JP7155471B2 - Positive photosensitive composition and method for producing photosensitive composition - Google Patents

Description

The present invention relates to a positive photosensitive composition and a method for producing a photosensitive composition.

A positive photoresist containing an alkali-soluble novolak resin and a photosensitive quinone diazide is known. When the positive photoresist is irradiated with ultraviolet light, the quinonediazide is photoexcited and converted to a carboxylic acid structure. As a result, the alkali solubility of the UV-irradiated regions increases. This develops the positive photoresist to form a positive relief structure.

The resolution of positive photoresist is higher than that of negative photoresist. For this reason, positive photoresists are known to be advantageous in miniaturization processes. For example, Patent Document 1 describes such a photosensitive polyimide composition.
Patent Document 1: International Publication No. 99/19771

A positive photoresist used for an interlayer insulating layer of electronic parts is required to have high resolution. Furthermore, in electronic parts, warpage occurs due to differences in coefficients of linear expansion between constituent materials. A positive photoresist is required to have toughness to withstand such warping. However, since resolution and toughness generally have a trade-off relationship, it has been difficult to achieve both. Good dielectric properties (eg, low dissipation factor) are also desired for positive photoresists for improved electrical performance.

In order to solve the above problems, a first aspect of the present invention provides a positive photosensitive composition. A positive photosensitive composition has a structure in which a binder component having an alkali-soluble group is crosslinked with a first crosslinking agent. Here, the first cross-linking agent has a slide ring structure.

A second aspect of the present invention provides a method for producing a photosensitive composition comprising the following steps (1) to (3).
(1) A first reaction step of mixing a tetracarboxylic dianhydride, a diamine compound containing a carboxyl group, and a diamine compound containing a phenolic hydroxyl group with a solvent. In the first reaction stage the mixture is reacted at room temperature.
(2) A second reaction step of further adding a first cross-linking agent having a slide ring structure, a weak acid, and an azeotropic solvent with water and heating. In the second reaction stage, dehydration and cross-linking reactions occur.

It should be noted that the above summary of the invention does not list all the necessary features of the invention. Subcombinations of these feature groups can also be inventions.

4 is an SEM photograph of a pattern obtained by this embodiment. It is a comparison result of toughness in Example 2, Example 5, and Comparative Example 1.

Hereinafter, the present invention will be described through embodiments of the invention. The following embodiments do not limit the claimed invention. Also, not all combinations of features described in the embodiments are essential for the solution of the invention. In the following embodiments, unless otherwise specified, operations, measurements, and the like may be performed under conditions of room temperature and a relative humidity of 40% RH or more and 60% RH or less. Room temperature may be, for example, 20-25°C.

[1] Composition of positive photosensitive composition The composition of the positive photosensitive composition according to this embodiment will be described.

In this embodiment, a positive photosensitive composition containing a binder component is provided. The binder component has a structure crosslinked by the first crosslinker. The binder component may have alkali-soluble groups. The first cross-linking agent may have a slide ring structure. A positive photosensitive composition is developed by irradiation with light such as ultraviolet rays. Only the light-irradiated portions of the positive-working photosensitive composition are developed with the developer.

The positive photosensitive composition of this embodiment provides particularly excellent toughness. The reason for this is not necessarily clear. According to this embodiment, the binder component is crosslinked via the slide ring structure. As a result, the bridging portion can move through the slide ring structure. For this reason, it is considered that the stretchable range of the resin is greatly expanded. Therefore, it is considered that the toughness of the resin is excellent.

The binder component may have a structure further crosslinked by a second crosslinking agent in addition to the first crosslinking agent. The second cross-linking agent may be different than the first cross-linking agent. For example, the second cross-linking agent does not have a slide ring structure. Moreover, the positive photosensitive composition may contain a photoacid generator. Also, the positive photosensitive composition may contain a surfactant and/or other additives.

[1.1] Binder Component The binder component is a polymer that is the main component of the positive photosensitive composition. The binder component can be a single type of resin. Alternatively, the binder component may be a mixture of multiple types of resins. The binder component may include a polyamideimide resin containing a polyamideimide structure and/or a polyimide resin containing a polyimide structure. Hereinafter, in the present specification, the imide structure and the amide-imide structure are collectively referred to simply as "the imide structure, etc.". In addition, the polyimide structure and the polyamideimide structure are collectively referred to simply as "polyimide structure, etc.". Polyamide-imide resin and polyimide resin may be collectively referred to simply as "polyimide resin or the like".

