JP2020091323A - Positive photosensitive composition, patterned cured film and production method of the same - Google Patents

Abstract

To provide a positive photosensitive composition having high stability of line width and a wide process margin even when a time period from exposure to development is long.SOLUTION: The positive photosensitive composition comprises: a compound the an alkali solubility of which increases by an action of an acid as (A) component; a photoacid generator as (B) component; a basic compound having a morpholine ring as (C1) component; and at least one compound selected from a group consisting of a basic compound having an oxazoline ring and a compound having two or more piperidine rings in one molecule as (C2) component. The content of (C1) component with respect to 100 pts.wt of (B) component is 1 to 25 pts.wt., and the content of (C2) component with respect to 100 pts.wt. of (B) component is 1 to 25 pts.wt.SELECTED DRAWING: None

Description

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

Positive type photosensitive compositions are used for manufacturing display devices, semiconductor elements, integrated circuits and the like. The positive photosensitive composition contains a compound (resin material) as a base and a photo-acid generator. The compound serving as the base of the positive photosensitive composition is a compound whose alkali solubility is increased by the action of an acid, and the alkali solubility is increased by the acid generated from the photo-acid generator upon exposure. When development is performed with an alkali after the exposure, the exposed portion is selectively dissolved in the alkali, so that a pattern film is obtained.

The positive photosensitive material used as a permanent resist is required to have higher durability because the cured film after patterning remains as a functional film on the device, and a positive photosensitive composition based on polyimide or silicone polymer is proposed. Has been done. Patent Document 1 discloses a positive photosensitive composition based on a polymer having a siloxane structure.

In the positive-type photosensitive material, when the standing time from exposure to alkali development becomes long, the acid generated in the exposed area diffuses to the non-exposed area, and the non-exposed area becomes soluble in alkali, resulting in contrast. And the line width of the pattern film is reduced.

It has been proposed to add a basic compound as an acid quencher in order to increase the degree of freedom (process margin) from exposure to development in the production of a pattern film using a positive photosensitive composition. There is. For example, in Patent Document 2, a polysiloxane-based positive-type photosensitive composition to which a morpholine derivative or a piperidine derivative is added as an acid quencher has a line width stability (pattern shape) when development is started 15 minutes after exposure. Stability) is described.

WOWO2014/007231 JP, 2017-198841, A

In the formation of a pattern film using a positive photosensitive composition, when exposure and development are continuously carried out while transporting a substrate, the time from exposure to development is several minutes to several tens of minutes. On the other hand, if exposure and development are not carried out continuously, the exposure time from exposure to development may be several hours to several tens of hours, and it is required that the change in line width is small even when left for a long time. Has been done. The composition disclosed in Patent Document 2 has high line width stability when the standing time from exposure to development is about 15 minutes, but the line width stability when the standing time is long can be said to be sufficient. Absent.

In view of the above, it is an object of the present invention to provide a positive photosensitive composition having high line width stability and a wide process margin even when the time from exposure to development is long.

The positive photosensitive composition contains, as the component (A), a compound whose alkali solubility is increased by the action of an acid, and as the component (B), a photoacid generator. The positive photosensitive composition further comprises a basic compound having a morpholine ring as the component (C1), a basic compound having an oxazoline ring as the component (C2), and a compound having two or more piperidine rings in one molecule. One or more selected from the group consisting of:

The positive photosensitive composition may further contain a crosslinking agent as the component (E). The cross-linking agent is a compound containing two or more functional groups capable of reacting with the component (A) in one molecule.

The positive photosensitive composition preferably contains 1 to 25 parts by weight of the component (C1) and preferably 1 to 25 parts by weight of the component (C2) per 100 parts by weight of the component (B).

The component (A) is, for example, a polysiloxane compound. The polysiloxane compound may have a SiH group. When the component (A) is a polysiloxane compound containing a SiH group, the component (E) is preferably a compound having reactivity with the SiH group of the component (A).

A pattern film is obtained by applying the positive photosensitive composition described above on a substrate and performing patterning by exposure and alkali development. The effect of the patterned film may be obtained by heating after the development.

Since the photosensitive composition contains the (C1) component and the (C2) component, the time from exposure to development is long, and even when the acid diffuses in the non-exposed area, the solubility of the non-exposed area in the alkali is improved. The increase can be suppressed. Even when the time from exposure to development is long, the line width stability is high and the process margin is wide, so that the productivity of the pattern film and the yield can be expected to improve.

[Photosensitive composition]
The photosensitive composition of the present invention is a positive photosensitive composition containing (A) a compound whose alkali solubility is increased by the action of an acid, (B) a photoacid generator, and (C) a basic compound. is there. Hereinafter, a compound whose alkali solubility is increased by the action of an acid may be referred to as “(A) component”, a photoacid generator as “(B) component”, and a basic compound as “(C) component”. .. The photosensitive composition may further contain a photosensitizer as the component (D), and a crosslinking agent (a compound having a functional group capable of introducing a crosslinked structure into the component (A)) as the component (E). You can leave. Unless otherwise specified, the compounds and functional groups exemplified in the present specification may be used alone or in combination of two or more kinds (coexistence).

<(A) component>
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 (deprotected) by the reaction with an acid generated from the photo-acid generator to increase 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 carboxylic acids and acidic groups such as phenolic hydroxyl groups.

Examples of the protective group for the phenolic hydroxyl group include a tert-butoxycarbonyl group and a trialkylsilyl group. For example, a phenolic hydroxyl group can be protected by a tert-butoxycarbonyl group by a reaction using a Boc-forming reagent. The alkyl group in the trialkylsilyl group as the protective 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 with 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 carboxylic acid include tertiary alkyl ester and acetal. Examples of the tertiary alkyl group in the tertiary alkyl ester of carboxylic acid include tert-butyl group, adamantyl group, tricyclodecyl group, norbornyl group and the like.

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

When a permanent resist is produced from a positive photosensitive 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 (E) described below, and a crosslinked structure is introduced to obtain a patterned cured film.

