JP7482637B2 - Positive-type photosensitive resin composition, patterned cured film, and method for producing same - Google Patents

Description

The present invention relates to a positive-type photosensitive resin composition. The present invention also relates to a patterned cured film using the positive-type photosensitive resin composition and a method for producing the same.

In the field of displays such as liquid crystal displays and organic electroluminescence displays, there is a demand for photosensitive compositions that can form highly sensitive and reliable insulating films that can be patterned in a positive manner. A positive photosensitive resin composition is a type of resin composition that leaves an image in the areas that are not irradiated with actinic rays. In the positive type, a photoacid generator is used to increase the solubility of the exposed areas by irradiating them with actinic rays, so that neither the exposed nor unexposed areas are cured at the time of pattern exposure. If the pattern shape obtained is poor or if residues or foreign matter are generated in the pattern area, the substrate can be reused (reworked) by exposure to the entire surface. For this reason, positive photosensitive resin compositions are preferably used from the viewpoint of excellent reworkability.

For example, Patent Document 1 describes that adding a carboxylic acid or its derivative having an unsaturated bond to a phenolic resin can suppress the generation of residues after development and produce a cured film with excellent mechanical properties. However, these monomers remain in the phenolic resin, and if the subsequent process includes a heating step or other process, there is a possibility that the monomer components will seep onto the surface of the cured product or volatilize into the air, contaminating the resin surface and the equipment in the process, leaving room for improvement in terms of process stability.

JP 2014-186124 A

In view of the above, the present invention aims to provide a positive-type photosensitive resin composition that is less likely to cause tack, has excellent substrate reworkability, and can provide a cured film that does not allow added components to bleed out during processes such as heating.

The positive-type photosensitive resin composition according to the present invention comprises: component (A): a compound whose alkali solubility increases under the action of an acid; component (B): a photoacid generator; component (C): a copolymer composed of at least two monomers selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid ester, styrene, a styrene derivative, and maleic anhydride, one of which is (meth)acrylic acid or maleic anhydride, and the content of component (C) relative to 100 parts by weight of component (A) is 1 to 10 parts by weight.

In the positive-type photosensitive resin composition, the component (A) preferably contains a structure in which a phenolic hydroxyl group is protected by a protecting group.

In the positive-type photosensitive resin composition, the component (D) is preferably a compound containing two or more functional groups in one molecule that can react with the component (A).

Component (A) is, for example, a polysiloxane compound. The polysiloxane compound may have a cyclic siloxane structure.

The positive photosensitive resin composition is applied onto a substrate, and then patterned by exposure and alkaline development to obtain a patterned film. After development, the patterned film may be cured by heating.

By using the positive photosensitive resin composition of the present invention, it is possible to provide a cured film that has excellent substrate reworkability and does not allow added components to bleed out during processes such as heating.

[Photosensitive composition]
The photosensitive composition of the present invention is a positive photosensitive resin composition which is a copolymer constituted of at least two monomers selected from the group consisting of (A) a compound whose alkali solubility increases under the action of an acid, (B) a photoacid generator, and (C) (meth)acrylic acid, a (meth)acrylic acid ester, styrene, a styrene derivative, and maleic anhydride, one of which is (meth)acrylic acid or maleic anhydride, and in which the content of the component (C) per 100 parts by weight of the component (A) is 1 to 10 parts by weight.

Hereinafter, a compound whose alkali solubility increases under the action of an acid will be referred to as "component (A)", a photoacid generator as "component (B)", and a copolymer composed of at least two monomers of (meth)acrylic acid, (meth)acrylic acid ester, styrene, a styrene derivative, and maleic anhydride, in which one of the monomers constituting the copolymer is (meth)acrylic acid or maleic anhydride, as "component (C)". The photosensitive composition may further contain a crosslinking agent (a compound having a functional group capable of introducing a crosslinking structure into component (A)) as component (D). Unless otherwise specified, the compounds and functional groups exemplified in this specification may be used alone or in combination (coexist) of two or more kinds.

<Component (A)>
The component (A) is a compound in which an alkali-solubility-imparting group is protected by a protecting group, and the protecting group is removed (deprotected) by reaction with an acid generated from a photoacid generator, increasing the alkali solubility. Therefore, by including the component (A) and the photoacid generator (B), a positive pattern can be formed. Examples of the alkali-solubility-imparting group include acidic groups such as carboxylic acid and phenolic hydroxyl groups.

Examples of the protecting group for the phenolic hydroxyl group include a tert-butoxycarbonyl group and a trialkylsilyl group. For example, the phenolic hydroxyl group can be protected with a tert-butoxycarbonyl group by a reaction using a Boc reagent. From the viewpoint of ease of deprotection with an acid, the alkyl group in the trialkylsilyl group as the protecting group for the phenolic hydroxyl group is preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group is particularly preferred. The phenolic hydroxyl group can be protected with a trimethylsilyl group by a reaction using a silylating agent such as hexamethyldisilazane or trimethylchlorosilane.

Protective groups for carboxylic acids include tertiary alkyl esters and acetals. Tertiary alkyl groups in tertiary alkyl esters of carboxylic acids include tert-butyl, adamantyl, tricyclodecyl, and norbornyl groups.

