Polymer, positive photosensitive resin composition, insulating film, and method for producing the same

Abstract

To provide a polymer and a positive type photosensitive composition.SOLUTION: A positive type photosensitive composition contains a polymer and an optical acid generator. The polymer has one or more structures selected from the group consisting of a structure represented by the following general formula (X1) and a structure represented by the following general formula (X2), and exhibits alkali solubility in the presence of an acid. R1 is a tertiary alkyl group, an acyl group, a tertiary alkoxycarbonyl group, a C1-6 alkoxyalkyl group, a tertiary alkoxycarbonylalkyl group, a tri(C1-6 alkyl)silyl group or a cyclic ether group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer containing a structure derived from an isocyanuric acid derivative in which a protecting group is bonded to the nitrogen atom of the isocyanuric acid skeleton, a positive photosensitive composition containing the polymer, an insulating film, and a method for producing the same. [Background technology]

[0002] Positive photosensitive compositions are used in the manufacture of display devices, semiconductor elements, integrated circuits, and the like. Positive photosensitive compositions contain a base polymer and a photoacid generator. The base polymer of a positive photosensitive composition contains a structure that increases its alkali solubility under the action of acid, and the alkali solubility is increased by the acid generated from the photoacid generator upon exposure. When development is performed with alkali after exposure, the exposed areas are selectively dissolved in alkali, resulting in a patterned film.

[0003] Examples of structures that exhibit increased alkali solubility due to the action of an acid include structures in which acidic groups such as carboxyl groups and phenolic hydroxyl groups are protected with protecting groups. In the presence of an acid, the protecting groups are eliminated to generate acidic groups, thereby increasing the alkali solubility of the base polymer.

[0004] Positive photosensitive materials used as permanent resists require higher durability because the cured film after patterning remains as a functional film on the device, and positive photosensitive compositions based on polyimide or silicone polymers have been proposed. Patent Document 1 discloses a positive photosensitive composition based on a polymer having a siloxane structure. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] WO2014 / 007231 issue Summary of the Invention [Problem to be solved by the invention]

[0006] Polymers with phenolic hydroxyl groups protected by protecting groups, which have a structure that increases alkaline solubility under the action of acid, inevitably absorb light in the short wavelength region of visible light (near 400 nm wavelength) due to the conjugated structure of phenol. Furthermore, polymers with phenolic structures tend to have a reduced visible light transmittance after heating, leaving room for improvement in transparency.

[0007] In view of the above, an object of the present invention is to provide a polymer that is alkali-soluble in the presence of an acid and has excellent transparency, and a positive-working photosensitive composition containing the polymer. [Means for solving the problem]

[0008] One embodiment of the present invention is an isocyanuric acid derivative used in the preparation of a polymer, and has a structure represented by the following general formula (I):

[0009] [ka]

[0010] In general formula (I), R 1 is a protecting group that generates an NH group upon elimination, and R 2 is a substituent having a polymerizable functional group. 3 is a halogen or a monovalent group, and R 1 and R 2 It may be the same as either one of the above.

[0011] The protecting group R 1 is eliminated in the presence of an acid to generate an NH group of the isocyanuric acid skeleton, and is also used as a tertiary alkyl group, an acyl group, a tertiary alkoxycarbonyl group, C 1-6 Alkoxyalkyl groups, tertiary alkoxycarbonylalkyl groups, tri(C 1-6 alkyl)silyl group, cyclic ether group, etc. 1 As the alkyl group, a tert-butoxycarbonyl group is particularly preferred.

[0012] R 2 Examples of the polymerizable functional group contained in R include an alkenyl group, a (meth)acryloyl group, an epoxy group, an oxetane group, a hydrosilyl group, a silanol group, an alkoxysilyl group, a carboxy group, an amino group, an isocyanate group, a mercapto group, and a halogen atom. 2 may be an allyl group.

[0013] R 2 Examples of the isocyanuric acid derivative in which is an allyl group include a compound represented by the following general formula (Ia) or a compound represented by the following general formula (Ib).

[0014] [ka]

[0015] One embodiment of the present invention is a polymer having a structure represented by the following general formula (X1) and / or a structure represented by the following general formula (X2): 1 represents the protecting group R in the above general formula (I). 1 and is preferably a tert-butoxycarbonyl group.

[0016] [ka]

[0017] The polymer may contain a polysiloxane skeleton. The polymer may contain a crosslinkable functional group capable of forming a crosslinked structure by heating, such as an epoxy group or an oxetane group. The weight-average molecular weight of the polymer is, for example, about 1,000 to 200,000.

[0018] One embodiment of the present invention is a positive-type photosensitive composition containing (A) the above-described polymer and (B) a photoacid generator. The photosensitive composition may further contain (C) a photosensitizer, (D) a crosslinking agent, (E) a thermosetting resin, etc. Examples of crosslinking agents include compounds containing two or more functional groups per molecule that can react with the crosslinkable functional groups of the above-described polymer.

[0019] An insulating film can be obtained by applying a solution containing the above polymer to a substrate and then drying and removing the solvent. Alternatively, a patterned insulating film can be formed by applying the above positive photosensitive composition to a substrate and then patterning the composition through exposure and alkaline development. After alkaline development, the insulating film can be cured by heating (post-baking). [Effects of the Invention]

[0020] By using the above polymer or positive photosensitive composition, an insulating film with excellent transparency can be formed. DETAILED DESCRIPTION OF THE INVENTION

[0021] One embodiment of the present invention is a compound having a functionally protected isocyanuric acid structure, which is an isocyanuric acid derivative represented by the following general formula (I).

[0022] [ka]

[0023] In general formula (I), R 1 is a protecting group that generates an NH group upon elimination, and R 2 is a substituent having a polymerizable functional group. 3 is a halogen or any monovalent group, and R 1 or R 2 may be the same as

[0024] The above compound is R 2 By reacting with the polymerizable functional group of the compound, a protecting group R is attached to the nitrogen atom of the isocyanuric acid skeleton. 1This polymer can be formed by adding a protecting group R 1 The resulting polymer exhibits alkali solubility due to the elimination of the aryl group and the formation of an acidic NH group. The polymer can be used, for example, as a base polymer in a positive-type photosensitive composition.

[0025] Protecting group R that generates an NH group upon elimination 1 Examples of the alkyl group include an alkyl group, an aralkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an alkoxyalkyl group, a trialkylsilyl group, and a cyclic ether group.

[0026] In the positive photosensitive composition, a protecting group R is attached to the nitrogen atom of the isocyanuric acid skeleton. 1 The acid group is protected by the photoacid generator upon exposure, and the protecting group R 1 The protecting group R 1 is preferably one that is difficult to be eliminated from the nitrogen atom in an alkaline environment, but can be eliminated in an acidic environment to generate an NH group.

