JP2021120713A - Positive photosensitive resin composition, patterned cured film, and method for producing the same - Google Patents

Abstract

To provide a positive photosensitive resin composition which hardly causes tackiness in the positive photosensitive resin composition and gives a cured film excellent in reworkability.SOLUTION: The positive photosensitive resin composition contains a component (A): a compound whose alkali solubility increases by the action of an acid, a component (B): a photoacid generator, and a component (C): a copolymer which is composed of two or more monomers selected from the group consisting of (meth)acrylic acid, a (meth)acrylate, styrene, a styrene derivative, and maleic anhydride, provided that at least one of (meth)acrylic acid and maleic anhydride is an essential component. The content of the component (C) is 1-10 pts.wt. based on 100 pts.wt. of the component (A).SELECTED DRAWING: None

Description

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

In the field of displays such as liquid crystal displays and organic EL displays, there is a demand for a photosensitive composition capable of positive patterning and forming a highly sensitive and highly reliable insulating film. The positive photosensitive resin composition is a type of resin composition that leaves a portion not irradiated with active light as an image. In the positive type, since the solubility of the exposed part is increased by irradiating the active light with a photoacid generator, neither the exposed part nor the unexposed part is cured at the time of pattern exposure, and the obtained pattern shape is defective. If this is the case, or if residues or foreign matter are generated in the pattern portion, the substrate can be reused (reworked) by full exposure or the like. Therefore, a positive photosensitive resin composition is preferably used from the viewpoint of excellent reworkability.

For example, Patent Document 1 describes that by adding a carboxylic acid having an unsaturated bond or a derivative thereof to a phenol resin, it is possible to suppress the generation of a residue after development and prepare a cured film having excellent mechanical properties. However, these monomers remain in the phenol resin, and if a process such as heating is included in the subsequent process, the monomer component exudes to the surface of the cured product or volatilizes into the atmosphere, causing contamination of the resin surface or in the process. It can contaminate the equipment, leaving room for improvement in terms of process stability.

Japanese Unexamined Patent Publication No. 2014-186124

In view of the above, an object of the present invention is to provide a positive photosensitive resin composition which is less likely to cause tackiness, has excellent substrate reworkability, and can provide a cured film in which additive components do not exude due to steps such as heating. do.

The positive photosensitive resin composition according to the present invention comprises (A) component: a compound whose alkali solubility is increased by the action of an acid; (B) component: a photoacid generator; (C) component: (meth) acrylic acid. , (Meta) acrylic acid ester, styrene, styrene derivative, maleic acid anhydride is a copolymer composed of at least two or more monomers, and one of the monomers constituting the copolymer is (meth) acrylic acid. It is a copolymer which is an acid or a maleic anhydride, and the content of the component (C) is 1 to 10 parts by weight with respect to 100 parts by weight of the component (A).

The positive photosensitive resin composition preferably contains a structure in which the component (A) has a phenolic hydroxyl group protected by a protecting group.

The positive photosensitive resin composition is preferably a compound containing two or more functional groups capable of reacting with the component (A) as the component (D) in one molecule.

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

A pattern film is obtained by applying the above-mentioned positive photosensitive resin composition on a substrate and performing patterning by exposure and alkaline development. After the development, the pattern 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 having excellent substrate reworkability and in which additive components do not exude due to steps such as heating.

[Photosensitive composition]
The photosensitive composition of the present invention comprises (A) a compound whose alkali solubility is increased by the action of an acid, (B) a photoacid generator, (C) (meth) acrylic acid, (meth) acrylic acid ester, styrene, and the like. A copolymer composed of at least two or more monomers of a styrene derivative and maleic acid anhydride, and one of the monomers constituting the copolymer is (meth) acrylic acid or maleic acid anhydride. It is a positive photosensitive resin composition which is a coalescence and the content of the component (C) is 1 to 10 parts by weight with respect to 100 parts by weight of the component (A).

In the following, compounds whose alkali solubility is increased by the action of acid are "component (A)", photoacid generators are "component (B)", (meth) acrylic acid, (meth) acrylic acid ester, styrene, and styrene. A copolymer composed of at least two or more monomers of a derivative and maleic acid anhydride, and one of the monomers constituting the copolymer is (meth) acrylic acid or maleic acid anhydride. Is described as "(C) component". The photosensitive composition may further contain a cross-linking agent (a compound having a functional group capable of introducing a cross-linked structure into the component (A)) as the component (D). Unless otherwise specified, the compounds and functional groups exemplified in the present specification may be used alone or in combination (coexistence) of two or more.

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

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 by the tert-butoxycarbonyl group by a reaction using a Bocification reagent. 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 particularly preferably a methyl group, from the viewpoint of ease of deprotection by an acid. A phenolic hydroxyl group can be protected by a trimethylsilyl group by a reaction using a silylating agent such as hexamethyldisilazane or trimethylchlorosilane.

Examples of the protecting group for the carboxylic acid include tertiary alkyl esters and acetals. Examples of the tertiary alkyl group in the tertiary alkyl ester of the carboxylic acid include a tert-butyl group, an adamantyl group, a tricyclodecyl group, a norbornyl group and the like.

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

When a permanent resist is prepared from a positive photosensitive resin composition, the component (A) preferably has a polymerizable functional group. When heating (post-baking) is performed after exposure and development, the polymerizable functional group of the component (A) reacts with the component (D) described later, and a crosslinked structure is introduced to obtain a pattern-cured film.