The content of the structure in which the alkali-solubility-imparting group in component (A) is protected by a protecting group is preferably 0.1 to 15 mmol/g, more preferably 0.2 to 10 mmol/g, and even more preferably 0.3 to 7 mmol/g, calculated as an equivalent using dibromoethane as the standard substance.

When a permanent resist is produced from a positive photosensitive resin composition, it is preferable that component (A) has a polymerizable functional group. When heating (post-baking) is performed after exposure and development, the polymerizable functional group of component (A) reacts with component (D) described below, introducing a crosslinked structure to obtain a patterned cured film.

The (A) component preferably includes a structure in which the alkali-solubility-imparting group is protected by a protecting group, and a polymer backbone structure other than the above-mentioned polymerizable functional group. Examples of the polymer backbone structure include polyacrylic, polyphenol, polyamide, polyanhydride, polycarbonate, polydiene, polyester, polyhaloolefin, polyimide, polyimine, polyketone, polyolefin, polyether, polyphenylene, polyphosphazene, polysiloxane, polysilane, polystyrene, polysulfide, polysulfone, polyurethane, polyurea, polyvinyl, etc.

<Component (A) Having a Polysiloxane Structure>
Since it is possible to form a cured film having high heat resistance and low dielectric constant, it is preferable that the component (A) has a polysiloxane structure, and it is particularly preferable that the component (A) has a cyclic polysiloxane structure. The component (A) containing a polysiloxane structure is a compound having a "compound having a siloxane unit" as the main skeleton and having a "structure in which an alkali-solubility-imparting group is protected by a protecting group", and specific examples thereof include the polysiloxane compounds disclosed in WO2014/007231 and the like.

In this specification, "polysiloxane structure" refers to a structural skeleton having siloxane units Si-O-Si, and "cyclic polysiloxane structure" refers to a cyclic molecular structural skeleton having siloxane units (Si-O-Si) as ring components. Compounds containing cyclic polysiloxane structures tend to have superior film-forming properties and the heat resistance of the resulting cured film compared to compounds containing only chain-like polysiloxane structures.

A polysiloxane compound having a "structure in which an alkali-solubility-imparting group is protected by a protecting group" (hereinafter, sometimes referred to as "structure X") introduced therein can be obtained, for example, by a hydrosilylation reaction. The hydrosilylation reaction has the advantage that structure X can be introduced into the polysiloxane skeleton via a chemically stable silicon-carbon bond (Si-C bond).

The hydrosilylation reaction is a reaction between a polysiloxane compound having at least two SiH groups (hydrosilyl groups) in one molecule and a compound having a carbon-carbon double bond that is reactive with the SiH groups. When at least one of these compounds (starting materials) has structure X in addition to the above functional groups, a polysiloxane compound having structure X is obtained.

For example, when a compound having a carbon-carbon double bond has a structure X, a polysiloxane compound having a structure X can be obtained by a hydrosilylation reaction using the following compounds (α) and (β) as starting materials. Compound (α): A compound having a carbon-carbon double bond reactive with a SiH group (hydrosilyl group) and a structure X in one molecule;
Compound (β): A polysiloxane compound having at least two SiH groups in one molecule.

(Compound (α): Compound containing Structure X and an ethylenically unsaturated group)
Compound (α) is a compound containing a structure X and a carbon-carbon double bond reactive with a SiH group. Examples of the group containing a carbon-carbon double bond reactive with a SiH group (hereinafter, sometimes simply referred to as an "ethylenically unsaturated group") include a vinyl group, an allyl group, a methallyl group, an acryl group, a methacryl group, a 2-hydroxy-3-(allyloxy)propyl group, a 2-allylphenyl group, a 3-allylphenyl group, a 4-allylphenyl group, a 2-(allyloxy)phenyl group, a 3-(allyloxy)phenyl group, a 4-(allyloxy)phenyl group, a 2-(allyloxy)ethyl group, a 2,2-bis(allyloxymethyl)butyl group, a 3-allyloxy-2,2-bis(allyloxymethyl)propyl group, and a vinyl ether group.

It is preferable that compound (α) has multiple ethylenically unsaturated groups in one molecule. When compound (α) has multiple ethylenically unsaturated groups in one molecule, multiple polysiloxane compounds (compound (β)) are crosslinked by the hydrosilylation reaction, which increases the molecular weight of component (A) and tends to improve film-forming properties and the heat resistance of the cured film.

As described above, Structure X may be a structure in which a protecting group is bonded to an acidic group such as a carboxylic acid or a phenolic hydroxyl group. When component (A) is a polysiloxane compound, Structure X is preferably a structure in which a protecting group is bonded to a phenolic hydroxyl group. From the viewpoint of the chemical resistance and insulating properties of the cured film, it is also preferable that Structure X contains a bisphenol structure.

Examples of the bisphenol structure include the bisphenol A structure, the bisphenol AP structure, the bisphenol AF structure, the bisphenol B structure, the bisphenol BP structure, the bisphenol E structure, the bisphenol M structure, the bisphenol F structure, the bisphenol S structure, the bisphenol PH structure, the bisphenol C structure, the bisphenol G structure, the bisphenol TMC structure, and the bisphenol Z structure. Among these, the bisphenol A structure, the bisphenol B structure, the bisphenol C structure, the bisphenol E structure, the bisphenol F structure, the bisphenol AF structure, the bisphenol S structure, the bisphenol AP structure, and the bisphenol PH structure are preferred because they have excellent solubility in an alkaline developer and are likely to produce a pattern with excellent contrast, and among these, the bisphenol S structure or the bisphenol F structure is preferred from the viewpoint of ease of deprotection with an acid.

