higher-order cross-linked structure, it is preferable to contain three or more acryloyloxy or methacryloyloxy groups.

[0079] 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. The polyol compound (α) includes compounds whose basic skeleton can be a saturated or unsaturated aliphatic hydrocarbon, aromatic hydrocarbon, heterocyclic hydrocarbon, primary amine, secondary or tertiary amine, ether, etc., and whose substituents can be two or more hydroxyl groups. The polyol compound may also contain other substituents, such as carboxyl, carbonyl, amino, ether bond, thiol group, thioether bond, etc., as long as they do not affect the effects of the present invention.

[0080] 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 must react with (meth)acrylic acid; they can be partially esterified. This means that the ester can contain 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, polytetramethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, di(trimethylolpropane)tetraacrylate, tricyclodecanediethanol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, etc. From the perspective 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 used in combination. Specifically, compounds containing three (meth)acryloyloxy groups and compounds containing two (meth)acryloyloxy groups can be combined.

[0081] From the perspective of reactivity, this compound is preferably a relatively small molecule compared to components (I) and (II). For this reason, its molecular weight is preferably 2000 or less, more preferably 1500 or less.

[0082] Component (III) can be a single type or two or more types. The content of component (III) is adjusted according to the type of polymer or (meth)acryloyloxy compound used. Based on the total mass of the composition (excluding solvent), the content of component (III) is preferably 5.0 to 35.0% by mass, more preferably 10.0 to 25.0% by mass.

[0083] (IV) Polymerization initiators

[0084] The compositions according to the invention comprise polymerization initiators (IV). These polymerization initiators include initiators that generate acids, bases, or free radicals under radiation irradiation, and initiators that generate acids, bases, or free radicals under heating conditions. In the present invention, since the reaction begins immediately after radiation irradiation and the reheating step after radiation irradiation and before the development step can be omitted, the former is superior from the perspective of process simplification and cost reduction, and photoradioactive agents are more preferred.

[0085] Photoradical generators can improve resolution by enhancing pattern shape and increasing development contrast. The photoradical generator used in this invention is one that releases free radicals under radiation irradiation. Examples of radiation include visible light, ultraviolet light, infrared light, X-rays, electron beams, alpha rays, and gamma rays.

[0086] Examples of photoradical generators include azo, peroxide, phosphine oxide, alkyl phenyl ketone, oxime ester, and titanoceramnetin initiators. Alkyl phenyl ketone, phosphine oxide, and oxime ester initiators are preferred, and more preferably include 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-methylpropanoyl)-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.

[0087] Component (IV) may be a single type or two or more types. Based on the total mass of the composition (excluding solvent), the content of component (IV) is preferably 0.50 to 10.0% by mass, more preferably 1.0 to 8.0% by mass.

[0088] (V) Thiol compounds containing two or more thiol groups

[0089] The compositions according to the invention comprise a thiol compound (V) containing two or more thiol groups.

[0090] By including component (V), the compositions according to the invention can be cured at sufficiently low temperatures and impart appropriate hardness to the cured film. While not theoretically limited, it can be considered that thiol compounds facilitate the crosslinking of polysiloxanes, acrylic polymers, and (meth)acryloyloxy compounds under heat and light.

[0091] Component (V) contains two or more thiol groups (-SH), preferably 2 to 8 thiol groups, more preferably 2 to 6 thiol groups, and even more preferably 3 or 4 thiol groups.

[0092] Component (V) may be a primary thiol compound or a secondary thiol compound. Preferably, component (V) is a secondary thiol compound.

[0093] Preferably, this component (V) does not contain Si atoms.

[0094] Examples of primary thiols include ethylene glycol bis(3-mercaptopropionate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrapropanethiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.