[1.1.1] Polyimide resin, etc. The polyimide resin, etc. may be a polymer containing at least one of the following (i) to (iv) in a repeating unit.
(i) an aromatic amide imide structure;
(ii) an aromatic imide structure;
(iii) an aliphatic amide imide structure;
(iv) an aliphatic imide structure;

A polyimide resin or the like may be a polymer containing a repeating unit containing a phenolic hydroxyl group in addition to an imide structure or the like. For example, the content of repeating units containing a phenolic hydroxyl group may be 80 mol % or more and 95 mol % or less in all repeating units of the binder component. Moreover, the polyimide resin or the like may be a polymer containing a repeating unit containing a carboxyl group in addition to an imide structure or the like. The content of repeating units containing a carboxyl group may be 5 mol % or more and 20 mol % or less in all repeating units of the binder component.

Moreover, when the content of the repeating unit having a phenolic hydroxyl group is less than 80 mol %, the metal corrosion resistance may deteriorate. In addition, since the binder component becomes difficult to dissolve in a solvent or the like, there is a possibility that the intended positive photosensitive composition cannot be produced. On the other hand, when it exceeds 95 mol %, the pattern developability, toughness and metal corrosion resistance are lowered.

The content of repeating units having a phenolic hydroxyl group is preferably 87 mol % or more and 95 mol % or less. The content of repeating units having a phenolic hydroxyl group is more preferably 90 mol % or more and 95 mol % or less.

If the content of the repeating unit having a carboxyl group is less than 5 mol %, at least one of pattern developability, toughness and corrosion resistance to metal deteriorates. On the other hand, if the content exceeds 20 mol %, the metal corrosion resistance may be lowered. Furthermore, the binder component may become difficult to dissolve in a solvent or the like. As a result, the desired positive photosensitive composition may not be produced.

The content of repeating units having a carboxyl group is preferably 5 mol % or more and 13 mol % or less. The content of repeating units having a carboxyl group is more preferably 5 mol % or more and 10 mol % or less.

The content of each repeating unit can be calculated by chemical analysis. For example, the composition/structure of a polyimide resin or the like may be analyzed by 1H-NMR, IR, or the like.

It is desirable that the total amount of the repeating units having the carboxyl group and the repeating units having the phenolic hydroxyl group is within a predetermined range with respect to all the repeating units of the polyimide resin or the like. For example, the total amount is preferably 70 mol % or more and 100 mol % or less in all repeating units of the binder component. More preferably, the total amount is 80 mol % or more and 100 mol % or less. More preferably, the total amount is 90 mol % or more and 100 mol % or less. As an example, the total amount may be 100 mol % of all repeating units of the binder component.

…（化学式１）
化学式１において、Ｒ_１は、アルキレン基、又は、アリーレン基である。ここで、アルキレン基は、フッ素原子、エーテル結合もしくはエステル結合を含んでもよい。また、アルキレン基は、炭素数１以上１０以下であってよい。また、アルキレン基は、直鎖状、分枝状、もしくは環状であってよい。アリーレン基は、エーテル結合もしくはエステル結合を含んでもよい。アリーレン基は、炭素数６以上２０以下であってよい。 As an example, a repeating unit containing a phenolic hydroxyl group may have the structure shown in Formula 1.

... (chemical formula 1)
In Chemical Formula 1, R ₁ is an alkylene group or an arylene group. Here, the alkylene group may contain a fluorine atom, an ether bond or an ester bond. Moreover, the alkylene group may have from 1 to 10 carbon atoms. Alkylene groups may also be linear, branched, or cyclic. The arylene group may contain an ether bond or an ester bond. The arylene group may have from 6 to 20 carbon atoms.

…（化学式２）
化学式２において、Ｒ_２は、アルキレン基、又は、アリーレン基であってよい。アルキレン基は、フッ素原子、エーテル結合もしくはエステル結合を含んでもよい。アルキレン基は、炭素数１以上１０以下であってよい。アルキレン基は、直鎖状、分枝状、もしくは環状であってよい。アリーレン基は、エーテル結合もしくはエステル結合を含んでもよい。アリーレン基は、炭素数６以上２０以下であってよい。 For example, a repeating unit containing a carboxyl group may have a structure represented by Formula 2 below.

... (chemical formula 2)
In Formula 2, R ₂ may be an alkylene group or an arylene group. The alkylene group may contain a fluorine atom, an ether bond or an ester bond. The alkylene group may have from 1 to 10 carbon atoms. Alkylene groups may be linear, branched, or cyclic. The arylene group may contain an ether bond or an ester bond. The arylene group may have from 6 to 20 carbon atoms.