The component (A) preferably contains a structure in which the alkali-soluble imparting group is protected by a protecting group, and a polymer skeleton structure other than the above-mentioned polymerizable functional group. Polymer skeleton structures include polyacrylic, polyphenol, polyamide, polyacid anhydride, polycarbonate, polydiene, polyester, polyhaloolefin, polyimide, polyimine, polyketone, polyolefin, polyether, polyphenylene, polyphosphazene, polysiloxane, polysilane, polystyrene. , Polysulfide, polysulfone, polyurethane, polyurea, polyvinyl and the like.

<Component (A) having a polysiloxane structure>
Since a cured film having high heat resistance and low dielectric constant can be formed, the component (A) preferably has a polysiloxane structure, and particularly preferably has a cyclic polysiloxane structure. The component (A) containing a polysiloxane structure is a compound in which a "compound having a siloxane unit" is used as a main skeleton and a "structure in which an alkali-soluble imparting group is protected by a protecting group" is introduced, and a specific example thereof. Examples thereof include polysiloxane compounds disclosed in WO2014 / 007231 and the like.

In the present specification, the "polysiloxane structure" means a structural skeleton having a siloxane unit Si—O—Si, and the “cyclic polysiloxane structure” means a siloxane unit (Si—O—Si) as a ring component. ) Means a cyclic molecular structure skeleton. A compound containing a cyclic polysiloxane structure tends to be superior in film forming property and heat resistance of the obtained cured film as compared with a compound containing only a chain polysiloxane structure.

A polysiloxane compound introduced with "a structure in which an alkali-soluble imparting group is protected by a protecting group" (hereinafter, may be referred to as "structure X") is obtained by, for example, a hydrosilylation reaction. The hydrosilylation reaction has the advantage that the 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 reactive with the SiH group. When at least one of these compounds (starting substances) has a structure X in addition to the above functional groups, a polysiloxane compound having a structure X can be 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. (Α): A compound having a carbon-carbon double bond having reactivity 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 ethylenically unsaturated group)
Compound (α) is a compound containing a carbon-carbon double bond having reactivity with a structure X and a SiH group. Examples of the group containing a carbon-carbon double bond reactive with the SiH group (hereinafter, may be simply referred to as "ethylenically unsaturated group") include a vinyl group, an allyl group, a metalyl group, an acrylic group, and methacryl. Group, 2-Hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- Examples thereof include (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group and vinyl ether group. ..

Compound (α) preferably has a plurality of ethylenically unsaturated groups in one molecule. When one molecule has a plurality of ethylenically unsaturated groups, the plurality of polysiloxane compounds (compound (β)) are crosslinked by the hydrosilylation reaction, so that the molecular weight of the component (A) is increased and the film-forming property is formed. And the heat resistance of the cured film tends to improve.

As the structure X, as described above, a structure in which a protecting group is bonded to an acidic group such as a carboxylic acid or a phenolic hydroxyl group can be mentioned. When the component (A) is a polysiloxane compound, the structure X is preferably one in which a protective group is bonded to a phenolic hydroxyl group. Further, from the viewpoint of chemical resistance and insulating property of the cured film, the structure X preferably contains a bisphenol structure.

The bisphenol structure includes bisphenol A structure, bisphenol AP structure, bisphenol AF structure, bisphenol B structure, bisphenol BP structure, bisphenol E structure, bisphenol M structure, bisphenol F structure, bisphenol S structure, bisphenol PH structure, bisphenol C structure, and bisphenol. G structure, bisphenol TMC structure, bisphenol Z structure and the like can be mentioned. Among these, bisphenol A structure, bisphenol B structure, bisphenol C structure, bisphenol E structure, bisphenol F structure, bisphenol AF structure, bisphenol, because it is easy to obtain a pattern with excellent solubility in alkaline developing solution and excellent contrast. The S structure, bisphenol AP structure or bisphenol PH structure is preferable, and the bisphenol S structure or bisphenol F structure is particularly preferable from the viewpoint of ease of deprotection by acid.

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

In the general formula (I), R ¹ is a divalent organic group and may have a structure that can be taken as a bisphenol structure. For example, when compound (α) has a bisphenol S structure, R ¹ is SO ₂ , and when compound (α) has a bisphenol F structure, R ¹ is CH ₂ . A plurality of R ² are each independently an alkyl group having 1 to 6 carbon atoms, preferably, all of R ² is a methyl group. The compound represented by the general formula (I) is 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, for example, the compound described in WO96 / 15194, which has at least two SiH groups in one molecule, and the like. Can be used. Specific examples of the compound (β) include a hydrosilyl group-containing polysiloxane having a linear structure, a polysiloxane having a hydrosilyl group at the molecular terminal, and a cyclic polysiloxane containing a hydrosilyl group. The cyclic polysiloxane may have a polycyclic structure, and the polycyclic may have a polyhedral structure. In order to form a cured film having high heat resistance and mechanical strength of a polyhedral skeleton, it is preferable to use a cyclic polysiloxane compound having at least two SiH groups in one molecule as the compound (β). Compound (β) preferably contains 3 or more SiH groups in one molecule. From the viewpoint of heat resistance and light resistance, the group existing on the Si atom is preferably either a hydrogen atom or a methyl group.

Examples of the hydrosilyl group-containing polysiloxane having a linear structure include a copolymer of a dimethylsiloxane unit and a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a combination of a diphenylsiloxane unit and a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. Examples thereof include polymers, copolymers of methylphenylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units, and polysiloxanes whose ends are blocked by a dimethylhydrogensilyl group.