[0027] Protective group R that can be removed in an acidic environment 1 Examples of the alkyl group include tertiary alkyl groups such as tert-butyl and tert-pentyl groups; aralkyl groups such as trityl, diphenylmethyl and 4,4'-dimethoxytrityl groups; acyl groups such as formyl, acetyl, propionyl, butyryl and benzoyl groups; fluorinated acyl groups in which some or all of the hydrogen atoms of the above-mentioned acyl groups have been substituted with fluorine atoms; tertiary alkoxycarbonyl groups such as tert-butoxycarbonyl and tert-pentyloxycarbonyl groups; and lower (C alkyl) groups such as methoxymethyl, 1-ethoxy-1-ethyl and 1-methoxy-1-propyl groups. 1-6)alkoxyalkyl groups; tertiary alkoxycarbonylalkyl groups such as tert-butoxycarbonylmethyl group, tert-butoxycarbonylethyl group, tert-pentyloxycarbonylmethyl group, and tert-pentyloxycarbonylethyl group; tri(C) groups such as trimethylsilyl group, dimethylethylsilyl group, triethylsilyl group, and tert-butyldimethylsilyl group. 1-6 and cyclic ether groups such as a tetrahydropyranyl group, a tetrahydrofuranyl group, etc. Among these, a tert-butyl group, a tert-butoxycarbonyl group, an acetyl group, a trifluoroacetyl group, a trityl group, a methoxymethyl group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a tetrahydropyranyl group, and a tetrahydrofuranyl group are preferred, with a tert-butyl group and a tert-butoxycarbonyl group being particularly preferred, because they have high storage stability, can be easily deprotected in the presence of an acid, and have excellent photosensitivity.

[0028] R 2 The polymerizable functional group contained in may be either one that is reactive with the same type of functional group (typically, a chain-polymerizable reactive group such as radical polymerization or ionic polymerization) or one that is reactive with a different type of functional group (typically, a step-growth polymerizable reactive group). The polymerization reaction caused by the polymerizable functional group may be addition polymerization, ring-opening polymerization, polycondensation, polyaddition, addition-condensation, or the like. Examples of the polymerizable functional group include alkenyl groups (such as vinyl groups, allyl groups, butenyl groups, and hexenyl groups), (meth)acryloyl groups, epoxy groups, oxetane groups, hydrosilyl groups, silanol groups, alkoxysilyl groups, carboxy groups, amino groups, isocyanate groups, mercapto groups, and halogens.

[0029] R 2 The polymerizable functional group R may be bonded directly to the nitrogen atom of the isocyanuric acid skeleton, or may be bonded via a divalent organic group such as alkylene or oxyalkylene. 2Specific examples of R include a vinyl group, an allyl group, a carboxyethyl group, a hydroxyethyl group, a tri(methoxysilyl)propyl group, a glycidyl group, an acryloyloxyethyl group, and halogens (chlorine atom, bromine atom, iodine atom). 2 is a functional group having an ethylenically unsaturated group such as a vinyl group, an allyl group, an acryloyloxyethyl group, or a (meth)acryloyl group, a hydrosilylation reaction occurs between a compound having a hydrosilyl (SiH) group and the ethylenically unsaturated group to form an Si-C bond, thereby obtaining a polymer.

[0030] R 3 is any group, and the protecting group R 1 may be the same as R 2 It may be the same as R 3 is R 2 For example, R 2 is a substituent having an ethylenically unsaturated group such as an allyl group, and R 3 R may be a substituent having a polymerizable functional group such as a glycidyl group. 1 R is different from R and does not have a polymerizable functional group 3 Examples of R include primary alkyl groups such as methyl, ethyl, and propyl groups, secondary alkyl groups such as isopropyl and isobutyl groups, phenyl groups, and benzyl groups. 3 By selecting 1 The ease of deprotection, the acidity of the NH group generated by deprotection, and the alkali solubility after deprotection can be adjusted.

[0031] Examples of the isocyanuric acid derivative include R 2 and R 3 is an allyl group (general formula (Ia) below); and 2 is an allyl group, and R 3 R 1 Examples of such a compound include a compound having the same protecting group as the compound (general formula (Ib) below).

[0032] [ka]

[0033] The method for synthesizing the compound represented by general formula (I) is not particularly limited. For example, a compound represented by general formula (I) can be synthesized by using a method in which one or two of the three NH groups of isocyanuric acid are substituted with a substituent R containing a polymerizable functional group. 2 The isocyanuric acid derivative represented by general formula (I) is obtained by preparing an isocyanuric acid derivative substituted with the formula (I) and substituting the hydrogen atoms of one or two remaining NH groups with protecting groups.

[0034] For example, the compound represented by the general formula (Ia) can be obtained by reacting diallyl isocyanurate with a protecting group introduction reagent. The compound represented by the general formula (Ib) can be obtained by reacting monoallyl isocyanurate with a protecting group introduction reagent. If a Boc reagent such as di-tert-butyl dicarbonate is used as the protecting group introduction reagent, the protecting group R 1 An isocyanuric acid derivative having a tert-butoxycarbonyl group as a protecting group can be obtained. If an acylating reagent such as an acetyl halide is used as a protecting group introduction reagent, the protecting group R 1 As a result, an isocyanuric acid derivative having an acyl group such as an acetyl group is obtained.

[0035] [polymer] The above isocyanuric acid derivatives are R 2 By reacting with the polymerizable functional group of the compound, a protecting group R is attached to the nitrogen atom of the isocyanuric acid skeleton. 1 A polymer having a structure in which the nitrogen atom of the isocyanuric acid skeleton is bonded to the protecting group R can be formed. 1 Examples of the bonded structure include the following X1 and X2. [ka]

[0036] Hereinafter, the structure represented by the general formula X1 and the structure represented by the general formula X2 will be referred to as "Structure X". A polymer having Structure X can be prepared by adding a protecting group R 1When the NH group is eliminated, an acidic group, an NH group, is generated, and the compound exhibits alkali solubility. That is, in the structure X, the NH group of the isocyanuric acid skeleton, which is the alkali solubility-imparting group, is protected by a protecting group R 1 The polymer containing Structure X has its protecting group removed (deprotected) by reaction with the acid generated from the photoacid generator, and its alkaline solubility increases, making it usable as a photosensitive resin capable of forming positive patterns.

[0037] The polymer of this embodiment preferably includes, in addition to the above-described structure X, a polymer skeleton structure other than structure X. Examples of the polymer skeleton structure include polyacrylic, polyphenol, polyamide, polyacid anhydride, polycarbonate, polydiene, polyester, polyhaloolefin, polyimide, polyimine, polyketone, polyolefin, polyether, polyphenylene, polyphosphazene, polysiloxane, polysilane, polystyrene, polysulfide, polysulfone, polyurethane, polyurea, and polyvinyl.

[0038] For example, a polymer having a polysiloxane skeleton in addition to the structure X is expected to have excellent heat resistance and a low dielectric constant. From the viewpoint of high heat resistance and low dielectric constant, a cyclic polysiloxane structure is particularly preferred.

[0039] In this specification, the term "polysiloxane structure" refers to a structural skeleton having siloxane units Si-O-Si, and the term "cyclic polysiloxane structure" refers to a cyclic molecular structural skeleton having siloxane units (Si-O-Si) as ring components. A positive photosensitive resin containing a polysiloxane structure is a polymer having a structure X (i.e., structure X1 and / or structure X2) with a "compound having siloxane units" as the main skeleton.

[0040] When a permanent resist is prepared using a positive photosensitive composition, the polymer preferably has a polymerizable functional group. When heating (post-baking) is performed after exposure and development, crosslinked structures are introduced by reactions between the polymerizable functional groups of the polymer and between the polymerizable functional groups of the polymer and a crosslinking agent (component (D) described below), and a patterned cured film is obtained.

[0041] Polysiloxane polymers can be obtained, for example, by a hydrosilylation reaction. The hydrosilylation reaction is a reaction between a polysiloxane compound having at least two SiH groups (hydrosilyl groups) per molecule and a compound having a carbon-carbon double bond reactive with the SiH groups. When at least one of these compounds (starting materials) has a structure X in addition to the above functional groups, a polysiloxane polymer having a structure X can be obtained.