The protecting group for the phenolic hydroxyl group is preferably an organic group or an organosilicon group having 1 to 50 carbon atoms, and a trialkylsilyl group is particularly preferred. An example of a compound (α) in which the phenolic hydroxyl group of a bisphenol is protected by a trialkylsilyl group and which has an ethylenically unsaturated group is a compound represented by the following general formula (I).

In the general formula (I), R ¹ is a divalent organic group, and may be any structure that can be a bisphenol structure. For example, when the compound (α) has a bisphenol S structure, R ¹ is SO ₂ , and when the compound (α) has a bisphenol F structure, R ¹ is CH _2. Each of the multiple R ² is independently an alkyl group having 1 to 6 carbon atoms, and preferably, all of the R ² are methyl groups. The compound represented by the general formula (I) can be obtained, for example, by reacting diallyl bisphenol with a silylating agent.

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

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.

Examples of polysiloxanes having hydrosilyl groups at the molecular terminals include polysiloxanes whose terminals are blocked with dimethylhydrogensilyl groups, and polysiloxanes composed of dimethylhydrogensiloxane units (H( _CH3 ) _{2SiO1 /2} units) and at least one siloxane unit selected from the group consisting of _SiO2 units, SiO3 _/2 units, and SiO units.

Cyclic polysiloxanes are, for example, represented by the following general formula (II):

In the formula, R ⁴ , R ⁵ and R ⁶ each independently represent 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.

R ⁴ , R ⁵ and R ⁶ are preferably organic groups composed of elements selected from the group consisting of C, H and O. Examples of R ⁴ , R ⁵ and R ⁶ include alkyl groups, hydroxyalkyl groups, alkoxyalkyl groups, oxyalkyl groups, aryl groups and the like. Among them, 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, or phenyl groups are preferred. From the viewpoint of availability of compound (β), R ⁴ , R ⁵ and R ⁶ are preferably methyl groups, propyl groups, hexyl groups or phenyl groups. R ⁴ and R ⁵ are more preferably chain alkyl groups having 1 to 6 carbon atoms, and particularly preferably methyl groups.

Examples of the cyclic polysiloxane compound represented by the 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 viewpoints of availability and reactivity of the SiH group, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (a compound in which, in general formula (II), m=4, n=0, and ^R4 is a methyl group) is preferred.

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 a polysiloxane having a polyhedral skeleton is silsesquioxane (number of Si atoms = 8) represented by the following general formula (III).

In the above formula, R ¹⁰ to R ¹⁷ are each independently a monovalent group selected from hydrogen atoms, chain alkyl groups (methyl, ethyl, propyl, butyl, etc.), cycloalkyl groups (cyclohexyl, etc.), aryl groups (phenyl, tolyl, etc.), 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, etc. (chloromethyl, trifluoropropyl, cyanoethyl, etc.), alkenyl groups (vinyl, allyl, butenyl, hexenyl, etc.), (meth)acryloyl groups, epoxy groups, and organic groups containing a mercapto group or an amino group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 20, more preferably 1 to 10.

The cyclic polysiloxane may be a silylated silicic acid having a polyhedral skeleton. A specific example of a silylated silicic acid having a polyhedral skeleton is a compound represented by the following general formula (IV) (number of Si atoms = 8).

In the above formula, R ¹⁸ to R ⁴¹ are the same as the specific examples of R ¹⁰ to R ¹⁷ in the above general formula (III).

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 and the like. 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, and the like. A commercially available polysiloxane compound may be used as compound (β).

(Other Starting Materials)
In the synthesis of component (A) by hydrosilylation reaction, in addition to the above-mentioned compound (α) and compound (β), other starting materials may be used. For example, an ethylenically unsaturated group-containing compound other than the above-mentioned compound (α) may be used as a starting material.

For example, in addition to compound (α) and compound (β), it is preferable to use a compound having two or more ethylenically unsaturated groups in one molecule (hereinafter, "compound (γ)") as a starting material. When compound (γ) 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 heat resistance of the cured film.

The compound (γ) may be either an organic polymer compound or an organic monomer compound. Examples of the organic polymer compound include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylic acid ester, polyamide, phenol-formaldehyde (phenolic resin), and polyimide compounds. Examples of the organic monomer compound include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene; aliphatic hydrocarbons such as linear and alicyclic compounds; and heterocyclic compounds.
If compound (γ) is used,

Specific examples of 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 Examples of such epoxy resins 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. In addition, compounds in which the allyl group in the above example compounds is replaced with a (meth)acryloyl group (e.g., polyfunctional (meth)acrylates) can also be suitably used as compound (γ).

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 the Si of compound (β) are replaced with ethylenically unsaturated groups. Among these, from the viewpoint of improving the heat resistance of the cured film, cyclic polysiloxane compounds having two or more ethylenically unsaturated groups are preferred.

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 an ethylenically unsaturated group. Examples of cyclic polysiloxane compounds having two or more vinyl groups bonded to silicon 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.