The component (A) preferably contains a structure in which the alkali-solubility-imparting group is protected by a protective group, and a polymer skeleton structure other than the above-mentioned polymerizable functional group. As the polymer skeleton structure, polyacryl, polyphenol, polyamide, polyanhydride, 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 Polysiloxane Structure>
The component (A) preferably has a polysiloxane structure, particularly preferably a cyclic polysiloxane structure, since a cured film having high heat resistance and a low dielectric constant can be formed. The component (A) containing a polysiloxane structure is a compound in which "a structure having a siloxane unit" as a main skeleton and "a structure in which an alkali-solubilizing group is protected by a protecting group" is introduced, and specific examples thereof Examples of the polysiloxane compound include those disclosed in WO2014/007231.

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 constituent element. ). The 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 the compound containing only a chain polysiloxane structure.

The polysiloxane compound having the “structure in which the alkali-solubility-imparting group is protected by a protective group” (hereinafter, may be referred to as “structure X”) is obtained, for example, by 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 SiH groups. Since at least one of these compounds (starting material) has the structure X in addition to the above functional group, the polysiloxane compound having the structure X is obtained.

For example, when the compound having a carbon-carbon double bond has the structure X, a polysiloxane compound having the structure X can be obtained by a hydrosilylation reaction using the following compounds (α) and (β) as starting materials. (Α): a compound having a structure X and a carbon-carbon double bond reactive with a SiH group (hydrosilyl group) 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)
The compound (α) is a compound containing a structure X and a carbon-carbon double bond having reactivity with a SiH group. Examples of the group containing a carbon-carbon double bond having reactivity with a SiH group (hereinafter, may be simply referred to as “ethylenically unsaturated group”) include vinyl group, allyl group, methallyl group, acryl group and methacryl group. 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- (Allyloxy)phenyl group, 2-(allyloxy)ethyl group, 2,2-bis(allyloxymethyl)butyl group, 3-allyloxy-2,2-bis(allyloxymethyl)propyl group, vinyl ether group and the like. .

The compound (α) preferably has a plurality of ethylenically unsaturated groups in one molecule. In the case of having a plurality of ethylenically unsaturated groups in one molecule, a 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 improved. And the heat resistance of the cured film tends to be improved.

Examples of the structure X include a structure in which a protective group is bonded to an acidic group such as carboxylic acid or phenolic hydroxyl group as described above. When the component (A) is a polysiloxane compound, the structure X preferably has a protective group bonded to the phenolic hydroxyl group. Further, it is preferable that the structure X contains a bisphenol structure from the viewpoint of the chemical resistance of the cured film, the insulating property, and the like.

As the bisphenol structure, 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, bisphenol C G structure, bisphenol TMC structure, bisphenol Z structure, etc. are mentioned. Among these, bisphenol A structure, bisphenol B structure, bisphenol C structure, bisphenol E structure, bisphenol F structure, bisphenol AF structure, and bisphenol are excellent in solubility in an alkali developing solution and a pattern with excellent contrast is easily obtained. The S structure, the bisphenol AP structure or the bisphenol PH structure is preferable, and among them, the bisphenol S structure or the bisphenol F structure is preferable from the viewpoint of easy deprotection with an acid.

The protective group for the phenolic hydroxyl group is preferably an organic group having 1 to 50 carbon atoms or an organic silicon group, and among them, a trialkylsilyl group is preferable. Examples of the compound (α) in which the phenolic hydroxyl group of bisphenol is protected by a trialkylsilyl group and which has an ethylenically unsaturated group include compounds represented by the following general formula (I).

In the general formula (I), R ¹ is a divalent organic group as long as it has 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 . A plurality of R ^{2 s} are each independently an alkyl group having 1 to 6 carbon atoms, and preferably all R ^{2 s} 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)
The compound (β) is a polysiloxane compound having at least two SiH groups in one molecule, for example, the compound described in WO96/15194 and having at least two SiH groups in one molecule, etc. 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 end, and a cyclic polysiloxane containing a hydrosilyl group. 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 a polyhedral skeleton with high heat resistance and mechanical strength, it is preferable to use a cyclic polysiloxane compound having at least two SiH groups in one molecule as the compound (β). The 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 with a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit with 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 with dimethylhydrogensilyl groups.

Examples of the polysiloxane having a hydrosilyl group at the molecular end include a polysiloxane whose end is blocked by a dimethylhydrogensilyl group, a dimethylhydrogensiloxane unit (H(CH ₃ ) ₂ SiO _1/2 unit), and a SiO ₂ unit. , A polysiloxane having at least one siloxane unit selected from the group consisting of SiO _3/2 units and SiO units.

The cyclic polysiloxane is represented by, for example, 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.

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 an alkyl group, a hydroxyalkyl group, an alkoxyalkylalkyl group, an oxyalkyl group and an aryl group. 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 the 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 a chain alkyl group 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. Among them, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (in the general formula (II), m= 4, a compound in which n=0 and R ⁴ is a methyl group) is preferable.

The 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 forming the polyhedral skeleton, 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 each independently a hydrogen atom, a chain alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), a cycloalkyl group (cyclohexyl group, etc.), an aryl group (phenyl). Groups and tolyl groups, etc.), groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups have been replaced with halogen atoms, cyano groups, etc. (chloromethyl group, trifluoropropyl group, cyanoethyl group, etc.), alkenyl It is a monovalent group selected from groups (vinyl group, allyl group, butenyl group, hexenyl group, etc.), (meth)acryloyl group, epoxy group, and organic group containing a mercapto group or amino group. The number of carbon atoms in the hydrocarbon group is preferably 1-20, more preferably 1-10. The cyclic polysiloxane having a polyhedral skeleton has two or more hydrosilyl groups which are reactive groups in the hydrosilylation reaction. Therefore, at least two of R ^{10 to} R ¹⁷ are hydrogen atoms.

The cyclic polysiloxane may be silylated silicic acid having a polyhedral skeleton. Specific examples of the silylated silicic acid having a polyhedral skeleton include compounds represented by the following general formula (IV) (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 general formula (III) described above, and at least two of R ^{18 to} R ⁴¹ are hydrogen atoms.

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

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

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 the compound (γ) is used, a 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 and the heat resistance of the cured film are improved. Tend to do.