[0042] For example, a polysiloxane polymer having the structure X can be obtained by a hydrosilylation reaction using the following compounds (α) and (β) as starting materials. Compound (α): In the above general formula (I), R 2 isocyanuric acid derivatives having a carbon-carbon double bond (ethylenically unsaturated group) as a polymerizable functional group; Compound (β): A polysiloxane compound having at least two SiH groups in one molecule.

[0043] (Compound (α): Isocyanuric acid derivative) Compound (α) is a compound represented by the formula (I) 2is an isocyanuric acid derivative having a carbon-carbon double bond (ethylenically unsaturated group) as a polymerizable functional group. Examples of ethylenically unsaturated groups reactive with SiH groups include vinyl, allyl, methallyl, acrylic, methacrylic, 2-hydroxy-3-(allyloxy)propyl, 2-allylphenyl, 3-allylphenyl, 4-allylphenyl, 2-(allyloxy)phenyl, 3-(allyloxy)phenyl, 4-(allyloxy)phenyl, 2-(allyloxy)ethyl, 2,2-bis(allyloxymethyl)butyl, 3-allyloxy-2,2-bis(allyloxymethyl)propyl, and vinyl ether groups.

[0044] Compound (α) may have multiple (two) ethylenically unsaturated groups in one molecule, as in the compound represented by general formula (Ia) above, or may have one ethylenically unsaturated group in one molecule, as in the compound represented by general formula (Ib) above. When an isocyanuric acid derivative having two ethylenically unsaturated groups in one molecule is used as compound (α), a polymer having structure X1 is obtained. When an isocyanuric acid derivative having one ethylenically unsaturated group in one molecule is used as compound (α), a polymer having structure X2 is obtained.

[0045] When compound (α) having multiple ethylenically unsaturated groups in one molecule is used, multiple polysiloxane compounds (compound (β)) are crosslinked by a hydrosilylation reaction, which increases the molecular weight of component (A) and tends to improve film-forming properties and the mechanical strength, heat resistance, and chemical resistance of the insulating film. As compound (α), an isocyanuric acid derivative having multiple ethylenically unsaturated groups in one molecule and an isocyanuric acid derivative having one ethylenically unsaturated group in one molecule may be used in combination.

[0046] (Compound (β): Polysiloxane compound) Compound (β) is a polysiloxane compound having at least two SiH groups per molecule. For example, compounds described in WO96 / 15194 having at least two SiH groups per molecule can be used. Specific examples of compound (β) include hydrosilyl group-containing polysiloxanes with a linear structure, polysiloxanes having hydrosilyl groups at the molecular terminals, and cyclic polysiloxanes containing hydrosilyl groups. The cyclic polysiloxane may have a polycyclic structure, and the polycyclic ring may have a polyhedral structure. To form an insulating film with high heat resistance and mechanical strength, it is preferable to use a cyclic polysiloxane compound having at least two SiH groups per molecule as compound (β). Compound (β) preferably contains three or more SiH groups per molecule. From the viewpoint of heat resistance and light resistance, the group present on the Si atom is preferably either a hydrogen atom or a methyl group.

[0047] Examples of hydrosilyl group-containing polysiloxanes having a linear structure include copolymers of dimethylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units, copolymers of diphenylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units, copolymers of methylphenylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units, and polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups.

[0048] Polysiloxanes having hydrosilyl groups at the molecular terminals include polysiloxanes whose terminals are blocked with dimethylhydrogensilyl groups, and polysiloxanes containing dimethylhydrogensiloxane units (H(CH3)2SiO 1 / 2 units), and SiO2 units, SiO 3 / 2 units and at least one siloxane unit selected from the group consisting of SiO units.

[0049] The cyclic polysiloxane is represented by, for example, the following general formula (II).

[0050] [ka]

[0051] R in the formula 4 , R 5 and R 6 each independently represents an organic group having 1 to 20 carbon atoms. m represents an integer of 2 to 10, and n represents an integer of 0 to 10. m is preferably 3 or more. m+n is preferably 3 to 12.

[0052] R 4 , R 5 and R 6 R is preferably an organic group composed of an element selected from the group consisting of C, H, and O. 4 , R 5 and R 6 Examples of R include alkyl groups, hydroxyalkyl groups, alkoxyalkyl groups, oxyalkyl groups, and aryl groups. Among these, chain alkyl groups such as methyl groups, ethyl groups, propyl groups, hexyl groups, octyl groups, decyl groups, and dodecyl groups, cyclic alkyl groups such as cyclohexyl groups and norbornyl groups, and phenyl groups are preferred. From the viewpoint of availability of compound (β), R 4 , R 5 and R 6 is preferably a methyl group, a propyl group, a hexyl group or a phenyl group. 4 and R 5 is more preferably a chain alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0053] Examples of cyclic polysiloxane compounds represented by general formula (II) include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, and 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane. Among these, from the viewpoint of availability and reactivity of the SiH group, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (in general formula (II), m=4, n=0, and R 4 is a methyl group).

[0054] The compound (β) may be a polycyclic polysiloxane. The polycyclic ring may have a polyhedral structure. The polysiloxane having a polyhedral skeleton preferably has 6 to 24 Si atoms constituting the polyhedral skeleton, and more preferably has 6 to 10 Si atoms. A specific example of the polysiloxane having a polyhedral skeleton is silsesquioxane (number of Si atoms = 8) represented by the following general formula (III).

[0055] [ka]

[0056] In the above formula, R 10 ~R 17are each independently a monovalent group selected from the group consisting of a hydrogen atom, a chain alkyl group (e.g., methyl, ethyl, propyl, and butyl), a cycloalkyl group (e.g., cyclohexyl), an aryl group (e.g., phenyl and tolyl), groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups have been substituted with halogen atoms or cyano groups (e.g., chloromethyl, trifluoropropyl, and cyanoethyl), an alkenyl group (e.g., vinyl, allyl, butenyl, and hexenyl), a (meth)acryloyl group, an epoxy group, and an organic group containing a mercapto group or an amino group. The carbon number of the hydrocarbon group is preferably 1 to 20, and more preferably 1 to 10. A cyclic polysiloxane having a polyhedral skeleton has two or more hydrosilyl groups, which are reactive groups in a hydrosilylation reaction. Therefore, R 10 ~R 17 At least two of these are hydrogen atoms.

[0057] The cyclic polysiloxane may be a silylated silicic acid having a polyhedral skeleton. Specific examples of the silylated silicic acid having a polyhedral skeleton include compounds represented by the following general formula (IV) (number of Si atoms = 8):

[0058] [ka]

[0059] In the above formula, R 18 ~R 41 represents R in the above general formula (III). 10 ~R 17 Similar to the specific example of R 18 ~R 41 At least two of these are hydrogen atoms.

[0060] Polysiloxanes can be obtained by known synthesis methods. For example, cyclic polysiloxanes represented by general formula (II) can be synthesized by methods described in WO96 / 15194, etc. Polysiloxanes having a polyhedral skeleton, such as silsesquioxanes, and silylated silicas having a polyhedral skeleton can be synthesized by methods described in, for example, JP-A-2004-359933, JP-A-2004-143449, JP-A-2006-269402, etc. As compound (β), commercially available polysiloxane compounds may be used.

[0061] (Other starting materials) In preparing a polymer by hydrosilylation reaction, other starting materials may be used in addition to the above-mentioned compound (α) and compound (β). For example, an ethylenically unsaturated group-containing compound other than the above-mentioned compound (α) may be used as a starting material.

[0062] For example, in addition to compound (α) and compound (β), a compound having two or more ethylenically unsaturated groups in one molecule (hereinafter referred to as "compound (γ)") may be used as a starting material. When compound (γ) is used, the polysiloxane compound (compound (β)) is crosslinked by a hydrosilylation reaction, which increases the molecular weight of the polymer and tends to improve film-forming properties and the heat resistance of the insulating film.