As a starting material for the hydrosilylation reaction, a compound having only one functional group participating in the hydrosilylation reaction in one molecule (hereinafter referred to as "compound (δ)") may be used. The functional group participating in the hydrosilylation reaction is a 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.

For example, by using a siloxane compound having one SiH group as the compound (δ), a siloxane structural portion can be introduced to the end of the polymer. Specific examples of the siloxane compound having one SiH group include a cyclic polysiloxane compound in which m=1 in the above-mentioned general formula (II), a polyhedral polysiloxane compound in which one of R ¹⁰ to R ¹⁷ in the above-mentioned general formula (III) is a hydrogen atom, and a silylated silicic acid compound in which one of R ¹⁸ to R ⁴¹ in the above-mentioned general formula (IV) is a hydrogen atom. The siloxane compound having one SiH group may be a chain siloxane compound.

By using a compound containing one ethylenically unsaturated group as compound (δ), the desired functional group can be introduced to the end of the polymer. In addition to the above, compounds that participate in the hydrosilylation reaction, such as linear polysiloxanes having two or more SiH groups, may also be included in the starting material.

(Hydrosilylation reaction)
The order and method of the hydrosilylation reaction are not particularly limited. From the viewpoint of simplifying the synthesis process, it is preferable to carry out the hydrosilylation reaction by charging all starting materials into one pot, and finally remove the unreacted compounds. On the other hand, from the viewpoint of suppressing the production of low molecular weight substances, it is preferable to carry out the hydrosilylation reaction of a compound containing multiple ethylenically unsaturated groups (e.g., compound (α) and compound (γ)) and a compound containing multiple SiH groups (e.g., compound (β)) with one of them in excess, remove the unreacted compound, and then add a compound having only one functional group participating in the hydrosilylation reaction in one molecule (e.g., compound (δ)) to carry out the hydrosilylation reaction.

The ratio of each compound in the hydrosilylation reaction is not particularly limited, but it is preferable that the total amount A of ethylenically unsaturated groups in the starting material and the total amount B of SiH groups satisfy 1≦B/A≦30, and more preferably 1≦B/A≦10. If B/A is 1 or more, unreacted ethylenically unsaturated groups are unlikely to remain, and if B/A is 30 or less, unreacted compound (β) is unlikely to remain, improving the properties of the cured film.

For the hydrosilylation reaction, a hydrosilylation catalyst such as chloroplatinic acid, a platinum-olefin complex, or a platinum-vinylsiloxane complex may be used. The hydrosilylation catalyst may be used in combination with a co-catalyst. The amount of the hydrosilylation catalyst added is not particularly limited, but is preferably 10 ⁻⁸ to 10 ⁻¹ times, and more preferably 10 ⁻⁶ to 10 ⁻² times, the total amount (number of moles) of ethylenically unsaturated groups contained in the starting material.

The reaction temperature for hydrosilylation may be set appropriately, and is preferably 30 to 200°C, and more preferably 50 to 150°C. An appropriate solvent may be used in the hydrosilylation reaction. A gelation inhibitor may be used in the hydrosilylation reaction, if necessary.

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 compound having structure X, but the method for synthesizing component (A) is not limited to this. Component (A) can also be obtained by a hydrosilylation reaction using a starting material other than those described above.

For example, instead of compound (α), a compound having a SiH group and structure X in one molecule may be used as a starting material to synthesize a polysiloxane compound having structure X. In this case, a polysiloxane compound having structure X is obtained by a hydrosilylation reaction between the compound containing a SiH group and structure X and a polysiloxane compound having an ethylenically unsaturated group. The polysiloxane compound having an ethylenically unsaturated group may contain multiple ethylenically unsaturated groups.

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.

<(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 acid generated from the photoacid generator decomposes component (A) to generate acidic groups or hydroxyl groups, thereby increasing the alkali solubility.

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, and onium salts; and nonionic photoacid generators such as imide sulfonates, oxime sulfonates, and sulfonyl diazomethanes. Examples of anions contained in ionic photoacid generators include B(C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , and C ₄ F ₉ SO ₃ ⁻ . As the photoacid generator, imide sulfonates and oxime sulfonates are preferred because of their high photosensitivity.

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). If the amount of the 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.

<(C) A copolymer composed of at least two monomers selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid esters, styrene, styrene derivatives, and maleic anhydride, and one of the monomers constituting the copolymer is (meth)acrylic acid or maleic anhydride>

The photosensitive composition contains, as component (C), a copolymer composed of at least two monomers selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid esters, styrene, styrene derivatives, and maleic anhydride, and one of the monomers constituting the copolymer is (meth)acrylic acid or maleic anhydride. Component (C) is alkaline soluble, and by adding it to a photosensitive resin, the solubility of the photosensitive resin in an alkaline developer can be increased, so that a dissolution-promoting effect in an alkaline developer can be expected.

On the other hand, there are various possible causes for residues that occur during rework, including foreign matter mixed in from the environment, redeposition of low-solubility components in the photosensitive resin, and insolubilization due to denaturation of the photosensitive resin itself during the film-forming process. Of these causes, it is believed that by increasing the solubility of the photosensitive resin through the addition of component (C), redeposition and insolubilization of residues originating from the photosensitive resin can be suppressed, thereby reducing residues during rework.