The compound (γ) may be either an organic polymer compound or an organic monomer compound. Examples of the organic polymer compound 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 compound may be used. Examples of the organic monomer compounds include phenolic compounds, bisphenolic compounds, aromatic hydrocarbon compounds such as benzene and naphthalene; aliphatic hydrocarbon compounds such as linear and alicyclic compounds, and heterocyclic compounds. ..

Specific examples of the compound (γ) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1 , 1,2,2-Tetraallyloxyethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monomethyl isocyanurate, 1,2,4-trivinylcyclohexane, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, diallyl ether of bisphenol S, divinyl Benzene, 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-diallyl Phenol allyl ethers and oligomers thereof, 1,2-polybutadiene (one having a ratio of 1,2 to 10 to 100%, preferably one having a ratio of 1,2 to 50 to 100%), allyl ether of novolac phenol, and allylated polyphenylene oxide. Other examples include those in which all of the glycidyl groups of conventionally known epoxy resins are replaced with allyl groups. Further, a compound in which the allyl group in the above-exemplified compound is replaced with a (meth)acryloyl group (for example, polyfunctional (meth)acrylate) is also suitably 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 obtained by replacing some or all of the hydrogen atoms bonded to Si of the above compound (β) 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.

A specific example of the cyclic polysiloxane compound having two or more ethylenically unsaturated groups is a cyclic polysiloxane having a Si atom to which a vinyl group is bonded as an ethylenically unsaturated group. Examples of the cyclic polysiloxane compound 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 in one molecule (hereinafter referred to as “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 terminal of the polymer.

For example, by using a siloxane compound having one SiH group as the compound (δ), a siloxane structure site can be introduced at the terminal of the polymer. Specific examples of the siloxane compound having one SiH group include a cyclic polysiloxane compound in which m=1 in the general formula (II), and one of R ^{10 to} R ¹⁷ in the general formula (III) is hydrogen. Examples thereof include a polyhedral polysiloxane compound which is an 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 the compound (δ), a desired functional group can be introduced at the terminal of the polymer. In addition to the above, compounds that participate in the hydrosilylation reaction, such as a chain polysiloxane having two or more SiH groups, may be included in the starting materials.

(Hydrosilylation reaction)
The order and method of the hydrosilylation reaction are not particularly limited. From the viewpoint of simplifying the synthesis process, a method is preferred in which all starting materials are charged in one pot to carry out the hydrosilylation reaction, and finally unreacted compounds are removed. On the other hand, from the viewpoint of suppressing the production of low molecular weight compounds, compounds containing a plurality of ethylenically unsaturated groups (eg compound (α) and compound (γ)) and compounds containing a plurality of SiH groups (eg compound (β) ) And a hydrosilylation reaction with one of them in excess, and after removing unreacted compounds, a compound having only one functional group involved in the hydrosilylation reaction in one molecule (for example, compound (δ)) is added. A method of performing a hydrosilylation reaction is preferable.

The proportion 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 that /A≦10 is satisfied. 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. Can be improved.

For the hydrosilylation reaction, a hydrosilylation catalyst such as chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex may be used. You may use together a hydrosilylation catalyst and a cocatalyst. The addition amount of the hydrosilylation catalyst is not particularly limited, but is preferably 10 ⁻⁸ to 10 ⁻¹ times, more preferably 10 ⁻⁶ to the total amount (mole number) of ethylenically unsaturated groups contained in the starting material. It is 10 ^-2 times.

The reaction temperature for hydrosilylation may be set appropriately, and is 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 used. Although the hydrosilylation reaction with (β) has been described as an example, the synthesis method of 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 by using a compound having a SiH group and a structure X in one molecule as a starting material. In this case, the polysiloxane compound having the structure X is obtained by the hydrosilylation reaction of the compound containing the SiH group and the structure X with the polysiloxane compound having the ethylenically unsaturated group. The polysiloxane compound having an ethylenically unsaturated group may contain a plurality of ethylenically unsaturated groups.

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

<(B) Photo-acid generator>
The photosensitive composition contains a photo-acid generator as the component (B). When the photoacid generator is exposed to an active energy ray by exposure, an acid is generated. 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 photo-acid generator decomposes the component (A) to develop 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 can generate a Lewis acid upon 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 imidosulfonates, 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. Imidosulfonates and oxime sulfonates are preferred as the photoacid generator 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 100 parts by weight of the component (A). 5 parts by weight is more preferred. When the amount of the photo-acid generator is within the above range, it is possible to sufficiently enhance the alkali solubility of the component (A) in the exposed portion to improve the patterning property, and it is possible to suppress the decrease in contrast due to excess acid.

<(C) Basic compound>
The photosensitive composition contains a basic compound as the component (C). The basic compound has an action of suppressing an increase in alkali solubility of the non-exposed portion due to diffusion of the Lewis acid generated from the photo-acid generator upon exposure to the non-exposed portion. The photosensitive composition of the present invention contains a component (C1) and a component (C2) as a basic compound. By using multiple basic compounds together, even if the exposure time from development to development is long, the alkali solubility in the unexposed areas is suppressed and the pattern film space width is expanded (line width reduction). It can be prevented.

The component (C1) is a basic compound having a morpholine ring. The component (C2) is at least one selected from the group consisting of (C2a) a basic compound having an oxazoline ring and (C2b) a compound having two or more piperidine rings in one molecule.

((C1) Morpholine-based basic compound)
The component (C1) is a basic compound having a morpholine ring. As the basic compound having a morpholine ring, morpholine, 4-methylmorpholine, 4-morpholineacetonitrile, 4-acetylmorpholine, 4-acetoacetylmorpholine, 4-acryloylmorpholine, 4-allylmorpholine, 4-(2-acetoxyethyl) ) Morpholine, 4-(2-hydroxyethyl)morpholine, 4-(2-pivaloyloxyxyethyl)morpholine, 4-[2-(2-methoxyethoxycarbonyloxy)ethyl]morpholine, 4-[2-(ethoxy) Carbonyloxy)propyl]morpholine, 4-[2-(methoxycarbonyloxy)ethyl]morpholine, 4-[2-(methoxymethoxy)ethyl]morpholine, 1-(4-morpholinyl)ethanol, 3-(N-morpholino) -1,2-Propanediol, 2-methoxyethyl morpholinoacetate, methyl morpholinoacetate, 2-morpholinoethyl acetate, 2-acetoxyethyl 3-morpholinopropionate, 2-methoxyethyl 3-morpholinopropionate, 3-morpholinopropionate Methyl, ethyl 3-morpholinopropionate, tetrahydrofurfuryl 3-morpholinopropionate, 4-morpholinepropiononitrile, 4-morpholinepropionate (2-cyanoethyl), cyanomethyl 4-morpholinepropionate, β-morpholino-δ-valero Lactone, 2-morpholinoethyl acetoxyacetate, N-cyclohexyl-N′-[2-(4-morpholinyl)ethyl]thiourea and the like can be mentioned. The morpholine-based basic compound may be a compound having two or more morpholine rings in one molecule such as bis(2-morpholinoethyl)ether. The morpholine-based basic compounds include 2-methyl-4′-(methylthio)-2-morpholinopropiophenone, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone, 2 Ketones (phenones) such as -(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone may be used.