[0095] Examples of secondary thiols include pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tetra(2-mercaptobutyrate), dipentaerythritol hexa(3-mercaptobutyrate), dipentaerythritol hexa(2-mercaptobutyrate), trimethylolpropane tri(3-mercaptobutyrate), trimethylolpropane tri(2-mercaptobutyrate), 1,3,5-tris(2-(3-mercaptobutyryloxy)ethyl)-1,3,5-triazine-2,4,6-trione, 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tri(2-mercaptopropionate), ethylene glycol bis(2-mercaptopropionate), 2,3-butanedithiol, 2,5-hexanedithiol, etc.

[0096] In a preferred embodiment, component (V) is a secondary thiol compound having two or more (preferably 2 to 8, more preferably 2 to 6, and even more preferably 3 or 4) of the following structures:

[0097]

[0098] Where L represents a single bond or C 1-5 Alkylene, preferably methylene or ethylene, more preferably methylene.

[0099] R 2 C 1-5 Alkyl, preferably methyl or ethyl, more preferably methyl.

[0100] In another preferred embodiment, component (V) is represented by formula (Va):

[0101]

[0102] Where L represents a single bond or C 1-5 Alkyl group, preferably methylene or ethylene, more preferably methylene.

[0103] R is C 1-5 Alkyl, preferably methyl or ethyl, more preferably methyl.

[0104] n is 2 to 5, preferably 2 to 4, and more preferably 3 or 4.

[0105] X is C 1-20 The hydrocarbon group, in which the methylene group can be replaced by a nitrogen, carbonyl, or oxygen group. X is preferably C. 1-10 More preferably C 3-6 saturated hydrocarbon groups.

[0106] Component (V) is preferably selected from the group consisting of pentaerythritol tetra(3-mercaptobutyrate), trimethylolpropane tri(3-mercaptobutyrate), 1,3,5-tris(2-(3-mercaptobutyryloxy)ethyl)-1,3,5-triazine-2,4,6-trione and 1,4-bis(3-mercaptobutyryloxy)butane.

[0107] There is no particular limitation on the molecular weight of component (V). The molecular weight of component (V) is preferably from 100 to 1000, more preferably from 100 to 900, and even more preferably from 300 to 800.

[0108] Component (V) can be a single type or two or more types. Based on the total mass of components (I) and (II), the content of component (V) is preferably 0.1 to 5% by mass, more preferably 0.2 to 5% by mass, and even more preferably 0.2 to 3% by mass.

[0109] (VI) Solvents

[0110] The compositions according to the present invention comprise a solvent. The solvent is not particularly limited, as long as it can uniformly dissolve or disperse the components described above and any 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 (PGME) and propylene glycol monoethyl ether; propylene glycol alkyl ethers... Acetates, such as propylene glycol monomethyl ether acetate (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 pentyl 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; and cyclic esters, such as γ-butyrolactone, etc. Component (VI) is preferably PGMEA, PGME, or mixtures thereof.

[0111] The content of component (VI) can be freely adjusted according to factors such as the method of applying the composition. Based on the total mass of the composition, the content of component (V) is preferably 50 to 90% by mass, more preferably 50 to 80% by mass.

[0112] (VII) Surfactants

[0113] The compositions according to the present invention may further contain a surfactant (VII). The purpose of adding a surfactant is to improve coating properties, developability, etc. Surfactants that can be used in the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0114] Examples of nonionic surfactants include: polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene oil ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters; polyoxyethylene fatty acid monoesters; polyoxyethylene polyoxypropylene block polymers; alkynyl alcohols; alkynyl glycols; polyethoxylated alkynyl alcohols; alkynyl glycol derivatives, such as polyethoxylated alkynyl glycols; fluorinated surfactants, such as Fluorad (trade name, 3M Japan), Megafac (trade name, DIC), and Surflon (trade name, AGC); or organosiloxane surfactants, such as KP341 (trade name, Shin-Etsu Chemical). 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.

[0115] Examples of anionic surfactants include ammonium or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium or organic amine salts of alkyl diphenyl ether sulfonic acid, ammonium or organic amine salts of alkylbenzene sulfonic acid, ammonium or organic amine salts of polyoxyethylene alkyl ether sulfuric acid, and ammonium or organic amine salts of alkyl sulfuric acid.