In order for the copolymer to exhibit alkali solubility, an alkali-soluble monomer such as (meth)acrylic acid is required. Normally, maleic anhydride does not exhibit alkali solubility, but it is thought that when it reacts with an alkaline developer, the ring-opening structure exhibits alkali solubility. From the viewpoint of storage stability of the photosensitive resin, maleic anhydride is the preferred monomer for exhibiting alkali solubility.

A copolymer composed of at least two monomers of (meth)acrylic acid, (meth)acrylic acid ester, styrene, a styrene derivative, and maleic anhydride, and one of the monomers constituting the copolymer is (meth)acrylic acid or maleic anhydride, has a weight average molecular weight of 1,000 to 50,000, preferably 3,000 to 30,000. If it is less than 1,000, tackiness may occur due to exudation to the cured surface in a later process. If it exceeds 50,000, compatibility with component (A) deteriorates. Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate. Styrene derivatives are styrene in which the hydrogen atoms are replaced with substituents (organic groups such as alkyl groups, halogen atoms, etc.), and specific examples include α-methylstyrene, and compounds in which an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a phenyl group, or a hydroxyl group is substituted on the aromatic ring of styrene. Examples of maleic anhydride include maleic anhydride and methylmaleic anhydride.

(C) A copolymer composed of at least two monomers selected from (meth)acrylic acid, (meth)acrylic acid esters, styrene, styrene derivatives, and maleic anhydride, and in which one of the monomers constituting the copolymer is (meth)acrylic acid or maleic anhydride, it is preferable that the (meth)acrylic acid or maleic anhydride is contained in an amount of 5 to 60% by weight per repeating unit. If it exceeds 60% by weight, the developability becomes too high, and the pattern shape tends to deteriorate. Also, if it is less than 5% by weight, the alkali solubility is low, and sufficient reworkability tends to be difficult to obtain.

ａは１から８の整数、ｂは１から１２の整数である。 Examples of the component (C) include a copolymer of (meth)acrylic acid, a (meth)acrylic acid ester, a copolymer of (meth)acrylic acid, a (meth)acrylic acid ester, styrene or a styrene derivative, a copolymer of (meth)acrylic acid, styrene or a styrene derivative, and a copolymer of styrene and maleic anhydride shown in the following structure.

a is an integer from 1 to 8, and b is an integer from 1 to 12.

From the viewpoint of reworkability, the (C) component is preferably a copolymer of (meth)acrylic acid or a (meth)acrylic acid ester, and from the viewpoint of heat resistance, a copolymer of styrene and maleic anhydride is preferred.

The content of component (C) in the photosensitive composition is preferably 1 to 10 parts by weight, more preferably 3 to 8 parts by weight, per 100 parts by weight of component (A), from the viewpoint of heat resistance. Also, from the viewpoint of tackiness, the content is preferably 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, per 100 parts by weight of component (A).

(C) A copolymer composed of at least two monomers selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid esters, styrene, styrene derivatives, and maleic anhydride, and in which one of the monomers constituting the copolymer is acrylic acid or maleic anhydride, if the content of the copolymer is within the above range, a film with good reworkability can be obtained without tackiness due to seepage onto the cured surface.

<(D) Crosslinking Agent>
The photosensitive composition may contain, in addition to the above-mentioned component (C), a crosslinking agent capable of introducing a crosslinked structure into the component (A). The crosslinking agent is preferably a compound containing two or more functional groups capable of reacting with the above-mentioned component (A) in one molecule.

For example, when component (A) is a polysiloxane compound containing SiH groups that were not used in the hydrosilylation reaction, if a compound having two or more ethylenically unsaturated groups in one molecule is included in the photosensitive composition as a crosslinking agent, a crosslinked structure is introduced by the hydrosilylation reaction between component (A) and the crosslinking agent. As the compound having two or more ethylenically unsaturated groups in one molecule, a compound similar to compound (γ) exemplified in relation to the synthesis of component (A) above can be used.

When the photosensitive composition contains a crosslinking agent, the content of the crosslinking agent is preferably 0.5 to 40 parts by weight, more preferably 1 to 35 parts by weight, and even more preferably 2 to 30 parts by weight, per 100 parts by weight of component (A). When the photosensitive composition contains a crosslinking agent, it is preferable to introduce a crosslinked structure by reacting component (A) with the crosslinking agent through heating (post-baking) after patterning by exposure and development. The introduction of a crosslinking structure hardens the pattern film, improving the insulating properties, heat resistance, solvent resistance, etc. of the pattern film.

<Solvent>
The photosensitive composition can be obtained by dissolving or dispersing the above-mentioned components (A), (B), and (C), and optionally the component (D) in a solvent. The photosensitive composition may be prepared by mixing the components just before film formation, or may be stored in the form of a single liquid in which all the components are mixed in advance.

The solvent may be any solvent capable of dissolving component (A), and examples of the solvent 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), 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 halogen-based solvents such as chloroform, methylene chloride, and 1,2-dichloroethane. From the viewpoint of film formation stability, propylene glycol-1-monomethyl ether-2-acetate, diethylene glycol diethyl ether, and butyl acetate are preferred. The amount of the solvent used may be set appropriately. The preferred amount of the solvent used per 1 g of solid content of the photosensitive composition is 0.1 to 10 mL.