Among the compounds exemplified above, the basic compound having a morpholine ring includes bis(2-morpholinoethyl)ether 2-methyl-4′-(methylthio)-2-morpholinopropiophenone and 2-benzyl-2-(dimethyl). Selected from the group consisting of amino)-1-(4-morpholinophenyl)-1-butanone, and 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone. 1 or more are preferable.

((C2a) Oxazoline-based basic compound)
The component (C2a) is a basic compound having an oxazoline ring. Examples of the basic compound having an oxazoline ring include oxazoline; a compound in which a plurality of oxazoline rings such as 2,2′-bis(2-oxazoline) are directly bonded; methylenebis(2-oxazoline), 2,2′-isopropylidenebis A compound in which a plurality of oxazoline rings are bonded via an alkylene group such as (2-oxazoline); 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 1,4-bis(4,5-dihydro) Examples include compounds in which a plurality of oxazoline rings are bonded via an aromatic group such as (2-oxazolyl)benzene. The oxazoline compound may have a substituent on the oxazoline ring. Examples of the oxazoline compound having a substituent include 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-cyclopentyl-2-oxazoline, 2 -Isopropenyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,4,4-trimethyl-2-oxazoline, 2-phenyl-4,4-dimethyl-2-oxazoline and the like can be mentioned. The oxazoline compound having a plurality of oxazoline rings may have a substituent on each oxazoline ring.

Among the compounds exemplified above, the basic compounds having an oxazoline ring include 1,3-bis(4,5-dihydro-2-oxazolyl)benzene and 1,4-bis(4,5-dihydro-2-oxazolyl). ) One or more selected from the group consisting of benzene is preferred.

((C2b) Piperidine-based basic compound)
The component (C2b) is a compound having two or more piperidine rings in one molecule, and preferably contains two or more functional groups represented by the following general formula (V) in one molecule.

In formula X, R _{51 to} R ₅₅ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen-substituted alkyl group, a halogen-substituted alkoxy group, an alkylthio group, an acyloxy group, an alkyl-substituted amino group, an aryl group, a diarylamino. A group, an alkenyl group, an alkynyl group, an alkyloxycarbonyl group or an aryloxycarbonyl group. R ₅₁ is preferably a hydrogen atom or a methyl group, and R _{52 to} R ₅₅ are preferably methyl groups. The compound having a structure (2,2,6,6-tetramethylpiperidine skeleton) in which R _{52 to} R ₅₅ in General Formula X are methyl groups is a compound generally used as a hindered amine light stabilizer (HALS). Is.

The compound having two or more piperidine rings in one molecule preferably has a molecular weight of 400 or more. The compound having two or more piperidine rings in one molecule preferably has a structure in which 2,2,6,6-tetramethylpiperidine skeleton is bound via an ester bond. Specific examples of such compounds include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (“TINUVIN770” manufactured by BASF as a commercial product, “ADEKA STAB LA-77Y” manufactured by ADEKA, etc.), bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate ("TINUVIN765" manufactured by BASF as a commercial product, and ADEKA "Adeka Stab LA-72"), bis(N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl- 4-piperidyl) sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)2- (3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acroyl-2,2,6,6-tetramethyl-4-piperidyl)2,2-bis( 3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)decanedioate, bis(1,2,2) 2,6,6-Pentamethyl-4-piperidyl)decanedioate, bis(1-undecanoxy-2,2,6,6-tetramethyl-4-piperidyl)carbonate ("ADEKA STAB LA-81" manufactured by ADEKA as a commercial product) Etc.), 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis( 2,2,6,6-Tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate (“ADEKA STAB LA-57” manufactured by ADEKA as a commercial product), tetrakis (1,2,2,2) 6,6-Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate (“ADEKA STAB LA-52” manufactured by ADEKA as a commercial product), tetrakis (2,2,6,6-tetramethyl-) 4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, 2- [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphene Nyl]methyl]-2-butylpropanedioate bis[1,2,2,6,6-pentamethyl-4-piperidinyl] (such as BASF's "TINUVIN 144" as a commercial product).