[0063] Compound (γ) may be either an organic polymer compound or an organic monomer compound. Examples of organic polymer compounds include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylic ester, polyamide, phenol-formaldehyde (phenolic resin), and polyimide compounds. Examples of organic monomer compounds include phenol, bisphenol, aromatic hydrocarbon compounds such as benzene or naphthalene; aliphatic hydrocarbon compounds such as linear and alicyclic compounds; and heterocyclic compounds.

[0064] Specific examples of the compound (γ) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1,1,2,2-tetraallyloxyethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monomethyl isocyanurate, 1,2,4-trivinylcyclohexane, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, bisphenol A, Examples of the epoxy resin include diallyl ether of bisphenol S, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis(allyloxy)adamantane, 1,3-bis(vinyloxy)adamantane, 1,3,5-tris(allyloxy)adamantane, 1,3,5-tris(vinyloxy)adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl ether, 2,5-diallylphenol allyl ether, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), allyl ether of novolak phenol, allylated polyphenylene oxide, and other conventionally known epoxy resins in which all of the glycidyl groups have been replaced with allyl groups. Furthermore, compounds in which the allyl group in the above-exemplified compounds is replaced with a (meth)acryloyl group (for example, polyfunctional (meth)acrylates) can also be suitably used as compound (γ).

[0065] The compound (γ) may be a polysiloxane compound having two or more ethylenically unsaturated groups. Specific examples of polysiloxane compounds having two or more ethylenically unsaturated groups include compounds in which some or all of the hydrogen atoms bonded to Si in the compound (β) are replaced with ethylenically unsaturated groups. Among these, from the viewpoint of improving the heat resistance of the insulating film, cyclic polysiloxane compounds having two or more ethylenically unsaturated groups are preferred.

[0066] A specific example of a cyclic polysiloxane compound having two or more ethylenically unsaturated groups is a cyclic polysiloxane in which a vinyl group is bonded to a Si atom as the ethylenically unsaturated group. Examples of cyclic polysiloxane compounds having two or more vinyl groups bonded to Si atoms include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, and 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane.

[0067] As a starting material for the hydrosilylation reaction, a compound having only one functional group participating in the hydrosilylation reaction per molecule (hereinafter referred to as "compound (δ)") may be used. The functional group participating in the hydrosilylation reaction is an SiH group or an ethylenically unsaturated group. By using a compound having only one functional group participating in the hydrosilylation reaction, a specific functional group can be introduced at the end of a polymer.

[0068] For example, by using a siloxane compound having one SiH group as compound (δ), a siloxane structural moiety can be introduced into the polymer terminal. Specific examples of the siloxane compound having one SiH group include a cyclic polysiloxane compound having m=1 in the above-mentioned general formula (II), a cyclic polysiloxane compound having R10 ~R 17 a polyhedral polysiloxane compound in which one of R 18 ~R 41 and silylated silicate compounds in which one of the groups is a hydrogen atom. The siloxane compound having one SiH group may be a chain siloxane compound.

[0069] By using a compound containing one ethylenically unsaturated group as compound (δ), the desired functional group can be introduced into the polymer terminal. In addition to the above, compounds participating in the hydrosilylation reaction, such as linear polysiloxanes containing two or more SiH groups, may also be included in the starting materials.

[0070] The compounds (α), (β), (γ), and (δ) may each have, in addition to an ethylenically unsaturated group or SiH group, which is a polymerizable reactive group involved in the hydrosilylation reaction, a polymerizable reactive group (crosslinking reactive group) that is not involved in the hydrosilylation reaction. Examples of polymerizable reactive groups that are not involved in the hydrosilylation reaction include epoxy groups, oxetane groups, silanol groups, alkoxysilyl groups, carboxy groups, amino groups, isocyanate groups, and mercapto groups. The crosslinking reactive group is preferably one that can form a crosslinked structure by heating (post-baking) after exposure and development of a coating film of the photosensitive composition, and is preferably an epoxy group, oxetane group, or the like.

[0071] Examples of compounds having an alkenyl group and an epoxy group as a crosslinking reactive group in one molecule include allyl glycidyl ether, vinylcyclohexyl epoxide, etc. Examples of compounds having an alkenyl group and an oxetane group as a crosslinking reactive group in one molecule include 3-[(allyloxy)methyl]-3-methyloxetane, 3-[(allyloxy)methyl]-3-ethyloxetane, etc.

[0072] (hydrosilylation reaction) The order and method of the hydrosilylation reaction are not particularly limited. From the viewpoint of simplifying the synthesis process, a method in which all starting materials are charged into one pot and the hydrosilylation reaction is carried out, and unreacted compounds are finally removed is preferred. The hydrosilylation reaction may be carried out in two or more stages. For example, from the viewpoint of suppressing the formation of low-molecular-weight compounds, a method in which a compound containing multiple ethylenically unsaturated groups (e.g., an isocyanuric acid derivative represented by general formula (Ia) and compound (γ)) and a compound containing multiple SiH groups (e.g., compound (β)) are hydrosilylated in excess of one of them, and after removing the unreacted compounds as necessary, a compound having only one functional group participating in the hydrosilylation reaction per molecule (e.g., an isocyanuric acid derivative represented by general formula (Ib) and compound (δ)) is added to carry out the hydrosilylation reaction is preferred.

[0073] The ratio of each compound in the hydrosilylation reaction is not particularly limited, but the total amount A of ethylenically unsaturated groups in the starting materials and the total amount B of SiH groups preferably satisfy the relationship 1≦B / A≦30, and more preferably 1≦B / A≦10. When B / A is 1 or more, unreacted ethylenically unsaturated groups are unlikely to remain, and when B / A is 30 or less, unreacted compound (β) is unlikely to remain, thereby improving the properties of the insulating film.

[0074] The hydrosilylation reaction may be carried out using a hydrosilylation catalyst such as chloroplatinic acid, a platinum-olefin complex, or a platinum-vinylsiloxane complex. The hydrosilylation catalyst may be used in combination with a co-catalyst. The amount of the hydrosilylation catalyst to be added is not particularly limited, but is preferably 10 moles based on the total amount (number of moles) of ethylenically unsaturated groups contained in the starting material. -8 ~10 -1 times, more preferably 10 -6 ~10 -2 It's double.

[0075] The reaction temperature for the hydrosilylation may be appropriately set, and is preferably 30 to 200° C., more preferably 50 to 150° C. An appropriate solvent may be used in the hydrosilylation reaction. In the hydrosilylation reaction, a gelation inhibitor may be used as needed.

[0076] The weight-average molecular weight of the polymer in terms of polystyrene is, for example, about 1,000 to 200,000, and preferably 2,000 to 150,000. When the molecular weight of the polymer is within the above range, it is possible to form an insulating film (cured film) that has excellent solubility in organic solvents and in the developer during patterning, as well as excellent mechanical strength, film-forming properties, heat resistance, chemical resistance, etc.

[0077] In the above, the hydrosilylation reaction between a compound (α) having Structure X and an ethylenically unsaturated group in one molecule and a polysiloxane compound (β) having at least two SiH groups in one molecule was described as an example of a method for obtaining a polysiloxane polymer having Structure X, but the method for synthesizing a polymer having Structure X is not limited to this. A polymer having Structure X can also be obtained by a hydrosilylation reaction using a starting material other than those described above.