<Other ingredients>
The photosensitive composition may contain resin components and additives other than the above (A) to (D). For example, the photosensitive composition may contain various thermoplastic resins for the purpose of modifying properties. Examples of the thermoplastic resin 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, and an alkoxysilyl group.

The photosensitive composition may contain an alkali-soluble component other than the above component (A) from the viewpoint of improving solubility in an alkaline developer. Examples of the alkali-soluble component include resins having an alkali-soluble functional group. Examples of the resin include phenolic resins, acrylic resins, amide resins, polysiloxane resins, etc. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, and an isocyanuric acid derivative structure represented by Z1 or Z2 below.

From the viewpoint of achieving both improved alkali solubility and the insulating properties, heat resistance, and solvent resistance of the cured film, the alkali soluble component is preferably a resin having the above structure Z1 and/or structure Z2, and in particular, a polysiloxane resin having the above structure Z1 and/or structure Z2.

The polysiloxane resin having structure Z1 and/or Z2 can be obtained, for example, by a hydrosilylation reaction between a compound containing the above structure Z1 and an ethylenically unsaturated group (diallyl isocyanurate, etc.) and/or a compound containing the above structure Z2 and an ethylenically unsaturated group (monoallyl isocyanurate, etc.) and a polysiloxane compound having a SiH group. As the polysiloxane compound having a SiH group, the polysiloxane compound having at least two SiH groups in one molecule, as exemplified above as compound (β), is preferably used.

In addition to the above, the photosensitive composition may contain sensitizers, acid diffusion inhibitors (quenchers), adhesion improvers, coupling agents such as silane coupling agents, deterioration inhibitors, hydrosilylation reaction inhibitors, polymerization inhibitors, polymerization catalysts (crosslinking accelerators), release agents, flame retardants, flame retardant assistants, surfactants, defoamers, emulsifiers, leveling agents, anti-repellent agents, ion trapping agents, thixotropy agents, tackifiers, storage stability improvers, light stabilizers, thickeners, plasticizers, reactive diluents, antioxidants, heat stabilizers, electrical conductivity agents, antistatic agents, radiation shielding agents, nucleating agents, phosphorus-based peroxide decomposers, lubricants, metal deactivators, thermal conductivity agents, and physical property adjusters, etc., within the scope that does not impair the purpose and effect of the present invention.

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, white clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, and inorganic balloons. Examples of colorants include organic pigments, inorganic pigments, and dyes.

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

[Film formation and formation of patterned cured film]
The positive photosensitive resin composition is coated on various substrates to form a coating film, which is then exposed to light through a mask of a specific shape, and the exposed area is dissolved and removed by alkaline development to form a patterned film. A patterned cured film is obtained by post-baking after development.

<Formation of coating film>
The method for applying the photosensitive composition onto the substrate is not particularly limited as long as it is a method that allows uniform application, and general 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, 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, from the viewpoint of reliability.

<Pre-bake>
Before exposure, heating (prebaking) may be performed to dry the solvent. The heating temperature may be appropriately set, 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 before or simultaneously with heating. Photosensitive compositions containing thermosetting components (e.g., the above-mentioned components (C) and (D)) may have reduced developability as curing proceeds due to heating. For this reason, the heating temperature in prebaking is preferably 120°C or lower.

<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, and typically, a light source having a wavelength in the range of 200 to 450 nm (e.g., a high-pressure mercury lamp, an extra-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, etc.) is used.

The exposure dose is not particularly limited, but is preferably 1 to 5000 mJ/cm ² , more preferably 5 to 1000 mJ/cm ² , and even more preferably 10 to 500 mJ/cm ^2. If the exposure dose is too low, curing may be insufficient and the pattern contrast may decrease, while if the exposure dose is too high, the takt time may increase, leading to increased manufacturing costs.

<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 the post-exposure baking is preferably 40 to 120°C, more preferably 50 to 110°C, and even more preferably 60 to 100°C.

<Developing>
The exposed coating film is brought into contact with an alkali developer by immersion, spraying, or the like to dissolve and remove the coating film in the exposed areas, thereby obtaining a patterned film. In the exposed areas, the alkali solubility of component (A) is increased by the action of the acid generated by irradiation of the photoacid generator with active energy rays, and the coating film is dissolved by alkali development.

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.

<Post-bake>
After dissolving and removing the exposed portion by development, post-baking may be performed to harden the composition of the film in the remaining non-exposed portion. For example, when the component (A) is a compound containing a SiH group and the photosensitive composition contains a compound having a plurality of ethylenically unsaturated groups as the component (D), post-baking proceeds with hardening by hydrosilylation reaction between the SiH group of the component (A) and the ethylenically unsaturated group of the component (D). The photosensitive resin composition of the present invention contains the component (D). By crosslinking with the ethylenically unsaturated group of the component (D) in whole or in part, a crosslinked structure with the component (A) is formed, thereby improving the heat resistance and chemical resistance by post-baking. The post-baking conditions may be appropriately set. The post-baking temperature is preferably 100 to 400°C, more preferably 120 to 350°C.