The compound having two or more piperidine rings in one molecule may be a high molecular weight compound having a molecular weight of 1,000 or more. Specific examples of the high molecular weight piperidine-based compound include an ester of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol (such as BASF's "TINUVIN 622" as a commercial product), { 2,2,6,6-Tetramethyl-4-piperidyl/β,β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane ] Dimethyl}-1,2,3,4-butanetetracarboxylate (“ADEKA STAB LA-68” manufactured by ADEKA as a commercial product), {1,2,2,6,6-pentamethyl-4-piperidyl/β, β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]dimethyl}-1,2,3,4-butanetetracarboxylate ( "ADEKA STAB LA-63P" manufactured by ADEKA as a commercial product), a mixed ester of 1,2,3,4-butanetetrabonic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4 ,8,10-Tetraoxaspiro[5.5]undecane mixed ester, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9 -Bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane mixed ester, dimethylsuccinate and 1-(2-hydroxyethyl) A compound in which the piperidine ring is bonded through an ester bond, such as an ester with -4-hydroxy-2,2,6,6-tetramethylpiperidine; poly[(6-morpholino-1,3,5-triazine-2 ,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], poly[( 6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl((2,2,6,6-tetramethyl-4-piperidyl)imino)hexa Methylene ((2,2,6,6-tetramethyl-4-piperidyl)imino)], N,N',4,7-tetrakis[4,6-bis(N-butyl-N-(2,2,2 6,6-Tetramethyl-4 -Piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10diamine, N,N',4-tris[4,6-bis(N-butyl-N) -(2,2,6,6-Tetramethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N', 4,7-Tetrakis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl] -4,7-Diazadecane-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl )Amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine-N,N'-bis(2,2) ,6,6-Tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine polycondensate, dibutylamine and 1 , 3,5-triazine and N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)butylamine polycondensate, poly[{(1,1,3,3-tetramethyl Butyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetra Methyl-4-piperidyl)imino}],1,6-hexanediamine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) and morpholine-2,4,6-trichloro Polycondensation product with -1,3,5-triazine (Cytec UV-3529 manufactured by Cytec as a commercial product), poly[(6-morpholino-s-triazine-2,4-diyl)[(2,2,2 A compound in which a plurality of piperidine rings such as 6,6-tetramethyl-4-piperidyl)imino]-hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino]] are bonded via a triazine skeleton. A polycondensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 1,2-dibromoethane, with 2,2,6,6- Examples thereof include high molecular weight hindered amine compounds having a tetramethylpiperidine skeleton. The molecular weight of the compound having two or more piperidine rings in one molecule (in the case of a polymer, the number average molecular weight) is preferably 5000 or less.

Among the compounds exemplified above, compounds having two or more piperidine rings in one molecule are tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetra Carboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-undecaneoxy-2,2,6,6-tetramethyl-4-piperidyl)carbonate, 2-[[ 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioate bis[1,2,2,6,6-pentamethyl-4-piperidinyl], and {1 ,2,2,6,6-Pentamethyl-4-piperidyl/β,β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane ] One or more selected from the group consisting of dimethyl}-1,2,3,4-butanetetracarboxylate is preferred.

(Content of component (C) in the photosensitive composition)
The photosensitive composition contains 1 to 25 parts by weight of the component (C1) and 1 to 25 parts by weight of the component (C2) with respect to 100 parts by weight of the photoacid generator (B). When both the (C2a) basic compound having an oxazoline ring and the (C2b) compound having two or more piperidine rings in one molecule are contained as the (C2) component, the (C2a) component and the (C2b) The total amount of the components is preferably 1 to 25 parts by weight with respect to 100 parts by weight of the photo-acid generator.

By including each of the component (C1) and the component (C2) in an amount of 1 part by weight or more based on 100 parts by weight of the photo-acid generator, the alkali solubility of the non-exposed area is improved even when the exposure time to development is long. Is less likely to increase, and the line width and space width of the pattern film can be kept constant. That is, the (C1) component and the (C2) component have an action as a quencher that suppresses the reaction between the acid diffused in the unexposed portion and the (A) component.

Each of the component (C1) and the component (C2) has a function as an acid quencher by itself, but is not sufficiently long-term sustainability by itself. For example, the standing time from exposure to development is 12 hours or more. In this case, the space width of the pattern film tends to increase and the line width tends to decrease. When either the component (C1) or the component (C2) is used alone, it is difficult to sufficiently enhance the long-lasting effect even if the amount of addition is large.

By using (C1) and (C2) together, the line width and space width of the pattern film can be kept constant even when the standing time (storage time) from exposure to development is long, so that the process margin can be improved. Widely, the production efficiency and yield of the patterned film can be improved. In order to allow storage for a longer time after exposure and before development, the content of the component (C1) with respect to 100 parts by weight of the photoacid generator (B) is 1.5 parts by weight or more. More preferably, 2 parts by weight or more is further preferable, and 2.5 parts by weight or more is particularly preferable. The content of the component (C1) with respect to 100 parts by weight of the photoacid generator (B) may be 3 parts by weight or more, 3.3 parts by weight or more, or 3.5 parts by weight or more. From the same viewpoint, the content of the component (C2) per 100 parts by weight of the photoacid generator (B) is more preferably 1.5 parts by weight or more, further preferably 2 parts by weight or more, and 2.5 parts by weight or more. Particularly preferred. The content of the component (C2) with respect to 100 parts by weight of the photoacid generator (B) may be 3 parts by weight or more, 3.5 parts by weight or more, or 4 parts by weight or more.

The greater the contents of the component (C1) and the component (C2), the more the stability after exposure tends to increase. On the other hand, when the contents of the (C1) component and the (C2) component become excessively large, the acid generated from the photo-acid generator by exposure is excessively quenched even in the exposed portion, and the alkali solubility of the (A) component is increased. There is a case in which problems such as a decrease in contrast and an inability to form an appropriate pattern may occur without properly increasing. Further, if the content of the compound acting as an acid quencher is excessively large, the sensitivity may decrease and the exposure amount required for patterning may increase.

Therefore, the content of each of the component (C1) and the component (C2) relative to 100 parts by weight of the photo-acid generator is preferably 25 parts by weight or less. The content of the component (C1) with respect to 100 parts by weight of the photoacid generator (B) is more preferably 20 parts by weight or less, still more preferably 17 parts by weight or less. The content of the component (C1) with respect to 100 parts by weight of the photoacid generator (B) may be 15 parts by weight or less, 12 parts by weight or less, or 10 parts by weight or less. The content of the component (C2) with respect to 100 parts by weight of the photoacid generator (B) is more preferably 20 parts by weight or less, still more preferably 17 parts by weight or less. The content of the component (C2) with respect to 100 parts by weight of the photoacid generator (B) may be 15 parts by weight or less, 12 parts by weight or less, or 10 parts by weight or less.

The total content of the (C1) component and the (C2) component in the photosensitive composition is preferably 3 to 40 parts by weight, more preferably 5 to 35 parts by weight, relative to 100 parts by weight of the (B) photoacid generator. The amount is preferably 7 to 30 parts by weight, more preferably 9 to 25 parts by weight.