Polysiloxanes having a hydrosilyl group at the molecular end include polysiloxanes whose ends are blocked by a dimethylhydrogensilyl group, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _1/2 units), and SiO ₂ units. , Polysiloxane composed of at least one siloxane unit selected from the group consisting of _{SiO 3/2 unit and SiO unit, and the like.}

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

^{R 4} , R ⁵ and R ⁶ in the formula 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. The m is preferably 3 or more. m + n is preferably 3 to 12.

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

Examples of the cyclic polysiloxane compound represented by the general formula (II) include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 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 and the like are exemplified. Above all, from the viewpoint of availability and reactivity of SiH group, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (in the general formula (II), m = 4, n = 0, compounds wherein ^{R 4} is methyl group).

Compound (β) may be a polycyclic cyclic polysiloxane. The polycycle 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 6 to 10 Si atoms. Specific examples of the polysiloxane having a polyhedral skeleton include silsesquioxane (Si atom number = 8) represented by the following general formula (III).

In the above formula, R ^{10 to} R ¹⁷ are independently hydrogen atom, chain alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), cycloalkyl group (cyclohexyl group, etc.), aryl group (phenyl). Groups and trill groups, etc.), groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are replaced with halogen atoms or cyano groups (chloromethyl group, trifluoropropyl group, cyanoethyl group, etc.), alkenyl It is a monovalent group selected from a group (vinyl group, allyl group, butenyl group, hexenyl group, etc.), a (meth) acryloyl group, an epoxy group, and an organic group containing a mercapto group or an amino group. The hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

The cyclic polysiloxane may be silylated silicic acid having a polyhedral skeleton. Specific examples of silylated silicic acid having a polyhedral skeleton include a compound represented by the following general formula (IV) (Si atom number = 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).

Polysiloxane is obtained by a known synthetic method. For example, the cyclic polysiloxane represented by the general formula (II) can be synthesized by the method described in WO96 / 15194 or the like. Polysiloxane having a polyhedral skeleton such as silsesquioxane and silylated silicic acid having a polyhedral skeleton are described in, for example, JP-A-2004-359933, JP-A-2004-143449, JP-A-2006-269402 and the like. It can be synthesized by the method described. As the compound (β), a commercially available polysiloxane compound may be used.

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

For example, in addition to the compound (α) and the 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, a plurality of polysiloxane compounds (compound (β)) are crosslinked by a hydrosilylation reaction, so that the molecular weight of component (A) is increased, and the film-forming property and the heat resistance of the cured film are improved. Tend to do.

The compound (γ) may be either an organic polymerization system compound or an organic monomer system compound. Organic polymerization system compounds include polyether type, polyester type, polyarylate type, polycarbonate type, saturated hydrocarbon type, unsaturated hydrocarbon type, polyacrylic acid ester type, polyamide type, phenol-formaldehyde type (phenol resin type). Alternatively, a polyimide-based compound can be mentioned. Examples of the organic monomer-based compound include aromatic hydrocarbon-based compounds such as phenol-based, bisphenol-based, benzene and naphthalene; aliphatic hydrocarbon-based compounds such as linear and alicyclic-based compounds; and heterocyclic compounds. ..
If compound (γ) is used,

Specific examples of the compound (γ) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropandiallyl ether, trimethylolpropantriallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1 , 1,2,2-tetraallyloxyetane, diallylidene pentaerythlit, triallyl cyanurate, triallyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monomethyl isocyanurate, 1,2,4-trivinylcyclohexane, 1,4-Butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, trimethylpropantrivinyl ether, pentaerythritol tetravinyl ether, bisphenol S diallyl ether, divinyl Benzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (allyloxy) adamantan, 1,3-bis (vinyloxy) adamantan, 1,3,5-tris (Allyloxy) adamantan, 1,3,5-tris (vinyloxy) adamantan, dicyclopentadiene, vinylcyclohexene, 1,5-hexadien, 1,9-decadien, diallyl ether, bisphenol A diallyl ether, 2,5-diallyl Phenol allyl ethers and their oligomers, 1,2-polybutadiene (1,2 ratio 10-100%, preferably 1,2 ratio 50-100%), novolak phenol allyl ether, allylated polyphenylene oxide In addition, those in which all the glycidyl groups of conventionally known epoxy resins are replaced with allyl groups and the like can be mentioned. Further, a compound in which the allyl group in the above-exemplified compound is replaced with a (meth) acryloyl group (for example, a polyfunctional (meth) acrylate) is also preferably used as the compound (γ).

The compound (γ) may be a polysiloxane compound having two or more ethylenically unsaturated groups. Specific examples of the polysiloxane compound having two or more ethylenically unsaturated groups include those in which a part or all of the hydrogen atoms bonded to Si of the above compound (β) are replaced with ethylenically unsaturated groups. Be done. Among them, a cyclic polysiloxane compound having two or more ethylenically unsaturated groups is preferable from the viewpoint of improving the heat resistance of the cured film.

Specific examples of the cyclic polysiloxane compound having two or more ethylenically unsaturated groups include cyclic polysiloxane in which a vinyl group is bonded to a Si atom as an ethylenically unsaturated group. 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 and the like.