[0116] Examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole betaine and laurylamidopropyl hydroxysulfone betaine.

[0117] Component (VII) may be of a single type or two or more types. Based on the total mass of the composition, the content of component (VII) is preferably 0.0001 to 0.05% by mass, more preferably 0.0005 to 0.01% by mass.

[0118] In the composition according to the invention, in addition to the components (I) to (VII) described above, other additives may be added if necessary. Based on the total mass of the composition, the content of the components other than components (I) to (VII) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass. It is also an embodiment of the invention that does not contain the components other than components (I) to (VII).

[0119] Examples of additives include developer dissolution promoters, scum removers, adhesion enhancers, polymerization inhibitors, defoamers, and sensitizers.

[0120] <Methods for forming a cured film>

[0121] The method for forming a cured film according to the present invention includes coating the above-described composition onto a substrate to form a coating film, exposing the coating film to light, and developing the coating film. The method for forming a cured film is described below in process order.

[0122] (1) Coating process

[0123] First, the above composition is coated onto a substrate. The coating film of the composition in this invention can be formed using any known method for coating photosensitive compositions. Specifically, dip coating, roll coating, rod coating, brush coating, spray coating, doctor blade coating, flow coating, spin coating, slot coating, etc., can be freely selected. Furthermore, suitable substrates, such as silicon substrates, glass substrates, resin films, etc., can be used as the substrate for coating the composition. Various semiconductor devices can be formed on these substrates as needed. When the substrate is a film, gravure printing can also be used. If necessary, a drying process can be performed after coating. Furthermore, if necessary, the coating can be repeated once, twice, or more times to achieve the desired coating thickness.

[0124] (2) Pre-baking process

[0125] After forming a coating film by coating the composition, it is preferable to pre-bake (heat treat) the coating film to dry it and reduce the amount of residual solvent in the coating film. Pre-baking can generally be carried out at a temperature of 50 to 150°C, preferably 70 to 120°C; on a hot plate, the baking time is 10 to 300 seconds, preferably 30 to 120 seconds; in a clean oven, the baking time is 1 to 30 minutes.

[0126] (3) Exposure process

[0127] After the coating is formed, the surface of the coating is irradiated with light. The light source for irradiation can be any light source conventionally used in pattern forming methods. Such light sources may include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps and xenon lamps, laser diodes, light-emitting diodes, etc. Ultraviolet light, such as g-lines, h-lines, and i-lines, is typically used as the irradiation light. Preferably, the peak wavelength of the exposure is 360 to 440 nm. 430 nm light is commonly used in liquid crystal display devices. In this case, as described above, it is advantageous to use the composition of the present invention in combination with a sensitizing dye. The energy of the irradiation light depends on the light source and the thickness of the coating, but is typically 5 to 2,000 mJ / cm². 2 Preferably 10 to 1,000 mJ / cm 2 If the energy of the irradiated light is less than 5 mJ / cm 2 If the resolution is too low, sufficient resolution may not be achieved; on the other hand, if the resolution is higher than 2,000 mJ / cm², it may not be possible to obtain sufficient resolution. 2 Overexposure can sometimes lead to a halo effect.

[0128] To illuminate a patterned shape, a general-purpose photomask can be used. This photomask can be freely selected from a variety of known photomasks. There are no particular restrictions on the irradiation environment; it can typically be set to ambient air or a nitrogen environment. Furthermore, if it is necessary to form a film on the entire surface of the substrate, the entire surface of the substrate can be irradiated. In this invention, patterned films also include cases where films are formed on the entire surface of the substrate.

[0129] (4) Post-exposure baking process

[0130] After exposure, post-exposure baking may be performed as needed to promote the reaction between polymers in the film via a polymerization initiator. Unlike the heating process (6) described later, this heat treatment is not for the complete curing of the coating, but rather to leave only the desired pattern on the substrate after development, allowing other areas to be removed by development. Therefore, this heat treatment is not necessary in this invention.