The content of the component (C1) in the photosensitive composition is preferably 0.03 to 0.9 part by weight, more preferably 0.05 to 0.7 part by weight, based on 100 parts by weight of the component (A). 0.08 to 0.5 parts by weight is more preferable, and 0.1 to 0.4 parts by weight is particularly preferable. The content of the component (C2) in the photosensitive composition is preferably 0.03 to 0.9 parts by weight, more preferably 0.05 to 0.7 parts by weight, based on 100 parts by weight of the component (A). 0.08 to 0.5 parts by weight is more preferable, and 0.1 to 0.4 parts by weight is particularly preferable. The total content of the component (C1) and the component (C2) in the photosensitive composition is preferably 0.1 to 1 part by weight, and 0.15 to 0.8 part by weight, relative to 100 parts by weight of the component (A). Parts is more preferable, and 0.2 to 0.7 parts by weight is even more preferable.

The content of the component (C1) with respect to the total content of the component (C1) and the component (C2) is preferably 5 to 95%, more preferably 10 to 90%, further preferably 20 to 80%, and further preferably 30 to 70. % Is particularly preferred.

<(D) Sensitizer>
The photosensitive composition may contain a sensitizer. The use of the sensitizer improves the exposure sensitivity during patterning. Examples of the sensitizer for the positive photosensitive composition include anthracene compounds and thioxanthone compounds. Among them, anthracene sensitizers are preferable because of their excellent photosensitizing effect. Specific examples of the anthracene compounds include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene (DBA), 9,10-dipropoxyanthracene, 9, 10-diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6 -Di-tert-butylanthracene and the like can be mentioned. Among them, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like are preferable from the viewpoint of compatibility with the photosensitive composition.

The content of the sensitizer in the photosensitive composition is not particularly limited and may be appropriately adjusted within the range where the sensitizing effect can be exhibited. From the viewpoint of the balance between the sensitizing effect and the characteristics of the cured film, the content of the sensitizer is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the component (A). , 0.5 to 35 parts by weight is more preferable, and 1 to 30 parts by weight is particularly preferable. In order to obtain the sensitizing effect, the molar ratio (D/B) of the (D) sensitizer to the (B) photoacid generator is preferably 0.01 to 300, more preferably 0.1 to 100. preferable.

<(E) Crosslinking agent>
The photosensitive composition may contain a cross-linking agent capable of introducing a cross-linking structure into the component (A). As the cross-linking agent, a compound containing two or more functional groups capable of reacting with the component (A) in one molecule is preferable.

For example, when the component (A) is a polysiloxane compound and contains a SiH group that has not been used in the hydrosilylation reaction, a compound having two or more ethylenically unsaturated groups in one molecule is used as a crosslinking agent. If included in the photosensitive composition, a 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 compounds as the compound (γ) exemplified for the synthesis of the component (A) 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 2 to 100 parts by weight of the component (A). 30 parts by weight is more preferable. When the photosensitive composition contains a crosslinking agent, it is preferable to introduce a crosslinked structure by reacting the component (A) with the crosslinking agent by heating (post-baking) after patterning by exposure and development. Since the pattern film is cured 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>
The photosensitive composition is obtained by dissolving or dispersing the above-mentioned component (A), component (B) and component (C), and optionally component (D) and component (E) in a solvent. .. The photosensitive composition may be prepared by mixing the respective components immediately before film formation, or may be stored in the state of one liquid prepared by mixing and preparing all the components in advance.

Any solvent may be used as long as it can dissolve the component (A), and specific examples thereof include hydrocarbon solvents such as benzene, toluene, hexane and heptane; tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and diethyl ether. Ether 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-based 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-forming stability, propylene glycol-1-monomethyl ether-2-acetate and diethylene glycol diethyl ether are preferable. The amount of solvent used may be set appropriately. The amount of the solvent used is preferably 0.1 to 10 mL with respect to 1 g of the solid content of the photosensitive composition.

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

From the viewpoint of simultaneously improving the alkali solubility and insulating properties of the cured film, heat resistance, solvent resistance, and the like, the alkali-soluble component is preferably a resin having the above structure Z1 and/or structure Z2, and above all, Polysiloxane resins having structure Z1 and/or structure Z2 of are preferred.

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 (diallyl isocyanurate, etc.) and/or a compound containing the above structure Z2 and an ethylenically unsaturated group. It is obtained by a hydrosilylation reaction of (monoallyl isocyanurate or the like) with 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, which is exemplified above as the compound (β), is preferably used.

In addition to the above, the photosensitive composition includes an adhesiveness improving agent, a coupling agent such as a silane coupling agent, a deterioration inhibitor, a hydrosilylation reaction inhibitor, a polymerization inhibitor, a polymerization catalyst (crosslinking accelerator), and a mold release agent. Agents, flame retardants, flame retardant aids, surfactants, defoamers, emulsifiers, leveling agents, repellants, ion trap agents, thixotropic agents, tackifiers, storage stability improvers, light stabilizers, Thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity enhancer, antistatic agent, radiation blocking agent, nucleating agent, phosphorus peroxide decomposer, lubricant, metal inert An 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 objects and effects of the present invention.

The photosensitive composition may contain a filler and a colorant. As the filler, silica-based filler (quartz, fume silica, precipitated silica, silicic acid anhydride, fused silica, crystalline silica and ultrafine amorphous silica, etc.), silicon nitride, silver powder, alumina, aluminum hydroxide, oxidation Titanium, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, inorganic balloons and the like can be mentioned. Examples of the colorant include organic pigments, inorganic pigments and dyes.

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

[Film formation and pattern hardening film formation]
A coating film is formed by coating the above-mentioned positive-type photosensitive composition on various base materials, exposing through a mask of a predetermined shape, and dissolving and removing the exposed area by alkali development to form a pattern film. it can. Post-baking is performed after development to obtain a patterned cured film.

<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, still more preferably 0.2 to 50 μm, from the viewpoint of reliability.

<Pre-baking>
Before exposure, heating (pre-baking) may be performed to dry the solvent. The heating temperature can be appropriately set, but is preferably 50 to 200°C, more preferably 60 to 150°C. Further, vacuum devolatilization may be performed before exposure. Vacuum devolatilization may be performed simultaneously with heating. A photosensitive composition containing a thermosetting component (for example, the above-mentioned component (E)) may have reduced developability as curing proceeds by heating. Therefore, the heating temperature in prebaking 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 ultrahigh pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a carbon arc lamp or a light emitting diode) is used.