[Application]
The photosensitive composition of the present invention can be used as an alkali-developable transparent resist, and is particularly suitable as a material for FPDs. More specifically, examples of the material include a passivation film for TFTs, a gate insulating film for TFTs, an interlayer insulating film for TFTs, a transparent flattening 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.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[Synthesis of polysiloxane compound]
In a reaction vessel, 100 parts by weight of diallyl bisphenol S and 400 parts by weight of tetrahydrofuran (THF) were placed and stirred at room temperature. A homogeneous solution was obtained. 50 parts by weight of hexamethyldisilazane was added to the reaction vessel and reacted at room temperature for 2 hours. After confirming the presence of a peak derived from a trimethylsilyl group and the disappearance of a peak derived from a hydroxyl group by ¹ H-NMR, THF and the reaction residue were distilled off under reduced pressure to obtain diallyl bisphenol S (compound 1) in which the hydroxyl group was protected with a trimethylsilyl group.

A reaction vessel was charged with 60 parts by weight of 1,3,5,7-tetramethylcyclotetrasiloxane and 400 parts by weight of toluene, and the gas phase was replaced with nitrogen. The inside temperature was then heated to 100° C., and a mixture of 100 parts by weight of the above compound 1, 15 parts by weight of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 0.14 parts by weight of a xylene solution of platinum vinylsiloxane complex (containing 3% by weight of platinum), and 100 parts by weight of toluene was added dropwise under stirring. After the addition, the disappearance of the peak derived from the allyl group was confirmed by ¹ H-NMR, and then the toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid (reactant A). It was confirmed by ¹ H-NMR that reactant A was a polysiloxane-based compound having a bisphenol S structure protected by a trimethylsilyl group and having 3.0 mmol/g of SiH groups in terms of dibromoethane equivalent.

[Preparation of positive-type photosensitive resin composition]
The reaction mixture was 100.00 parts by weight of the above reactant A, 2 parts by weight of an imide sulfonate compound ("SP-606" manufactured by ADEKA) and 1 part by weight of (4-tert-butylphenyl)sulfonium nonafluorobutane-1-sulfonate ("TTBPS-PFBS" manufactured by Toyo Gosei Chemical Industry Co., Ltd.) as photoacid generators, 4 parts by weight of 9,10-dibutoxyanthracene as a sensitizer, 0.05 parts by weight of a 3% by weight solution of [Pt-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in isopropanol (manufactured by NE Chemcat Co., Ltd.) as a catalyst, 5 parts by weight of "bis(2-ethylhexyl)adipate" (manufactured by Daihachi Chemical Industry Co., Ltd.) as a plasticizer, and 2-methyl- A positive photosensitive resin composition was prepared by mixing 2 parts by weight of 3-butyn-2-ol, 0.5 parts by weight of a silicone surface conditioner ("MQV6 Resin" manufactured by SiVance), 0.1 parts by weight of 1,3-bis(4,5-dihydro-2-oxazolyl)benzene ("1,3-PBO" manufactured by Mikuni Seiyaku Kogyo) as an acid diffusion inhibitor, 0.15 parts by weight of 2-methyl-4'-(methylthio)-2-morpholinopropiophenone ("OMNIRAD907" manufactured by IGM), 1 part by weight of "Adekastab AO-80" (manufactured by ADEKA) as an antioxidant, and 143.91 parts by weight of propylene glycol-1-monomethyl ether-2-acetate as a solvent. This composition is referred to as the "standard composition" (Comparative Example 1).

In the examples described below, a copolymer composed of at least two monomers of (meth)acrylic acid, (meth)acrylic acid ester, styrene, a styrene derivative, and maleic anhydride, one of which is (meth)acrylic acid or maleic anhydride, was added to the above standard composition in the ratio shown in Table 1 per 100 parts by weight of component (A) to prepare a positive photosensitive resin composition.

The alkali solubility of component (C) is thought to vary depending on the molecular weight of the copolymer and the content of monomers that exhibit alkali solubility. The copolymers used were SMA1000, SMA2000, and SMA3000, which have a relatively low molecular weight of less than 10,000 and a maleic anhydride monomer content of 25% or more that exhibit alkali solubility as styrene and maleic anhydride copolymers, EF40, EF60, and EF80 (manufactured by Cray Valley) which have a molecular weight of 10,000 or more and a maleic anhydride monomer content of 20% or less that are thought to be less likely to exhibit tackiness due to bleeding of added components, and FOLETT ZAH-110, FOLETT ZAH-310, and Actflow CB3098 (manufactured by Soken Chemical Industries, Ltd.) as copolymers of (meth)acrylic acid and (meth)acrylic acid esters with a (meth)acrylic acid structure that are thought to have high alkali solubility.

In Comparative Example 2, stearic acid (Tokyo Chemical Industry Co., Ltd.) was used as the carboxylic acid monomer in the above standard composition.

[Formation of patterned cured film and evaluation of hole width]
The positive photosensitive resin compositions of the examples and comparative examples were applied by spin coating onto a 50 mm x 50 mm alkali-free glass substrate, and heated (prebaked) at 110 ° C for 2 minutes using a hot plate to form a coating film with a thickness of 2.5 μm. Exposure was performed at each cumulative exposure dose through a photomask (hole 10 μm) using a mask aligner (Dainippon Kaken "MA-1300"). Two minutes after exposure, the substrate was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution, Tama Chemical Industry Co., Ltd.) at 23 ° C for 60 seconds to perform development processing. Further, postbaking was performed in an oven at 230 ° C for 30 minutes to form a patterned cured film.