[0078] For example, instead of compound (α), a substituent R 2 A polysiloxane polymer having Structure X may be prepared using an isocyanuric acid derivative having an SiH group as the reactive group as a starting material. In this case, a polysiloxane polymer having Structure X is obtained by a hydrosilylation reaction between the isocyanuric acid derivative having an SiH group and a polysiloxane compound having an ethylenically unsaturated group. The polysiloxane compound having an ethylenically unsaturated group may contain multiple ethylenically unsaturated groups.

[0079] Examples of cyclic siloxane compounds containing ethylenically unsaturated groups include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, and 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane. From the viewpoint of heat resistance and light resistance, it is preferable that the organic group present on the Si atom of the cyclic polysiloxane compound having an ethylenically unsaturated group is a vinyl group or a methyl group.

[0080] The polymer having Structure X is not limited to a polysiloxane-based polymer. Furthermore, the polymer having Structure X may have a structure in which an acidic group (alkali-solubility-imparting group) other than the NH group of Structure X (isocyanuric acid skeleton) is protected with a protecting group. Examples of the acidic group other than the NH group of the isocyanuric acid skeleton include acidic groups such as carboxylic acid and phenolic hydroxyl groups. By including a structure in which the acidic group of a carboxylic acid or phenolic hydroxyl group is protected in addition to Structure X, an increase in exposure sensitivity can be expected.

[0081] Examples of protecting groups for phenolic hydroxyl groups include tert-butoxycarbonyl and trialkylsilyl groups. For example, a phenolic hydroxyl group can be protected with a tert-butoxycarbonyl group by a reaction using a Boc reagent. Examples of protecting groups for carboxylic acids include tertiary alkyl esters and acetals. Examples of tertiary alkyl groups in tertiary alkyl esters of carboxylic acids include tert-butyl, adamantyl, tricyclodecyl, and norbornyl groups. Acidic groups having these protecting groups can be introduced into polymers by various known methods.

[0082] The polymer having structure X can be prepared by reacting the protecting group R in structure X with the protecting group R in the presence of an acid. 1 In the presence of an acid, the amount of NH groups generated by the elimination of the protecting group R of the structure X1 is preferably 0.1 mmol / g or more. 1 is eliminated to generate one NH group, and a protecting group R 1 is eliminated to generate two NH groups. Therefore, in the presence of acid, the protecting group R 1 The amount of NH groups produced by elimination is equal to the sum of twice the amount of Structure X2 and the amount of Structure X1.

[0083] In the presence of an acid, the protecting group R 1 The greater the number of NH groups generated by the elimination of the protecting group R, the higher the alkali solubility of the polymer tends to be. 1 The greater the number of NH groups generated by the elimination of the protecting group R in the presence of an acid, the greater the exposure sensitivity tends to be. 1 The amount of NH groups generated by elimination is more preferably 0.3 mmol / g or more, further preferably 0.5 mmol / g or more, and may be 0.8 mmol / g or more, 1 mmol / g or more, 1.2 mmol / g or more, or 1.4 mmol / g or more.

[0084] In the presence of an acid, the protecting group R 1 Although there is no particular upper limit to the amount of NH groups generated by the elimination of the protecting group R, if the content of the structure X is excessively large, it may be difficult to adjust the exposure dose or may cause a decrease in the heat resistance, transparency, etc. of the polymer. 1 The amount of NH groups generated by elimination of is preferably 15 mmol / g or less, more preferably 10 mmol / g or less, even more preferably 5 mmol / g or less, and may be 3 mmol / g or less, 2 mmol / g or less, or 1.8 mmol / g or less.

[0085] [Photosensitive composition] The polymer having the above structure X can be converted to a protecting group R by the action of an acid. 1The compound is cleaved to generate an NH group, which is an acidic group, and thus has increased alkali solubility, making it applicable as a positive-type photosensitive resin. One embodiment of the present invention is a positive-type photosensitive composition containing (A) a polymer having the above-described structure X and (B) a photoacid generator. In addition to components (A) and (B), the photosensitive composition may also contain a photosensitizer as component (C) and a crosslinker as component (D).

[0086] <(B) Photoacid generator> The photosensitive composition contains a photoacid generator as component (B). When the photoacid generator is exposed to active energy rays, an acid is generated. Examples of active energy rays include visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays. The action of the acid generated from the photoacid generator converts the protecting group R of the component (A) into a protective group R. 1 is released, and the alkali solubility increases.

[0087] The photoacid generator contained in the photosensitive composition is not particularly limited as long as it generates a Lewis acid upon exposure. Specific examples of the photoacid generator include ionic photoacid generators such as sulfonium salts, iodonium salts, ammonium salts, and other onium salts; and nonionic photoacid generators such as imide sulfonates, oxime sulfonates, and sulfonyldiazomethanes. Examples of anions contained in ionic photoacid generators include B(C6F5)4 - , PF6 - , SbF6 - , CH3SO3 - , C2H5SO3 - , C3H7SO3 - , camphorsulfonic acid anion, CH3C6H5SO3 - , CF3SO3 - , C4F9SO3 - , amide acid anion, methide acid anion, etc. As the photoacid generator, sulfonium salts, iodonium salts, imide sulfonates and oxime sulfonates are preferred because of their high photosensitivity, and imide sulfonates and oxime sulfonates are particularly preferred.

[0088] The content of the photoacid generator in the photosensitive composition is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 7 parts by weight, and even more preferably 0.5 to 5 parts by weight, per 100 parts by weight of component (A). When the amount of photoacid generator is within the above range, the alkali solubility of component (A) in the exposed area can be sufficiently increased to improve patterning properties, and a decrease in contrast caused by excess acid can be suppressed.

[0089] <(C) Sensitizer> The photosensitive composition may contain a sensitizer. The use of a sensitizer improves the exposure sensitivity during patterning. Examples of sensitizers for positive photosensitive compositions include naphthalene-based compounds, anthracene-based compounds, and thioxanthone-based compounds. Among these, anthracene-based sensitizers are preferred because of their excellent photosensitizing effect. Specific examples of anthracene-based sensitizers include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene (DBA), 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, 9,10-bis(octanoyloxy)anthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di-tert-butylanthracene, etc. Among these, from the viewpoint of compatibility with the photosensitive composition, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, 9,10-bis(octanoyloxy)anthracene, etc. are preferred.

[0090] The content of the sensitizer in the photosensitive composition is not particularly limited and may be adjusted appropriately within a range that allows the sensitizing effect to be exhibited. In consideration of the balance between the sensitizing effect and the properties of the insulating film, the content of the sensitizer is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 40 parts by weight, even more preferably 0.5 to 35 parts by weight, and particularly preferably 1 to 30 parts by weight, per 100 parts by weight of component (A). Furthermore, in order to obtain the sensitizing effect, the molar ratio (C / B) of the sensitizer (C) to the photoacid generator (B) is preferably 0.01 to 300, more preferably 0.1 to 100.

[0091] <(D) Crosslinking Agent> The photosensitive composition may contain, as a crosslinking agent, a compound having a functional group capable of reacting (bonding) with the crosslinkable functional group of the component (A) to introduce a crosslinked structure. The crosslinking agent is preferably a compound having two or more functional groups per molecule capable of reacting with the crosslinkable reactive group of the component (A).

[0092] For example, if component (A) has a polysiloxane skeleton and contains SiH groups that were not used in the hydrosilylation reaction, a crosslinked structure can be introduced by the hydrosilylation reaction between component (A) and the crosslinking agent by adding a compound having two or more ethylenically unsaturated groups per molecule to the photosensitive composition. Examples of the compound having two or more ethylenically unsaturated groups per molecule include compounds similar to compound (γ) exemplified in the synthesis of component (A) above.