[0131] When performing post-exposure baking, heating plates, ovens, furnaces, etc., can be used. The heating temperature should not be too high, as it is undesirable for acids, alkalis, or free radicals generated in the exposed area to diffuse into the unexposed area. Therefore, the preferred range of post-exposure heating temperature is 40–150°C, more preferably 60–120°C. Stepwise heating can be used to control the curing rate of the composition as needed. Furthermore, there are no particular limitations on the choice of heating atmosphere; inert gases (such as nitrogen), vacuum, reduced pressure, oxygen, etc., can be selected to control the curing rate of the composition. Additionally, the heating time is preferably longer than a certain value to maintain the uniformity of the wafer surface temperature history, but preferably not too long, to suppress the diffusion of generated acids, alkalis, or free radicals. From this perspective, the heating time is preferably 20 to 500 seconds, more preferably 40 to 300 seconds.

[0132] (5) Development process

[0133] After exposure, a post-heat treatment can be performed, followed by development of the coating. The developer used for development can be any developer conventionally used for developing photosensitive compositions. In this invention, an aqueous solution of tetraalkylammonium hydroxide (TMAH) is used to specify the dissolution rate of the alkali-soluble resin, but the developer used to form the cured film is not limited to this. Preferred developers include aqueous solutions of basic compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilicates (hydrates), alkali metal phosphates (hydrates), ammonia, alkylamines, alkanolamines, and heterocyclic amines; particularly preferred basic developers are aqueous solutions of TMAH, potassium hydroxide, or sodium hydroxide. If necessary, the basic developer may also contain a water-soluble organic solvent (e.g., methanol and ethanol) or a surfactant. The development method can also be freely chosen from conventionally known methods. Specifically, development methods include immersion in the developer, pulldle development, spray development, slit development, overcoat development, spray development, etc. After development, it is best to rinse with water to obtain the developed pattern.

[0134] (6) Heating process

[0135] After development, the resulting patterned film is cured by heating. The method for forming a cured film according to the invention further includes heating at a temperature of 70–110°C. The heating equipment used in the heating process can be the same as the equipment used for baking after exposure described above. There are no particular limitations on the heating temperature; it can be freely determined as long as the coating film can be cured. However, if silanol groups remain, the chemical resistance of the cured film may sometimes be insufficient, or the dielectric constant of the cured film may sometimes increase. From this perspective, a relatively high temperature is usually chosen as the heating temperature. To maintain a high residual rate of the cured film, the curing temperature is preferably below 350°C, more preferably below 250°C. On the other hand, to accelerate the curing reaction and obtain a fully cured film, the curing temperature is preferably 70°C or higher, more preferably 80°C or higher, and particularly preferably 90°C or higher. However, the composition according to the invention maintains sufficient chemical resistance even when cured at low temperatures of 70°C to 110°C. Furthermore, there are no particular limitations on the heating time, which is typically from 10 minutes to 24 hours, preferably from 30 minutes to 3 hours. Additionally, the heating time refers to the time calculated from the point when the temperature of the patterned film reaches the desired heating temperature. In addition, it takes approximately several minutes to several hours for the patterned film to reach the required temperature from its initial temperature before heating.

[0136] Furthermore, this heating process can reduce undercut during pattern formation. While this is not a definitive theoretical conclusion, it can be speculated that this is because even after the surface layer of the pattern has hardened, the interior of the pattern still retains a certain degree of fluidity due to the influence of the acrylic polymer (which has a low glass transition temperature). Upon heating, the undercut is reduced due to its own gravity.

[0137] The cured film obtained in this way has low residual stress and suitable hardness.

[0138] The hardness of the pencil cured according to the composition of the present invention is preferably 3 to 6H, more preferably 3 to 5H.

[0139] The resulting cured film can be used in various fields, such as as an interlayer insulating film or transparent protective film for various devices, or as an interlayer insulating film for low-temperature polycrystalline silicon or a buffer coating for IC chips.

[0140] The resulting cured film is then subjected to further post-processing, such as necessary fabrication and circuit formation on the substrate to construct electronic components. Any conventional known method can be applied to this subsequent processing.