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 dose is excessively low, curing may be insufficient and the pattern contrast may be reduced, and if the exposure dose is excessively high, the takt time may increase, resulting in an increase in manufacturing cost.

<Post exposure bake>
After exposure and before development, post-exposure bake (PEB) may be performed for the purpose of accelerating 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, and even more preferably 60 to 100°C.

<Development>
A pattern film is obtained by bringing the exposed coating film into contact with an alkali developer by a dipping method, a spray method or the like to dissolve and remove the coating film in the exposed area. In the exposed area, the action of the acid generated by irradiation of the photo-acid generator with the active energy ray increases the alkali solubility of the component (A), so that the coating film is dissolved by alkali development. The acid generated in the exposed portion diffuses into the non-exposed portion with the passage of time, but the (C1) component and the (C2) component contained in the photosensitive composition quench the acid diffused in the non-exposed portion. It is possible to prevent the coating film in the exposed area from being dissolved in alkali. In the present invention, by using the component (C1) and the component (C2) in combination as the basic compound (C), it is difficult for the unexposed portion to dissolve in alkali even when the time from exposure to development is long, and the pattern The line width of the film (the width of the region where the film is not dissolved in the alkaline developer and remains) and the space width (the width of the region dissolved in the alkaline developer) are kept constant.

As the alkali developing solution, a commonly used one can be used without particular limitation. Specific examples of the alkaline developer include organic alkali 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, 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 and the like.

<Post bake>
After the exposed portion is dissolved 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 (E), post-baking will result in the SiH group of the component (A). And the (E) component ethylenically unsaturated group causes a hydrosilylation reaction to proceed with curing. The post-bake conditions can be set appropriately. The post-baking temperature is preferably 100 to 400°C, more preferably 120 to 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 TFTs, a gate insulating film for TFTs, an interlayer insulating film for TFTs, a transparent flattening film for TFTs, a photo spacer material for liquid crystal cells, a transparent sealing material for OLED elements 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 compound]
100 parts by weight of diallyl bisphenol S and 400 parts by weight of tetrahydrofuran (THF) were placed in a reaction vessel and stirred at room temperature. A homogeneous solution was obtained. Hexamethyldisilazane: 50 parts by weight was added to the reaction vessel, and the mixture was reacted at room temperature for 2 hours, and after the presence of a trimethylsilyl group-derived peak and the disappearance of the hydroxyl group-derived peak were confirmed by ¹ H-NMR, THF and the reaction were performed. The residue was distilled off under reduced pressure to obtain diallyl bisphenol S (Compound 1) whose hydroxyl group was protected by a trimethylsilyl group.

In a reaction vessel, 1,3,5,7-tetramethylcyclotetrasiloxane: 60 parts by weight and toluene: 400 parts by weight were placed, and the gas phase part was replaced with nitrogen, and then the internal temperature was heated to 100°C and stirred. 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, 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 dropping, the disappearance of the peak derived from the allyl group was confirmed by ¹ H-NMR, and then toluene was distilled off under reduced pressure to obtain a colorless transparent liquid (reactant A). ^{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 composition]
96.15 parts by weight of the above reaction product A, 3.85 parts by weight of pentaerythritol tetraacrylate (“NK Ester A-TMMT” manufactured by Shin-Nakamura Chemical Co., Ltd.) as a cross-linking agent, and an imide sulfonate compound (ADEKA as a photo-acid generator). "SP-606") and 1 part by weight of (4-tert-butylphenyl)sulfonium nonafluorobutane-1-sulfonate ("TTBPS-PFBS" manufactured by Toyo Gosei Chemical Industry Co., Ltd.), and 9 parts as a sensitizer. , 10-dibutoxyanthracene and 0.05 parts of a 3 wt% isopropanol solution of [Pt-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (manufactured by NE Chemcat) as a catalyst. 2 parts by weight of 2-methyl-3-butyn-2-ol as a retarder, 0.5 parts by weight of a silicone-based surface conditioner ("MQV6 resin" manufactured by SiVance), and "Adeka Stab AO-" as an antioxidant. 80 parts (made by ADEKA) and 143.91 parts by weight of propylene glycol-1-monomethyl ether-2-acetate as a solvent were mixed to prepare a positive photosensitive composition. This composition is referred to as "standard composition" (Comparative Example 1).

In Examples and Comparative Examples, 100 parts by weight of a basic compound (a morpholine-based compound, an oxazoline-based compound, and a piperidine-based compound) and a curable resin component (the total of the reactant A and A-TMMT) were added to the above standard composition. On the other hand, the positive type photosensitive composition was prepared by adding it at a ratio shown in Tables 1 to 3.

Details of the basic compounds shown in Tables 1 to 3 are as follows.
<Morpholine compound>
A: 4-methylmorpholine B: 4-allylmorpholine C: 2-methyl-4'-(methylthio)-2-morpholinopropiophenone D: Bis(2-morpholinoethyl) ether E: N-cyclohexyl-N'- [2-(4-morpholinyl)ethyl]thiourea F:, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone G:2-(dimethylamino)-2-[ (4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone <oxazoline compound>
A: 2-ethyl-2-oxazoline B: 2,4,4-trimethyl-2-oxazoline C:1,3-bis(4,5-dihydro-2-oxazolyl)benzene D:1,4-Bis(4 ,5-Dihydro-2-oxazolyl)benzene E: 2,2′-bis(2-oxazoline)
<Piperidine compound>
A: {1,2,2,6,6-pentamethyl-4-piperidyl/β,β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5 , 5) Undecane]dimethyl}-1,2,3,4-butanetetracarboxylate (“ADEKA STAB LA-63P” manufactured by ADEKA)
B: Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (“ADEKA STAB LA-52” manufactured by ADEKA)
C: Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate ("ADEKA STAB LA-57" manufactured by ADEKA)
D: Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate ("ADEKA STAB LA-72" manufactured by ADEKA)
E: Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate ("ADEKA STAB LA-77Y" manufactured by ADEKA)
F: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate ("ADEKA STAB LA-82" manufactured by ADEKA)
G: 2,2,6,6-tetramethyl-4-piperidyl methacrylate ("ADEKA STAB LA-87" manufactured by ADEKA)

[Formation of patterned cured film and evaluation of space width]
The positive photosensitive compositions of Examples and Comparative Examples were applied onto a 50 mm×50 mm non-alkali glass substrate by spin coating, and heated (prebaked) at 110° C. for 2 minutes using a hot plate to give a film thickness. A 2.5 μm coating film was formed. Using a mask aligner (“MA-1300” manufactured by Dainippon Kaken), exposure was performed through a photomask (line/pace=5 μm/5 μm) at an integrated irradiation amount of 20 mJ/cm ² . Two minutes after the exposure, a developing treatment was carried out by immersing the substrate in an alkali developing solution (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tama Chemical Industry Co., Ltd.) at 23° C. for 60 seconds. Further, post baking was carried out at 230° C. for 30 minutes in an oven to form a patterned cured film.