[0093] When the photosensitive composition contains a crosslinking agent, the content of the crosslinking agent is preferably 0.1 to 40 parts by weight, more preferably 0.5 to 35 parts by weight, and even more preferably 1 to 30 parts by weight, per 100 parts by weight of component (A). When the photosensitive composition contains a crosslinking agent, after patterning by exposure and development, it is preferable to introduce a crosslinked structure by reacting component (A) with the crosslinking agent through heating (post-baking). The introduction of the crosslinked structure hardens the patterned film, thereby improving the insulating properties, heat resistance, solvent resistance, etc. of the patterned film.

[0094] <(E) Thermosetting resin> The photosensitive composition may contain a polymerizable compound (thermosetting resin) that is not reactive with the above-mentioned component (A) and can be thermoset independently. Examples of thermosetting resins include epoxy resins, oxetane resins, isocyanate resins, blocked isocyanate resins, bismaleimide resins, bisallylnadiimide resins, acrylic resins, allyl-cured resins, and unsaturated polyester resins. The thermosetting resin may be a side-chain reactive group-type thermosetting polymer having a reactive group such as an allyl group, a vinyl group, an alkoxysilyl group, or a hydrosilyl group in the side chain or at the end of the polymer chain.

[0095] The content of the thermosetting resin is preferably 0.1 to 40 parts by weight, more preferably 0.5 to 35 parts by weight, and even more preferably 1 to 30 parts by weight, per 100 parts by weight of component (A). When the photosensitive composition contains a thermosetting resin that does not exhibit reactivity with component (A), a polymer network of the thermosetting resin is formed surrounding component (A) by post-baking, and the pattern film is cured, thereby improving the insulating properties, heat resistance, solvent resistance, etc. of the pattern film.

[0096] The photosensitive resin composition may contain both the above-mentioned components (D) and (E). The component (E) may be reactive with the component (D).

[0097] <Solvent> The photosensitive composition can be obtained by dissolving or dispersing the above components (A) and (B), and optionally components (C), (D), and (E) in a solvent. The photosensitive composition can be prepared by mixing the components immediately before film formation, or it can be stored in the form of a single liquid in which all components have been mixed in advance.

[0098] Any solvent capable of dissolving component (A) may be used. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and diethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), propylene glycol diacetate (PGDA), diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol diethyl ether; ester solvents such as ethyl acetate, butyl acetate, isobutyl isobutyrate, and isobutyl butyrate; and halogenated solvents such as chloroform, methylene chloride, and 1,2-dichloroethane. From the viewpoint of film formation stability, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol diacetate, and diethylene glycol diethyl ether are preferred. The amount of solvent used can be determined appropriately. The amount of the solvent used is preferably 0.1 to 10 mL per 1 g of the solid content of the photosensitive composition.

[0099] <Other ingredients> The photosensitive composition may contain resin components and additives other than the above (A) to (E). For example, the photosensitive composition may contain various thermoplastic resins for the purpose of modifying properties, etc. Examples of thermoplastic resins include acrylic resins, polycarbonate resins, cycloolefin resins, olefin-maleimide resins, polyester resins, polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, polyethylene resins, polypropylene resins, polystyrene resins, polyamide resins, silicone resins, fluororesins, and rubber-like resins such as natural rubber and EPDM. The thermoplastic resin may have a crosslinkable group such as an epoxy group, an amino group, a radically polymerizable unsaturated group, a carboxy group, an isocyanate group, a hydroxy group, or an alkoxysilyl group.

[0100] The photosensitive composition may contain an alkali-soluble component other than the component (A) to improve solubility in an alkaline developer. Examples of the alkali-soluble component include a resin having an alkali-soluble functional group. Examples of the resin include a phenolic resin, an acrylic resin, an amide resin, and a polysiloxane resin.

[0101] In addition to the above, the photosensitive composition may contain an adhesion improver, a coupling agent such as a silane coupling agent, an antidegradant, a hydrosilylation reaction inhibitor, a polymerization inhibitor, a polymerization catalyst (crosslinking accelerator), a release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, an anti-repellent, an ion trapping agent, a thixotropy imparting agent, a tackifier, a storage stability improver, a light stabilizer, a thickener, a plasticizer, a reactive diluent, an antioxidant, a heat stabilizer, an electrical conductivity imparting agent, an antistatic agent, a radiation shielding agent, a nucleating agent, a phosphorus-based peroxide decomposer, a lubricant, a metal deactivator, a thermal conductivity imparting agent, a physical property adjuster, and the like, within a range that does not impair the objects and effects of the present invention.

[0102] The photosensitive composition may contain a filler or a colorant. Examples of fillers include silica-based fillers (quartz, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine amorphous silica), silicon nitride, silver powder, alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, and inorganic balloons. Examples of colorants include organic pigments, inorganic pigments, and dyes.

[0103] The total amount of components (A), (B), (C), (D), and (E) is preferably 50% by weight or more, more preferably 60% by weight or more, and even more preferably 70% by weight or more of the total solid content of the photosensitive composition.

[0104] [Insulating film formation] An insulating film can be formed by coating a substrate with a solution containing a polymer having Structure X to form a coating film. Alternatively, a patterned film can be formed by coating a substrate with the positive photosensitive composition to form a coating film, exposing the film through a mask of a predetermined shape, and dissolving and removing the exposed portion by alkaline development. A patterned cured film can be obtained by post-baking after development.

[0105] <Coating film formation> The method for applying the photosensitive composition to the substrate is not particularly limited as long as it allows for uniform application, and common coating methods such as spin coating, slit coating, and screen coating can be used. The thickness of the coating film is not particularly limited. When the pattern film is a permanent resist, from the viewpoint of reliability, the thickness is preferably 0.05 to 100 μm, more preferably 0.1 to 80 μm, and even more preferably 0.2 to 50 μm.

[0106] <Pre-bake> Before exposure, heating (pre-baking) may be performed to dry the solvent. The heating temperature can be set appropriately, but is preferably 50 to 200°C, more preferably 60 to 150°C. Furthermore, vacuum devolatilization may be performed before exposure. Vacuum devolatilization may be performed simultaneously with heating. Photosensitive compositions containing thermosetting components (for example, the above-mentioned component (D) and / or component (E)) may have reduced developability as curing proceeds due to heating. Therefore, the heating temperature in pre-baking is preferably 120°C or less.

[0107] <Exposure> The light source for exposure may be selected depending on the wavelength sensitivity of the photoacid generator and sensitizer contained in the photosensitive composition. Typically, a light source having a wavelength in the range of 200 to 450 nm (e.g., a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a high-power metal halide lamp, a xenon lamp, a carbon arc lamp, or a light-emitting diode) is used.

[0108] The exposure dose is not particularly limited, but is preferably 1 to 5000 mJ / cm 2is preferred, and 5 to 1000 mJ / cm 2 More preferably, 10 to 500 mJ / cm 2 If the exposure dose is too low, curing may be insufficient, resulting in a decrease in pattern contrast, whereas if the exposure dose is too high, the takt time may increase, resulting in an increase in manufacturing costs.

[0109] <Post-exposure bake> After exposure and before development, post-exposure baking (PEB) may be performed for the purpose of promoting the reaction between the acid and component (A), etc. The heating temperature in post-exposure baking is preferably 40 to 120°C, more preferably 50 to 110°C, and even more preferably 60 to 100°C.

[0110] <Developing> A patterned film is obtained by contacting the exposed coating film with an alkaline developer by immersion, spraying, or other methods to dissolve and remove the exposed areas of the coating film. In the exposed areas, the alkali solubility of component (A) increases due to the action of the acid generated by irradiating the photoacid generator with active energy rays, and the coating film dissolves during alkaline development.