[Sensitivity evaluation]
For the compositions of each of the Examples and Comparative Examples, films were formed by changing the exposure dose under the above conditions, and in a 10 μm hole pattern, the width at a position 1.25 μm high from the bottom (the portion where the coating film is dissolved and the glass substrate is exposed) was observed with a laser microscope (Olympus "OLS4000"), and the exposure dose at which the film thickness fell within 10±0.2 μm was defined as the optimal sensitivity.

[Formation of cured film for tackiness test and evaluation of tackiness test]
The positive photosensitive resin compositions of the examples and comparative examples were applied by spin coating onto a 50 mm x 50 mm alkali-free glass substrate, and heated (prebaked) at 110 ° C for 2 minutes using a hot plate to form a coating film with a thickness of 2.5 μm. Except for the exposure process, the substrate was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tama Chemical Industry Co., Ltd.) at 23 ° C for 60 seconds for development treatment. The substrate was further baked in an oven at 120 ° C for 30 minutes, and the tackiness was confirmed by touching the surface of the cured film with a finger. Those without tack were marked with ○, and those with tack were marked with ×.

[Formation of cured film for reworkability test and evaluation of reworkability test]
On a 50 mm x 50 mm alkali-free glass substrate, the positive photosensitive resin compositions of the examples and comparative examples were applied by spin coating, and heated (prebaked) at 110 ° C for 2 minutes using a hot plate to form a coating film with a thickness of 2.5 μm. Exposure was performed at the integrated dose of the optimum sensitivity using a mask aligner (Dainippon Kaken "MA-1300"). Two minutes after exposure, the patterned film was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution, Tama Chemical Industry Co., Ltd.) at 23 ° C for 60 seconds to perform development processing. This patterned film was stored in an environment of 23 ° C and humidity 50%, and the patterned film after a predetermined time was exposed to the entire surface at the integrated dose of the optimum sensitivity, and two minutes after exposure, the patterned film was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution, Tama Chemical Industry Co., Ltd.) at 23 ° C for 120 seconds to perform rework processing. The substrates after rework were observed under an optical microscope, and those without resin residue or patterning marks were marked with ◯, and those with resin residue or patterning marks were marked with ×. The compositions of the examples and comparative examples, and the above evaluation results are shown in Table 1.

In Comparative Example 1, which does not contain the (C) component, the sensitivity was low and the tackiness was good, but it was not possible to rework it. In Comparative Example 2, the sensitivity was slightly improved, and the reworkability immediately after development was good, but the tackiness was poor, and the reworkability deteriorated after 24 hours of storage. On the other hand, in Examples 1 to 27, in which the (C) component was added, high sensitivity was obtained depending on the amount of the (C) component added, and in Examples 1 to 9, when SMA1000, SMA2000, and SMA3000, which are styrene and maleic anhydride copolymers with relatively low molecular weights and high monomer content that exhibits alkali solubility, were added, the reworkability was good immediately, 24 hours, and 40 hours, and the tackiness was also good. In Examples 10 to 18, when EF40, EF60, and EF80, which are styrene and maleic anhydride copolymers with relatively high molecular weights and low content of monomers that are soluble in alkali, were added, the reworkability immediately after addition was good in all cases, and in Examples 12 and 15, which were added in large amounts, the reworkability after 24 hours and 40 hours was also good. In Examples 19 to 27, when FOLETT ZAH-110, FOLETT ZAH-310, and Actflow CB3098, which are copolymers of (meth)acrylic acid and (meth)acrylic acid ester, were added, the sensitivity was the highest and the reworkability was also good. Also, in Examples 19 and 22, in which a small amount of FOLETT ZAH-110 and FOLETT ZAH-310, which are copolymers of (meth)acrylic acid and (meth)acrylic acid ester and have relatively high molecular weights, were added, good reworkability was also shown.

These results show that the addition of component (C) produces a patterned film that has both tackiness and reworkability, and that a highly sensitive cured film can be obtained depending on the amount of component (C) added.

Claims (4)

Component (A): a compound whose alkali solubility increases under the action of an acid;
Component (B): a photoacid generator;
(C) component: a copolymer composed of at least two monomers selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid esters, styrene, styrene derivatives, and maleic anhydride, in which at least one of (meth)acrylic acid and maleic anhydride is an essential component;
The content of the (C) component relative to 100 parts by weight of the (A) component is 1 to 10 parts by weight,
the component (A) contains a polysiloxane compound having a structure in which a phenolic hydroxyl group is protected by a protecting group and a cyclic siloxane structure,
The component (C) contains 5 to 60% by weight of a total of repeating units derived from (meth)acrylic acid and repeating units derived from maleic anhydride that exhibit alkali solubility. The positive-type photosensitive resin composition according to claim 1, further comprising a compound (D) containing two or more functional groups in one molecule capable of reacting with the component (A). A patterned cured film comprising a cured product of the positive photosensitive resin composition according to claim 1 or 2. A method for producing a patterned cured film, comprising applying the positive photosensitive resin composition according to claim 1 or 2 onto a substrate, and carrying out patterning by exposure and alkaline development.