As a starting material for the hydrosilylation reaction, a compound having only one functional group involved in the hydrosilylation reaction (hereinafter, “compound (δ)”) may be used. The functional group involved in the hydrosilylation reaction is a SiH group or an ethylenically unsaturated group. By using a compound containing only one functional group involved in the hydrosilylation reaction, a specific functional group can be introduced at the end of the polymer.

For example, by using a siloxane compound having one SiH group as the compound (δ), a siloxane structural site can be introduced at 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), and one of R ^{10 to} R ^{17 in} the above-mentioned general formula (III) is hydrogen. Examples thereof include a polyhedron polysiloxane compound which is an atom, a silylated silicic acid compound in which one ^{of R 18 to} R ^{41 in the above general formula (IV) is a hydrogen atom, and the like.} The siloxane compound having one SiH group may be a chain siloxane compound.

By using a compound containing one ethylenically unsaturated group as the compound (δ), a desired functional group can be introduced at the end of the polymer. In addition to the above, compounds involved in the hydrosilylation reaction, such as chain polysiloxane having two or more SiH groups, may 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 step, it is preferable to charge all the starting materials in one pot, carry out a hydrosilylation reaction, and finally remove the unreacted compound. On the other hand, from the viewpoint of suppressing the formation of low molecular weight compounds, a compound containing a plurality of ethylenically unsaturated groups (for example, compound (α) and compound (γ)) and a compound containing a plurality of SiH groups (for example, compound (β)). ), And one of them is subjected to a hydrosilylation reaction, and after removing the unreacted compound, a compound having only one functional group involved in the hydrosilylation reaction (for example, compound (δ)) is added to one molecule. A method of carrying out a hydrosilylation reaction is preferable.

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 and the total amount B of SiH groups of the starting material satisfy 1 ≦ B / A ≦ 30. It is more preferable to satisfy / A ≦ 10. If the B / A is 1 or more, the unreacted ethylenically unsaturated group is unlikely to remain, and if the B / A is 30 or less, the unreacted compound (β) is unlikely to remain. Can be improved.

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

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

In the above, as a method for obtaining a polysiloxane compound having a structure X, a compound (α) having a structure X and an ethylenically unsaturated group in one molecule and a polysiloxane compound having at least two SiH groups in one molecule are combined. Although the hydrosilylation reaction with (β) has been described as an example, the method for synthesizing the component (A) is not limited to this. The component (A) can also be obtained by a hydrosilylation reaction using a starting material other than the above.

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

Cyclic siloxane compounds containing ethylenically unsaturated groups include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 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- Examples thereof include 1,3,5,7,9,11-hexamethylcyclosiloxane. In the cyclic polysiloxane compound having an ethylenically unsaturated group, the organic group existing on the Si atom is preferably a vinyl group or a methyl group from the viewpoint of heat resistance and light resistance.

<(B) Photoacid generator>
The photosensitive composition contains a photoacid generator as the component (B). Acid is generated when the photoacid generator is irradiated with active energy rays by exposure. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, and γ-rays. The acid generated from the photoacid generator decomposes the component (A) to express an acidic group or a hydroxyl group, thereby increasing the alkali solubility.

The photoacid generator contained in the photosensitive composition is not particularly limited as long as it generates Lewis acid by exposure. Specific examples of the photoacid generator include ionic photoacid generators such as sulfonium salts, iodonium salts and onium salts; nonionic photoacid generators such as imide sulfonates, oxime sulfonates and sulfonyldiazomethanes. .. The anion contained in the ionic photoacid ^{_{generator, B (C 6 F 5)}} 4 -, PF 6 -, SbF 6 -, CF 3 SO 3 - and _C 4 _F 9 SO ₃ ^-, and the like. As the photoacid generator, imide sulfonates and oxime sulfonates are preferable 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 0.5 to 0.5 parts by weight, based on 100 parts by weight of the component (A). 5 parts by weight is more preferable. When the amount of the photoacid generator is within the above range, the alkali solubility of the component (A) in the exposed portion can be sufficiently increased to improve the patterning property, and the decrease in contrast due to the excess acid can be suppressed.

<A copolymer composed of at least two or more monomers of (C) (meth) acrylic acid, (meth) acrylic acid ester, styrene, styrene derivative, and maleic anhydride, and constitutes the copolymer thereof. Copolymer in which one of the monomers is (meth) acrylic acid or maleic acid anhydride>

The photosensitive composition is a copolymer composed of at least two or more monomers of (meth) acrylic acid, (meth) acrylic acid ester, styrene, styrene derivative, and maleic anhydride as the component (C). Moreover, one of the monomers constituting the copolymer contains a copolymer of (meth) acrylic acid or maleic acid anhydride. The component (C) has alkali solubility, and by adding it to the photosensitive resin, the solubility of the photosensitive resin in the alkaline developer can be increased, so that the effect of promoting the dissolution in the alkaline developer can be expected.

On the other hand, various factors can be considered for the residue generated during rework. For example, foreign matter mixed from the environment or reattachment of a component having low solubility in the photosensitive resin, or under the film forming process of the photosensitive resin itself. Insolubilization due to denaturation of. Among these causes, with respect to the residue derived from the photosensitive resin, by increasing the solubility of the photosensitive resin by adding the component (C), reattachment and insolubilization can be suppressed, and the residue at the time of rework can be reduced. It is considered to be.