[0111] The alkaline developer may be any commonly used one without any particular limitations. Specific examples of alkaline developers include organic alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution, and inorganic alkaline aqueous solutions such as potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution, and lithium carbonate aqueous solution. The alkaline concentration of the developer is preferably 0.01 to 25% by weight, more preferably 0.1 to 10% by weight, and even more preferably 0.3 to 5% by weight. The developer may contain a surfactant or the like for the purpose of adjusting the dissolution rate, etc.

[0112] <Post-bake> After dissolving and removing the exposed areas by development, post-baking may be performed to harden the composition of the film in the remaining unexposed areas. Post-baking conditions can be appropriately set. The post-baking temperature is preferably 100 to 400°C, more preferably 120 to 350°C.

[0113] For example, if component (A) contains SiH groups, post-baking promotes reaction between the SiH groups, resulting in a cured film. If component (A) contains SiH groups and the photosensitive composition contains component (D), a compound with multiple ethylenically unsaturated groups, post-baking promotes curing (crosslinking) through a hydrosilylation reaction between the SiH groups in component (A) and the ethylenically unsaturated groups in component (D), which tends to improve the insulating properties, heat resistance, solvent resistance, etc. of the cured film.

[0114] When a polymer having a crosslinkable functional group such as an epoxy group or an oxetane group is used as component (A) instead of or in addition to component (D), a crosslinked structure is formed by post-baking, thereby hardening the insulating film. Also, when the photosensitive composition contains a thermosetting resin such as an epoxy resin or an oxetane resin as component (E), post-baking promotes the thermal curing of component (E), thereby hardening the insulating film.

[0115] [Application] The photosensitive composition of this embodiment can be used as an alkali-developable transparent resist. The photosensitive composition of this embodiment contains an isocyanuric acid skeleton structure X as the alkali-solubility-producing structure (an acidic group protected by a protecting group) of the base polymer component (A). Therefore, compared to polymers containing a phenol structure having a protecting group as the primary alkali-solubility-producing structure, the composition exhibits less light absorption in the short wavelength visible light region (near 400 nm wavelength) and superior transparency. Furthermore, polymers having an isocyanuric acid skeleton have superior heat resistance compared to phenolic polymers, and exhibit less change in light transmittance during a heat durability test.

[0116] Therefore, the photosensitive composition is particularly suitable as a material for FPDs. Examples of FPD materials include a passivation film for TFTs, a gate insulating film for TFTs, an interlayer insulating film for TFTs, a transparent planarizing film for TFTs, a photospacer material for liquid crystal cells, and a transparent sealing material for OLED elements. The photosensitive composition can also be used as a material for colored films such as color filters and black matrices. [Example]

[0117] The present invention will be described in more detail below based on examples, but the present invention is not limited to the following examples.

[0118] [Synthesis example: Synthesis of a compound with a protecting group attached to the nitrogen atom of an isocyanuric acid skeleton] <Synthesis Example 1> A flask was charged with 100 g of diallyl isocyanurate (DAIC), 400 g of tetrahydrofuran (THF), and 13.2 g of pyridine, and the mixture was stirred and then heated to 70°C. A solution of 120 g of di-tert-butyl dicarbonate and 60 g of THF was added dropwise, and after completion of the reaction, the solvent was removed. Recrystallization was carried out with hexane, yielding the following compound 1 (yield: 148 g), in which a tert-butoxycarbonyl group (Boc) was bonded to the nitrogen atom of the isocyanuric acid skeleton and two allyl groups were obtained.

[0119] [ka]

[0120] <Synthesis Example 2> 10 g of DAIC, 40 g of THF, and 33 g of potassium carbonate were added to a flask and stirred at room temperature. 60 g of tert-butyl bromide was added in two portions and allowed to react. After completion of the reaction, the liquid was separated and the solvent was removed. Recrystallization was carried out with hexane to obtain the following compound 2 (yield: 11 g), which has a tert-butyl group bonded to the nitrogen atom of the isocyanuric acid skeleton and two allyl groups.

[0121] [ka]

[0122] <Synthesis Example 3> A flask was charged with 10 g of monoallyl isocyanurate (MAIC), 30 g of tetrahydrofuran (THF), and 1.8 g of pyridine, and the mixture was stirred and then heated to 70°C. A solution of 36 g of di-tert-butyl dicarbonate and 18 g of THF was added dropwise, and after completion of the reaction, the solvent was removed. The resulting solid was dissolved in toluene to obtain a toluene solution of the following compound 3 (yield: 22 g), in which Boc is bonded to two nitrogen atoms of the isocyanuric acid skeleton and one allyl group is present.

[0123] [ka]

[0124] <Comparative synthesis example: Synthesis of a compound with a protecting group attached to a phenolic hydroxyl group> 5 g of diallyl bisphenol S and 20 g of dioxane were placed in a flask and stirred. 2.5 g of hexamethyldisilazane was added thereto, and after the reaction was completed, the solvent was removed. The resulting solid was dissolved in toluene to obtain a toluene solution of the following compound 4, which has a bisphenol S structure protected with a trimethylsilyl group (yield: 6.5 g).

[0125] [ka]

[0126] [Polymer preparation] Example 1 A flask was charged with 3.84 g of 1,3,5,7-tetramethylcyclotetrasiloxane (D4H) and an equal amount of toluene to D4H. The gas phase was replaced with nitrogen, and the internal temperature was heated to 105°C with stirring. A solution of 6.16 g of the above compound 1 and 5.2 mg of a platinum catalyst solution (a xylene solution of platinum vinylsiloxane complex: platinum content 3 wt%) dissolved in four times the amount of compound 1 in dioxane was added dropwise. After the reaction was completed, the solvent was distilled off under reduced pressure.

[0127] <Examples 2 to 4> A polymer was prepared in the same manner as in Example 1, except that the amounts of Compound 1 and D4H charged were changed as shown in Table 1.

[0128] <Example 5> A flask was charged with 4.68 g of D4H and the same amount of toluene as D4H, and the gas phase was replaced with nitrogen. The mixture was then heated to a temperature of 105° C. and stirred. A solution of 4.92 g of the compound 1, 0.40 g of diallyl monomethyl isocyanurate (DAMMIC), and 5.3 mg of a platinum catalyst solution dissolved in four times the amount of dioxane as the total amount of compound 1 and DAMMIC was added dropwise thereto. After completion of the reaction, the solvent was distilled off under reduced pressure.

[0129] <Examples 6 to 11> A polymer was prepared in the same manner as in Example 5, except that the amounts of Compound 1, D4H, and DAMMIC charged were changed as shown in Table 1.

[0130] Example 12 A polymer was prepared in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1 and the amounts charged were changed as shown in Table 1.

[0131] Example 13 A flask was charged with 3.72 g of D4H and an equal amount of toluene to D4H. The gas phase was replaced with nitrogen, and the internal temperature was heated to 105°C and stirred. A solution of 4.35 g of compound 1 and 4.2 mg of platinum catalyst solution dissolved in four times the amount of dioxane as compound 1 was added dropwise. After completion of the reaction, a solution of 1.93 g of allyl glycidyl ether (AGE) dissolved in twice the amount of toluene as AGE was added dropwise. After completion of the reaction, the solvent was distilled off under reduced pressure.

[0132] Example 14 A polymer was prepared in the same manner as in Example 13, except that 3-[(allyloxy)methyl]-3-ethyloxetane (AL-EOX) was used instead of AGE and the amounts charged were changed as shown in Table 1.