[0141] [Example]

[0142] The present invention will now be described in more detail with reference to embodiments and comparative examples, but the present invention is not limited to these embodiments and comparative examples.

[0143] The mass-average molecular weight (Mw) was determined using polystyrene-based gel permeation chromatography (GPC). GPC determinations were performed using Alliance. TM The system used was an e2695 high-speed GPC system (Nihon Waters KK) and a Super Multipore HZ-N GPC column (Tosoh Corporation). After measurements were performed using monodisperse polystyrene as the standard sample, tetrahydrofuran as the developing solvent, a flow rate of 0.6 mL / min, and a column temperature of 40 °C, the molecular weight relative to the standard sample was calculated as Mw.

[0144] Synthesis Example 1: Polysiloxane A

[0145] In a 2-liter flask equipped with a stirrer, thermometer, and condenser, 49.0 g of 25% (w / w) tetramethylammonium hydroxide (TMAH) aqueous solution, 600 mL of isopropanol (IPA), and 4.0 g of water were added. Then, a mixed solution of 60 g of methyltrimethoxysilane and 70 g of phenyltrimethoxysilane was prepared in a dropping funnel. This mixed solution was added dropwise to the flask at 50°C and stirred at the same temperature for 2 hours. Afterward, 10% (w / w) hydrochloric acid aqueous solution was added for neutralization. 400 mL of toluene and 600 mL of water were added to the neutralized solution, resulting in two phases, and the aqueous phase was removed. Furthermore, the organic phase was washed three times with 300 mL of water, and the solvent was removed by concentrating the obtained organic phase under reduced pressure. PGMEA was added to the concentrate to adjust the solids concentration to 30% (w / w), thus obtaining a polysiloxane A solution.

[0146] The Mw of the obtained polysiloxane A was 2400. The glass transition temperature of polysiloxane A was 530℃. The glass transition temperature was determined using a differential scanning calorimeter (DSC-8500, Perkin Elmer).

[0147] Synthesis Example 2: Polysiloxane B

[0148] In a 2-liter flask equipped with a stirrer, thermometer, and condenser, 36.7 g of a 25% (w / w) aqueous solution of tetramethoxysilane (TMAH), 600 mL of isopropanol (IPA), and 3.0 g of water were added. 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. This mixed solution was added dropwise to the flask at 40°C and stirred at the same temperature for 2 hours. Afterward, 10% hydrochloric acid was added for neutralization. 400 mL of toluene and 600 mL of water were added to the neutralized solution, resulting in two layers; the aqueous layer was removed. The organic layer was then washed three times with 300 mL of water, and the solvent was removed by concentrating the resulting organic layer under reduced pressure. PGMEA was added to the concentrate to adjust the solids concentration to 30% (w / w), thus obtaining a polysiloxane B solution.

[0149] The resulting polysiloxane B has a Mw of 2,100. The glass transition temperature of polysiloxane B is 330 °C.

[0150] <Preparation of the compositions of Examples 1 to 5 and Comparative Examples 1 to 3>

[0151] The compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were prepared as follows: Except for the solvent, the components and contents of the compositions are shown in Table 1 below. In the table, the values ​​of all components except surfactant A are parts by mass of each component, based on a total of 100 parts by mass of components (I) and (II). The surfactant values ​​are based on the total mass of the composition, in ppm. As the solvent, a mixed solvent of PGMEA / PGME (35% by mass / 65% by mass) was used, with a content based on 70% by mass of the total mass of the composition.