An alkali-soluble monomer such as (meth) acrylic acid is required to develop the alkali solubility of the copolymer. Normally, maleic anhydride does not show alkali solubility, but it is considered that the structure that opens the ring by reacting with an alkali developer exhibits alkali solubility. From the viewpoint of stability of the photosensitive resin during storage, maleic anhydride is preferable as the monomer that exhibits alkali solubility.

A copolymer composed of at least two or more monomers of (meth) acrylic acid, (meth) acrylic acid ester, styrene, styrene derivative, and maleic anhydride, and one of the monomers constituting the copolymer. The weight average molecular weight of the copolymer, which is (meth) acrylic acid or maleic anhydride, is 1,000 to 50,000, preferably 3,000 to 30,000. If it is less than 1,000, tack due to exudation to the surface of the cured product may occur in a later step. If it exceeds 50,000, the compatibility with the component (A) deteriorates. Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and phenyl (meth) acrylate. Benzyl (meth) acrylate and the like can be mentioned. The styrene derivative is one in which the hydrogen atom in styrene is substituted with a substituent (organic group such as an alkyl group, halogen atom, etc.), and specifically, α-methylstyrene, the number of carbon atoms on the aromatic ring of styrene. Examples thereof include compounds in which 1 to 6 alkyl groups, alkoxy groups, phenyl groups and hydroxy groups are substituted. Examples of maleic anhydride include maleic anhydride and methyl maleic anhydride.

(C) A copolymer composed of at least two or more monomers of (meth) acrylic acid, (meth) acrylic acid ester, styrene, styrene derivative, and maleic anhydride, and constitutes the copolymer thereof. The (meth) acrylic acid or maleic acid anhydride in the copolymer in which one of the monomers is (meth) acrylic acid or maleic acid anhydride is preferably contained in an amount of 5 to 60% by weight per repeating unit. If it exceeds 60% by weight, the developability tends to be too high and the pattern shape tends to deteriorate. Further, if it is less than 5% by weight, the alkali solubility is low, and there is a tendency that sufficient reworkability cannot be obtained.

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 (meth) acrylic acid, a copolymer of (meth) acrylic acid ester, (meth) acrylic acid, (meth) acrylic acid ester, a copolymer of styrene or a styrene derivative, (meth). Examples thereof include copolymers of acrylic acid, styrene or styrene derivatives, and copolymers of styrene and maleic acid anhydrides shown in the following structures.

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

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

The content of the component (C) in the photosensitive composition is preferably 1 to 10 parts by weight, more preferably 3 to 8 parts by weight, based on 100 parts by weight of the component (A), in terms of heat resistance. From the viewpoint of tackiness, 1 to 10 parts by weight is preferable, and 1 to 8 parts by weight is more preferable with respect to 100 parts by weight of the component (A).

(C) A copolymer composed of at least two or more monomers of (meth) acrylic acid, (meth) acrylic acid ester, styrene, styrene derivative, and maleic anhydride, and constitutes the copolymer thereof. When the content of the copolymer in which one of the monomers is acrylic acid or maleic anhydride is in the above range, a film having good reworkability can be obtained without causing tack due to exudation to the surface of the cured product. ..

<(D) Cross-linking agent>
The photosensitive composition may contain a cross-linking agent capable of introducing a cross-linked structure into the component (A) in addition to the above-mentioned component (C). As the cross-linking agent, a compound containing two or more functional groups capable of reacting with the above component (A) in one molecule is preferable.

For example, when the component (A) is a polysiloxane compound and contains a SiH group that was not used in the hydrosilylation reaction, a compound having two or more ethylenically unsaturated groups in one molecule is used as a cross-linking agent. When included in the photosensitive composition, the crosslinked structure is introduced by the hydrosilylation reaction between the component (A) and the crosslinking agent. As the compound having two or more ethylenically unsaturated groups in one molecule, the same compound as the compound (γ) exemplified for the synthesis of the component (A) above can be used.

When the photosensitive composition contains a cross-linking agent, the content of the cross-linking agent is preferably 0.5 to 40 parts by weight, more preferably 1 to 35 parts by weight, and 2 to 2 to 100 parts by weight of the component (A). 30 parts by weight is more preferable. When the photosensitive composition contains a cross-linking agent, it is preferable to introduce a cross-linked structure by reacting the component (A) with the cross-linking agent by heating (post-baking) after patterning by exposure and development. Since the pattern film is hardened by the introduction of the crosslinked structure, the insulating property, heat resistance, solvent resistance and the like of the pattern film can be improved.

<Solvent>
A photosensitive composition is obtained by dissolving or dispersing the above-mentioned component (A), component (B) and component (C), and if necessary, component (D) in a solvent. The photosensitive composition may be prepared by mixing each component immediately before film formation, or may be stored in a one-component state in which all the components are mixed and prepared in advance.

The solvent may be any solvent as long as the component (A) can be dissolved, and specifically, a hydrocarbon solvent such as benzene, toluene, hexane and heptane; tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether and the like. Ether-based solvents; Ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Glycol-based 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. Solvents: Ester solvents such as ethyl acetate, butyl acetate, isobutyl isobutyrate, isobutyl butyrate; 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 preferable. The amount of the solvent used may be set as appropriate. The preferable amount of the solvent used with respect to 1 g of the solid content of the photosensitive composition is 0.1 to 10 mL.