[0133] Example 15 A flask was charged with 3.73 g of D4H and an equal amount of toluene to D4H. The gas phase was replaced with nitrogen, and the internal temperature was heated to 105°C and stirred. A solution of 3.15 g of DAMMIC and 3.7 mg of platinum catalyst solution dissolved in dioxane in an amount four times the amount of DAMMIC was added dropwise. After completion of the reaction, a solution of 3.12 g of compound 3 dissolved in toluene in an amount twice the amount of compound 3 was added dropwise. After completion of the reaction, the solvent was distilled off under reduced pressure.

[0134] <Comparative Example 1> A flask was charged with 4.65 g of D4H and the same amount of toluene as D4H, and the gas phase was replaced with nitrogen. The mixture was then heated to a temperature of 105° C. and stirred. A solution of 3.85 g of the above compound 4, 1.50 g of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (D4Vi), and 2.2 mg of a platinum catalyst solution dissolved in 38.5 g of toluene was added dropwise thereto. After the reaction was completed, the solvent was distilled off under reduced pressure.

[0135] [evaluation] <Preparation of Composition> A positive-tone photosensitive composition was prepared by mixing 100 parts by weight of the polymer obtained in Examples 1 to 15 and Comparative Example 1, 1 part by weight of a photoacid generator (ADEKA "ADEKA Arcles SP-606"), 1 part by weight of a photosensitizer (9,10-dibutoxyanthracene), and 400 parts by weight of propylene glycol monomethyl ether acetate as a solvent. In Example 16, a positive-tone photosensitive composition was prepared by mixing the polymer obtained in Example 1, the photoacid generator, the photosensitizer, and the solvent, as well as 3 parts by weight of triallyl isocyanurate (TAIC) as a crosslinker and a platinum catalyst solution containing 0.05 parts by weight of platinum.

[0136] <Exposure sensitivity> The positive photosensitive composition was spin-coated onto a glass substrate (50 mm × 50 mm) so that the film thickness after drying would be 3 μm, and then heated on a hot plate heated to 100°C for 2 minutes. Next, a parallel light irradiation device equipped with a high-pressure mercury lamp ("UV-K160HC" manufactured by Minaga Electric Works) was used to irradiate the film through a photomask with a 10 μm hole pattern, with an accumulated light dose of 10 to 120 mJ / cm. 2 After heating at 60° C. for 1 minute, the film was immersed in an alkaline developer (aqueous solution of 2.38% TMAH) for 1 minute for development treatment to prepare a sample for evaluating patterning properties.

[0137] The pattern shape was observed for each sample at each exposure dose, and samples with hole diameters within the range of 10.0±0.2 μm were rated as OK. For each example and comparative example, the exposure dose required for patterning evaluation to be OK was used as an index of exposure sensitivity. The smaller the exposure dose required for patterning, the better the exposure sensitivity.

[0138] <Light transmittance> An insulating film was prepared on a glass substrate in the same manner as above, except that no exposure was performed. The sample was heated in an oven at 220°C for 30 minutes. After further heating at 240°C for 1 hour, the transmission spectrum was measured using a visible-ultraviolet spectrometer to determine the light transmittance at a wavelength of 400 nm.

[0139] <Chemical resistance> An insulating film was prepared in the same manner as above, except that the heating at 240°C for 1 hour was not performed. The insulating film was immersed for 5 minutes in a mixed solution of dimethyl sulfoxide / 2-aminoethanol (30 / 70 by weight) heated to 60°C, and then heated at 220°C for 10 minutes to remove the remaining solvent in the film. Then, from the film thicknesses of the insulating film before and after immersion, the film thickness retention rate (%) = 100 × (film thickness after immersion / film thickness before immersion) was calculated.

[0140] Table 1 shows the amounts of raw materials (monomers) used to prepare the polymers of the above Examples and Comparative Examples, the amount of NH groups generated in the presence of acid (theoretical value), and the evaluation results.

[0141] [Table 1]

[0142] As shown in Table 1, the polymers of Examples 1 to 15, which used compounds 1 to 3, which are isocyanuric acid derivatives, as monomers, were superior in transparency (transmittance) and chemical resistance (film thickness retention rate) to the polymer of Comparative Example 1, which had a phenol structure, and were also found to have sufficient exposure sensitivity as positive-type photosensitive compositions.

[0143] Comparison of Examples 1 to 4 and Examples 5 to 9 reveals that the greater the amount of Structure X introduced by the isocyanuric acid derivative, the higher the exposure sensitivity of the photosensitive composition tends to be. Furthermore, comparison of Examples 3 and 12 reveals that the presence of a Boc protecting group tends to increase the exposure sensitivity.

[0144] In Examples 13 and 14, in which crosslinkable functional groups were introduced into the polymer, the chemical resistance was improved compared to the other Examples. In addition, in Example 16, in which TAIC was added as a crosslinking agent, the chemical resistance was improved compared to Example 1. In these Examples, it is believed that the formation of crosslinks between polymers by post-baking contributed to the improvement in chemical resistance.

Claims

1. A positive-working photosensitive composition containing a polymer and a photoacid generator, The polymer has one or more structures selected from the group consisting of a structure represented by the following general formula (X1) and a structure represented by the following general formula (X2), 【Chemical 1】 R １ is a tert-butyl group or a tert-butoxycarbonyl group; Positive photosensitive composition.

2. 2. The positive-acting photosensitive composition of claim 1, wherein the polymer comprises a polysiloxane backbone.

3. The polymer is formed by reacting R １ 3. The positive photosensitive composition according to claim 1, wherein the amount of NH groups generated by elimination of is 0.1 mmol / g or more.

4. 4. The positive photosensitive composition according to claim 1, wherein the polymer has a weight average molecular weight of 1,000 to 200,000.

5. 5. The positive photosensitive composition according to claim 1, wherein the polymer contains a crosslinkable functional group capable of forming a crosslinked structure by heating.

6. 6. The positive photosensitive composition according to claim 5, wherein the crosslinkable functional group is at least one selected from the group consisting of an epoxy group and an oxetane group.

7. 7. The positive photosensitive composition according to claim 5, further comprising a compound containing, in one molecule, two or more functional groups capable of reacting with the crosslinkable functional group of the polymer.

8. The positive photosensitive composition according to any one of claims 1 to 7, further comprising a thermosetting resin.

9. A method for producing a patterned insulating film, comprising applying the positive photosensitive composition according to any one of claims 1 to 8 onto a substrate, and then patterning the composition by exposure and alkaline development.

10. A polymer used as a base polymer for a positive-working photosensitive composition, comprising: A polymer having one or more structures selected from the group consisting of a structure represented by the following general formula (X1) and a structure represented by the following general formula (X2): 【Chemistry 2】 R １ is a tert-butyl group or a tert-butoxycarbonyl group.

11. The polymer of claim 10 comprising a polysiloxane backbone.

12. In the presence of an acid, R in the general formula (X1) and R in the general formula (X2) １ The polymer according to claim 10 or 11, wherein the amount of NH groups generated by elimination of is 0.1 mmol / g or more.

13. The polymer according to any one of claims 10 to 12, having a weight average molecular weight of 1,000 to 200,000.

14. The polymer according to any one of claims 10 to 13, which contains a crosslinkable functional group capable of forming a crosslinked structure by heating.

15. 15. The alkali-soluble polymer according to claim 14, wherein the crosslinkable functional group is at least one selected from the group consisting of an epoxy group and an oxetane group.

16. An insulating film comprising the polymer according to any one of claims 10 to 15.

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