With respect to the compositions of Examples and Comparative Examples, the time until development after exposure was changed to 12 hours and 24 hours, and a patterned cured film was formed in the same manner as above. Each cured film was observed with a laser microscope ("OLS4000" manufactured by Olympus). In the obtained cross-sectional profile, the position of 0.5 μm in height from the bottom (the portion where the coating film is melted and the glass substrate is exposed) is taken as the line/space boundary, and the distance between two adjacent lines is set. Is the space width.

In each of the examples and comparative examples, the space width of the sample developed 12 hours after the exposure and the space width of the sample developed 24 hours after the exposure were compared with the space width of the sample developed 2 minutes after the exposure. The ratio was calculated. The type and addition amount of the basic compound in the positive photosensitive composition of each Example and Comparative Example, and the space width of the patterned cured film which was developed 12 hours and 24 hours after exposure (development immediately after exposure The ratio of the pattern-cured film to the space width) is shown in Tables 1 to 3.

In Comparative Example 1 containing no basic compound, the line width was 130% when the time from exposure to development was 12 hours, and the space width was 148% when the time from exposure to development was 24 hours. The space width was large (the line width was small). In Comparative Examples 1 to 9 and Comparative Examples 11 to 14 in which the morpholine compound was added as the basic compound, the increase in the space width (the decrease in the line width) was suppressed as compared with Comparative Example 1. When the same morpholine compound was used, the increase in the space width tended to be suppressed as the amount of addition increased, and in Comparative Example 9 and Comparative Example 12, when the time from exposure to development was 12 hours. The width of the space was 103%, and the width of the space when the time from exposure to development was 24 hours was 105%. However, in Comparative Example 10 in which 1 part by weight (33 parts by weight based on 100 parts by weight of the photo-acid generator) of solid content was added, the resin in the exposed part was not sufficiently dissolved. , The pattern could not be formed.

A similar tendency was observed in Comparative Examples 15 to 24 to which the oxazoline-based compound was added and Comparative Examples 25 to 28 to which the piperidine-based compound was added.

In Examples 1 to 19 in which a morpholine compound and an oxazoline compound were used in combination, the space width when the time from exposure to development was 12 hours was 101% or less, and the space width when time from exposure to development was 24 hours. Was 103% or less, and the line width and space width retention properties (line width stability) were improved as compared with Comparative Examples 1 to 28. However, in Comparative Example 29 in which 1 part by weight of each of the morpholine compound and the oxazoline compound was added to 100 parts by weight of the solid content, a pattern could not be formed as in Comparative Example 10.

When Comparative Example 8 is compared with Examples 1 to 5, Example 7 and Example 8, the amounts of the basic compounds added (total) are the same in these examples, but the morpholine compound and the oxazoline compound are used in combination. It can be seen that in Examples 1 to 5, Example 7, and Example 8, the space width when the time from exposure to development is long is small and the line width stability is excellent, as compared with Comparative Example 8. Further, in Example 4, the amount of the basic compound added was smaller than in Comparative Examples 9 and 21, but the line width stability was excellent. From these results, it is better to use the morpholine-based compound and the oxazoline-based compound in combination than the morpholine-based compound or the oxazoline-based compound alone to increase the addition amount, because the line width stability over time is excellent. I understand that

Also in Examples 20 to 38 in which a morpholine-based compound and a piperidine-based compound having two or more piperidine rings in one molecule were used in combination, the line width over time was the same as when the morpholine-based compound and the oxazoline-based compound were used in combination. It was excellent in stability. However, in Comparative Example 31 and Comparative Example 32 in which a compound containing only one oxazoline ring in one molecule was used as the oxazoline-based compound, a sufficient line width stability improving effect was not obtained. From these results, it is found that the line width stability with time is improved by using the morpholinic compound in combination with the compound having two or more piperidine rings in one molecule.

Also from the comparison of Comparative Examples 26 to 28 using the piperidine compound alone, and Examples 33 to 36 using the morpholine compound and the piperidine compound in combination, the combination system improves the line width stability over time, It can be seen that the process margin related to the standing time from exposure to development can be expanded.

Claims (7)

(A) component: a compound whose alkali solubility is increased by the action of an acid;
Component (B): photo-acid generator;
(C1) component: a basic compound having a morpholine ring; and (C2) component: one or more selected from the group consisting of a basic compound having an oxazoline ring and a compound having two or more piperidine rings in one molecule. ,
Including,
The content of the component (C1) is 1 to 25 parts by weight with respect to 100 parts by weight of the component (B),
The content of the component (C2) with respect to 100 parts by weight of the component (B) is 1 to 25 parts by weight.
Positive type photosensitive composition. The positive photosensitive composition according to claim 1, wherein the component (A) has a structure in which a phenolic hydroxyl group is protected by a protective group. The positive photosensitive composition according to claim 1, further comprising, as the component (E), a compound containing two or more functional groups capable of reacting with the component (A) in one molecule. The positive photosensitive composition according to claim 1, wherein the component (A) contains a polysiloxane compound. The positive photosensitive composition according to claim 4, wherein the siloxane compound has a SiH group. A patterned cured film comprising a cured product of the positive photosensitive composition according to claim 1. A method for producing a patterned cured film, which comprises applying the positive photosensitive composition according to any one of claims 1 to 5 onto a substrate and performing patterning by exposure and alkali development.