<Other ingredients>
The photosensitive composition may contain resin components, additives and the like other than the above (A) to (D). For example, the photosensitive composition may contain various thermoplastic resins for the purpose of modifying the properties and the like. Examples of the thermoplastic resin include acrylic resin, polycarbonate resin cycloolefin resin, olefin-maleimide resin, polyester resin, polyether sulfone resin, polyarylate resin, polyvinyl acetal resin, polyethylene resin, polypropylene resin, and polystyrene. Examples thereof include resins, polyamide resins, silicone resins, fluororesins, natural rubbers and rubber-like resins such as 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-mentioned component (A) from the viewpoint of improving the 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 phenol resin, acrylic resin, amide resin, polysiloxane resin and the like. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxy group, and an isocyanuric acid derivative structure represented by Z1 or Z2 below.

From the viewpoint of achieving both improvement in alkali solubility and insulation, heat resistance, solvent resistance, etc. of the cured film, the resin having the above-mentioned structure Z1 and / or structure Z2 is preferable as the alkali-soluble component, and above all, the above-mentioned resin has the above-mentioned structure Z1 and / or structure Z2. A polysiloxane resin having the structure Z1 and / or the structure Z2 of the above is preferable.

The polysiloxane resin having the structure Z1 and / or Z2 is, for example, a compound containing the above structure Z1 and an ethylenically unsaturated group (such as diallyl isocyanurate) and / or a compound containing the above structure Z2 and an ethylenically unnecessary sum group. It is obtained by a hydrosilylation reaction between (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 exemplified above as the compound (β) is preferably used.

In addition to the above, the photosensitive composition includes a sensitizer, an acid diffusion inhibitor (quencher), an adhesive improver, a coupling agent such as a silane coupling agent, a deterioration inhibitor, a hydrosilylation reaction inhibitor, and a polymerization agent. Prohibition agent, polymerization catalyst (crosslink accelerator), mold release agent, flame retardant, flame retardant aid, surfactant, antifoaming agent, emulsifier, leveling agent, repellent inhibitor, ion trapping agent, thixo-imparting agent, adhesive Sex-imparting agent, storage stability improving agent, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity-imparting agent, antistatic agent, radiation blocker, nucleating agent, A phosphorus-based peroxide decomposing agent, a lubricant, a metal inactivating agent, a heat conductivity imparting agent, a physical property adjusting agent and the like may be contained within a range that does not impair the object and effect of the present invention.

The photosensitive composition may contain a filler and a colorant. Fillers include silica-based fillers (quartz, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica and ultrafine powder atypical silica, etc.), silicon nitride, silver powder, alumina, aluminum hydroxide, and oxidation. Examples thereof include titanium, glass fiber, carbon fiber, mica, carbon black, graphite, silica clay, white clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate and an inorganic balloon. Examples of the colorant include organic pigments, inorganic pigments, dyes and the like.

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

[Film formation and pattern hardening film formation]
The above positive photosensitive resin composition is coated on various substrates to form a coating film, exposed through a mask having a predetermined shape, and the exposed portion is dissolved and removed by alkaline development to form a pattern film. Can be formed. By performing post-baking after development, a pattern cured film can be obtained.

<Formation of coating film>
The method of applying the photosensitive composition onto the substrate is not particularly limited as long as it can be applied uniformly, 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>
Prior to exposure, heating (pre-baking) may be performed to dry the solvent. The heating temperature can be set as appropriate, but is preferably 50 to 200 ° C, more preferably 60 to 150 ° C. Further, vacuum devolatile may be performed before exposure. Vacuum volatilization may be performed before or at the same time as heating. A photosensitive composition containing a thermosetting component (for example, the above-mentioned components (C) and (D)) may have a reduced developability as the curing progresses by heating. Therefore, the heating temperature in the prebake is preferably 120 ° C. or lower.

<Exposure>
The light source for exposure may be selected according to the sensitivity wavelengths of the photoacid generator and the sensitizer contained in the photosensitive composition. Usually, a light source having a wavelength in the range of 200 to 450 nm (for example, 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, a light emitting diode, etc.) is used.

Exposure is not particularly limited but is preferably 1~5000mJ / cm ^2, more preferably 5~1000mJ / cm ^2, more preferably 10 to 500 mJ / cm ^2. If the exposure amount is excessively small, curing may be insufficient and the pattern contrast may decrease, and if the exposure amount is excessively large, the manufacturing cost may increase due to an increase in tact time.

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

<Development>
A patterned film is obtained by contacting the exposed coating film with an alkaline developer by a dipping method, a spraying method, or the like to dissolve and remove the coating film in the exposed portion. In the exposed portion, the alkali solubility of the component (A) is increased by the action of the acid generated by irradiating the photoacid generator with the active energy ray, so that the coating film is dissolved by the alkaline development.

As the alkaline developer, generally used ones can be used without particular limitation. Specific examples of the alkaline developing solution include organic alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution. An inorganic alkaline aqueous solution and the like can be mentioned. The alkali concentration of the developer is preferably 0.01 to 25% by weight, more preferably 0.1 to 10% by weight, still 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 or the like.

<Post-bake>
After the exposed portion is melted and removed by development, post-baking may be performed to cure the composition of the film of 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 results in a SiH group of the component (A). Curing proceeds by a hydrosilylation reaction with the ethylenically unsaturated group of the component (D). The photosensitive resin composition of the present invention contains the component (D). By forming a crosslinked structure with the component (A) by fully or partially cross-linking with the ethylenically unsaturated group of the component (D), the heat resistance and chemical resistance due to post-baking can be improved. .. Post-baking conditions can be set as appropriate. The post-bake temperature is preferably 100-400 ° C, more preferably 120-350 ° C.