[0152] [Table 1]

[0153]

[0154] In the table,

[0155] • Acrylic polymer A: Mw=9,700, glass transition temperature: 40℃;

[0156] Acrylic polymer B: Mw=9,100, glass transition temperature: 25℃;

[0157] • Acrylic polymer C: Mw=5,800, glass transition temperature: 90℃;

[0158] • Compound A containing (meth)acryloyloxy group: ε-caprolactone-modified tris(2-acryloyloxyethyl)isocyanurate "A-9300-1CL", Shin-Nakamura Chemical;

[0159] • Polymerization initiator A: “Irgacure OXE-02”, BASF Japan;

[0160] • Thiol compound A: Pentaerythritol tetra(3-mercaptobutyrate);

[0161] • Thiol compound B: Trimethylolpropane tris(3-mercaptobutyrate);

[0162] Surfactant A: "AKS-10", Shin-Etsu Chemical.

[0163] <Membrane Stress>

[0164] Each of the resulting compositions was coated onto a 4-inch silicon wafer using a spin coater (1HDX2, Mikasa) at 1000 rpm. The coated substrate was pre-baked on a hot plate at 80°C for 90 seconds to form a film with a thickness of 1.5 μm. The pre-baked film was then further heated in an oven at 230°C in air for 60 minutes to form a cured film.

[0165] The film stress (residual stress) of the cured film was measured using a Tencor FLX-2320 (KLA Tencor). The results are described in Table 1.

[0166] <Pencil Hardness>

[0167] Each of the resulting compositions was coated onto a 4-inch silicon wafer using a spin coater at 1000 rpm. The coated substrate was pre-baked on a hot plate at 80°C for 90 seconds to form a film with a thickness of 1.5 μm. The pre-baked film was then further heated in an oven at 230°C in air for 60 minutes to form a cured film.

[0168] The cured film was subjected to a pencil scratch test using a Hi-uni (Mitsubishi Pencil) at a temperature of 23°C and a relative humidity of 50% to evaluate its pencil hardness. The pencil tip was adjusted so that a load of 750g was applied to the cured film. The manual scratch method (JIS K5600-5-4) was used, with a speed of 1mm / s to scratch 10mm for measurement. The measurement was repeated twice, and the results are described in Table 1.

Claims

1. A negative photosensitizing composition comprising: (I) Polysiloxane, (II) Acrylic polymers, (III) Compounds containing two or more (meth)acryloyloxy groups, (IV) Polymerization initiators, (V) Thiol compounds containing at least two thiol groups, and (VI) Solvents, The glass transition temperature of component (II) is 0 to 60°C.

2. The composition according to claim 1, wherein, Polysiloxane (I) contains repeating units represented by formula (Ia): Where R Ia Represents hydrogen, C 1-30 Straight-chain, branched, or cyclic saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or (meth)acryloyloxy groups; and any -CH2- in the aliphatic hydrocarbon group or aromatic hydrocarbon group may be replaced by -O- or -CO-.

3. The composition according to claim 2, wherein the polysiloxane (I) further comprises a repeating unit represented by formula (Ic): 。 4. The composition according to one or more of claims 1 to 3, wherein the content of polysiloxane (I) is from 8.0 to 35.0 by mass based on the total mass of polysiloxane (I) and acrylic polymer (II).

5. The composition according to one or more of claims 1 to 4, wherein the thiol compound (V) is a secondary thiol compound.

6. The composition according to one or more of claims 1 to 5, wherein the thiol compound (V) is represented by formula (Va): Where L represents a single bond or C 1-5 Alkylene; R is C 1-5 alkyl; n is 2 to 5; and X is C 1-20 The hydrocarbon group, in which the methylene group can be replaced by nitrogen, carbonyl or oxygen.

7. The composition according to one or more of claims 1 to 6, wherein the content of the thiol compound (V) is 0.1 to 5% by mass based on the total mass of the polysiloxane (I) and the acrylic polymer (II).

8. A method for preparing a cured film, comprising: The composition according to one or more of claims 1 to 7 is coated onto a substrate to form a film; Expose the film; The film was then developed.

9. The method of claim 8, wherein the exposure is performed at a peak wavelength of 360 to 440 nm.

10. The method according to claim 8 or 9, further comprising the step of heating at a temperature of 70 to 110°C after development.

11. A cured film formed by the method of one or more of claims 8 to 10.

12. An electronic device comprising the cured film according to claim 11.

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