[Use]
The photosensitive composition of the present invention can be used as an alkali-developable transparent resist, and is particularly suitable as a material for FPD. More specifically, a passivation film for a TFT, a gate insulating film for a TFT, an interlayer insulating film for a TFT, a transparent flattening film for a TFT, a photospacer material for a liquid crystal cell, a transparent sealing material for an OLED element, and the like can be mentioned. The photosensitive composition can also be used as a material for a colored film such as a color filter or a black matrix.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the following Examples.

[Synthesis of polysiloxane compounds]
100 parts by weight of diallyl bisphenol S and 400 parts by weight of tetrahydrofuran (THF) were placed in the reaction vessel, and the mixture was stirred at room temperature. A uniform solution was obtained. A reaction vessel hexamethyldisilazane: 50 parts by weight was added, reacted for 2 hours at room temperature, by ^{1 H-NMR,} after confirming the disappearance of the peak of the presence and the hydroxyl group-derived peak derived from trimethylsilyl group, THF and the reaction The residue was distilled off under reduced pressure to obtain diallyl bisphenol S (Compound 1) having a hydroxyl group protected by a trimethylsilyl group.

Put 1,3,5,7-tetramethylcyclotetrasiloxane: 60 parts by weight and toluene: 400 parts by weight in a reaction vessel, replace the gas phase part with nitrogen, heat the internal temperature to 100 ° C., and stir. Below, 100 parts by weight of the above compound 1, 15 parts by weight of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, and a xylene solution of a platinum vinylsiloxane complex (platinum). 0.14 parts by weight and 100 parts by weight of toluene were added dropwise. After the dropwise addition, after ^{confirming the disappearance of the peak derived from the allyl group by 1} H-NMR, toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid (reactant A). ¹ By 1 H-NMR, it was confirmed that the reaction product A was a polysiloxane compound having a bisphenol S structure protected by a trimethylsilyl group and having a SiH group of 3.0 mmol / g in terms of dibromoethane equivalent.

[Preparation of positive photosensitive resin composition]
100.00 parts by weight of the above reaction product A, 2 parts by weight of an imide sulfonate compound (“SP-606” manufactured by ADEKA) as a photoacid generator, and (4-tert-butylphenyl) sulfonium nonafluorobutane-1-sulfonate. (1 part by weight of "TTBPS-PFBS" manufactured by Toyo Synthetic Chemical Industry Co., Ltd.), 4 parts by weight of 9,10-dibutoxyanthracene as a sensitizer, and [Pt-1,3-divinyl-1,1,3, as a catalyst. 0.05 parts by weight of a 3 wt% isopropanol solution (manufactured by NEchemcat) of 3-tetramethyldisiloxane complex, and 5 parts by weight of "bis (2-ethylhexyl) adipate" (manufactured by Daihachi Chemicals) as a plasticizing agent. , 2 parts by weight of 2-methyl-3-butin-2-ol as a retarder, 0.5 parts by weight of a silicone-based surface conditioner ("MQV6 resin" manufactured by SiVance), and 1,3-bis as an acid diffusion inhibitor. 0.1 part by weight of (4,5-dihydro-2-oxazolyl) benzene (“1,3-PBO” manufactured by Mikuni Pharmaceutical Co., Ltd.), 2-methyl-4'-(methylthio) -2-morpholinopropiophenone ( 0.15 parts by weight of IGM "OMNIRAD907"), 1 part by weight of "Adecastab AO-80" (made by ADEKA) as an antioxidant, and 143.91 parts by weight of propylene glycol-1-monomethyl ether-2-acetate as a solvent. The parts were mixed to prepare a positive photosensitive resin composition. This composition is referred to as "standard composition" (Comparative Example 1).

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

The alkali solubility of the component (C) is considered to differ depending on the molecular weight of the copolymer and the content of the monomer exhibiting alkali solubility. SMA1000 and SMA2000 have a relatively low molecular weight of less than 10,000, which is considered to have high alkali-dissolving ability as a copolymer of styrene and maleic acid anhydride, and have an alkali-soluble maleic acid anhydride monomer content of 25% or more. , SMA3000, EF40, EF60, EF80 (manufactured by Cray Valley) having a molecular weight of 10,000 or more and a maleic acid anhydride monomer content of 20% or less, which are considered to be difficult to develop tackiness due to bleeding of additive components, alkaline dissolution. As a copolymer of (meth) acrylic acid having a (meth) acrylic acid structure considered to have high ability and (meth) acrylic acid ester, follet ZAH-110, follet ZAH-310, Actflow CB3098 (manufactured by Soken Kagaku Co., Ltd.) )It was used.

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

[Formation of pattern cured film and evaluation of hole width]
The positive photosensitive resin compositions of Examples and Comparative Examples were applied by spin coating on a 50 mm × 50 mm non-alkali glass substrate, and heated (prebaked) at 110 ° C. for 2 minutes using a hot plate to form a film. A coating film having a thickness of 2.5 μm was formed. Using a mask aligner (“MA-1300” manufactured by Dainippon Kaken), exposure was performed through a photomask (hole 10 μm) at each integrated irradiation dose. Two minutes after the exposure, the developer was immersed in an alkaline developer at 23 ° C. (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tama Chemical Industries, Ltd.) for 60 seconds for development. Further, post-baking was performed at 230 ° C. for 30 minutes in an oven to form a pattern cured film.

[Evaluation of sensitivity]
For the compositions of each Example and Comparative Example, a film was formed by changing the exposure amount under the above conditions, and in a hole pattern of 10 μm, the height was 1 from the bottom (the portion where the coating film was melted and the glass substrate was exposed). The width of the position of .25 μm was observed with a laser microscope (“OLS4000” manufactured by Olympus), and the exposure amount with a film thickness of 10 ± 0.2 μm was taken as the optimum sensitivity.

[Formation of cured film for tackiness test and evaluation of tackiness test]
The positive photosensitive resin compositions of Examples and Comparative Examples were applied by spin coating on a 50 mm × 50 mm non-alkali glass substrate, and heated (prebaked) at 110 ° C. for 2 minutes using a hot plate to form a film. A coating film having a thickness of 2.5 μm was formed. Except for the exposure step, the development process was carried out by immersing in an alkaline developer at 23 ° C. (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tama Chemical Industry Co., Ltd.) for 60 seconds. Further, it was baked in an oven at 120 ° C. for 30 minutes, and the surface of the cured film was touched with a finger to confirm the tackiness. Those without tack were marked with ◯, and those with tack were marked with x.

[Formation of cured film for reworkability test and evaluation of reworkability test]
The positive photosensitive resin compositions of Examples and Comparative Examples were applied by spin coating on a 50 mm × 50 mm non-alkali glass substrate, and heated (prebaked) at 110 ° C. for 2 minutes using a hot plate to form a film. A coating film having a thickness of 2.5 μm was formed. An exposure was performed through a photomask (hole 10 μm) using a mask aligner (“MA-1300” manufactured by Dainippon Kaken Co., Ltd.) with the integrated irradiation amount of the optimum sensitivity. Two minutes after the exposure, the developer was immersed in an alkaline developer at 23 ° C. (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tama Chemical Industries, Ltd.) for 60 seconds for development. This patterning film is stored in an environment of 23 ° C. and 50% humidity, and the patterning film after a predetermined time is exposed to the entire surface with the integrated irradiation amount of the optimum sensitivity. Two minutes after the exposure, alkaline development at 23 ° C. is performed. It was immersed in a solution (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tama Chemical Industry Co., Ltd.) for 120 seconds to perform a rework treatment. The substrate after rework was observed with an optical microscope, and those without resin residue and patterning marks were marked with ◯, and those with resin residue and patterning marks were marked with x. The compositions of Examples and Comparative Examples and the above evaluation results are shown in Table 1.

It was found that in Comparative Example 1 containing no component (C), the sensitivity was low and the tackiness was good, but rework was not possible. Further, in Comparative Example 2, the sensitivity was slightly improved, the reworkability immediately after development was good, but the tackiness was deteriorated, and the reworkability was deteriorated 24 hours after storage. On the other hand, in Examples 1 to 27 to which the component (C) was added, high sensitivity was obtained according to the number of copies of the component (C) added, the molecular weight of Examples 1 to 9 was relatively low, and the monomer content exhibiting alkali solubility. When SMA1000, SMA2000, and SMA3000, which are copolymers of styrene and maleic anhydride having a high molecular weight, are added, the reworkability is good immediately after, 24 hours, and 40 hours later, and the tackiness is also good. It was confirmed. In Examples 10 to 18, when styrene and maleic anhydride copolymers EF40, EF60, and EF80 having a relatively high molecular weight and a low monomer content showing alkali solubility were added, the reworkability immediately after all was good. In addition, in Examples 12 and 15 in which the number of added portions was large, the reworkability after 24 hours and 40 hours was also good. In Examples 19 to 27, when the copolymers of (meth) acrylic acid and (meth) acrylic acid ester, Foret ZAH-110, Foret ZAH-310, and Actflow CB3098 were added, the sensitivity was the highest and the reworkability was the highest. Was also good. Further, even in Examples 19 and 22 in which a small amount of follet ZAH-110 and follet 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 exhibited. rice field.

From the above results, it was found that a patterning film having both tackiness and reworkability can be obtained by adding the component (C), and a highly sensitive cured film can be obtained depending on the amount of the component (C) added.

Claims (7)

Ingredient (A): A compound whose alkali solubility is increased by the action of an acid;
(B) Ingredient: Photoacid generator;
Component (C): A copolymer composed of at least two or more monomers selected from the group of (meth) acrylic acid, (meth) acrylic acid ester, styrene, styrene derivative, and maleic anhydride. Contains a copolymer in which at least one of (meth) acrylic acid or maleic anhydride is an essential component;
A positive photosensitive resin composition in which the content of the component (C) is 1 to 10 parts by weight with respect to 100 parts by weight of the component (A). The positive photosensitive resin composition according to claim 1, wherein the component (A) contains a structure in which a phenolic hydroxyl group is protected by a protecting group. The positive photosensitive resin composition according to claim 1 or 2, further comprising a compound containing two or more functional groups capable of reacting with the component (A) in one molecule as the component (D). The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the component (A) contains a polysiloxane compound. The positive photosensitive resin composition according to claim 4, wherein the siloxane compound has a cyclic siloxane structure. A pattern cured film made of a cured product of the positive photosensitive resin composition according to any one of claims 1 to 5. A method for producing a pattern cured film, wherein the positive photosensitive resin composition according to any one of claims 1 to 5 is applied onto a substrate, and patterning is carried out by exposure and alkaline development.