Examples of alkylene groups in chemical formula 1 and/or chemical formula 2 include methylene group, ethylene group, n-propylene group, n-butylene group, 2-methylpropylene group, pentylene group, 2,2-dimethylpropylene group, 2-ethyl propylene group, n-hexylene group, n-heptylene group, n-octylene group, 2-ethylhexylene group, nonylene group, decylene group, cyclopropylene group, cyclopentylene group, cyclohexylene group, methylcyclohexylene group, dimethyl cyclohexylene group, cycloheptylene group, 1-ethylcyclopentylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, bicyclodecylene group, norbornylene group, cyclohexanedimethylene group and the like.

Examples of the arylene group in chemical formula 1 and/or chemical formula 2 include phenylene group, biphenylene group, naphthylene group, terphenylene group, anthranylene group and the like.

Examples of the alkylene group or arylene group containing an ether bond or an ester bond in Chemical Formula 1 and/or Chemical Formula 2 include groups represented by the following formulae. In the formula below, Ph' represents a phenylene group.
_{-OCH2CH2O- _}
—OCH ₂ —CH(CH ₃ )O—
_{-OCH2CH2CH2O- _ _}
-O-Ph'-O-
-CO-O _- CH2CH2 _- O-CO-
-CO-O- _CH2 -CH( _CH3 )-CO-O-
-CO _{- OCH2CH2CH2O -} CO-
-CO-O-Ph'-O-CO-

…（化学式３） A preferred example of the repeating unit containing a carboxyl group is the structure represented by the following chemical formula 3.

... (chemical formula 3)

The repeating unit represented by the chemical formula 3 is obtained by reacting 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester with methylenebisaminobenzoic acid. have a structure. The repeating unit represented by Chemical Formula 3 may be obtained by reacting other raw materials.

…（化学式４） A preferred example of a repeating unit containing a phenolic hydroxyl group is the structure represented by the chemical formula 4 below.

... (chemical formula 4)

The repeating unit represented by the above chemical formula 4 includes 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester and 2,2-bis(3-amino-4-hydroxy It has a structure obtained by reacting with phenyl)hexafluoropropane. The repeating unit represented by Chemical Formula 4 may be obtained by reacting other raw materials.

There are no particular restrictions on the method for producing the polyimide resin or the like. For example, it may be obtained by reacting (for example, polycondensing) a tetracarboxylic dianhydride, a diamine compound containing a carboxyl group, and a diamine compound containing a phenolic hydroxyl group.

As an example, a tetracarboxylic dianhydride, a diamine compound containing a carboxyl group, a diamine compound containing a phenolic hydroxyl group, and optionally other diamine compounds that do not contain a carboxyl group and a phenolic hydroxyl group (hereinafter referred to as These compounds are sometimes referred to as monomers). This reaction yields a polyimide precursor. The resulting polyimide precursor may then be imidized to synthesize a polyimide resin. This method is referred to as method A. Alternatively, the tetracarboxylic dianhydride and the diamine compound may be directly reacted to synthesize a polyimide resin. This method is referred to as method B.

…（化学式５）
ここでＲ_３は、アルキレン基、又は、アリーレン基である。アルキレン基は、フッ素原子、エーテル結合もしくはエステル結合を含んでもよい。アルキレン基は、炭素数１以上１０以下であってよい。アルキレン基は、直鎖状、分枝状、もしくは環状であってよい。アリーレン基は、エーテル結合もしくはエステル結合を含んでもよい。アリーレン基は、炭素数６以上２０以下であってよい。Ｒ_３の例として、化学式１及び化学式２で説明したＲ_１及びＲ_２と同様のものが挙げられる。 The tetracarboxylic dianhydride may be a compound represented by Formula 5 below.

... (chemical formula 5)
Here, R ₃ is an alkylene group or an arylene group. The alkylene group may contain a fluorine atom, an ether bond or an ester bond. The alkylene group may have from 1 to 10 carbon atoms. Alkylene groups may be linear, branched, or cyclic. The arylene group may contain an ether bond or an ester bond. The arylene group may have from 6 to 20 carbon atoms. Examples of R ₃ include those similar to R ₁ and R ₂ described in Chemical Formula 1 and Chemical Formula 2.

Specific examples of the tetracarboxylic dianhydride include, for example, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 3,3'-oxydiphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bicyclo[2,2,2]octo -7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 5,5′-methylene-bis(anthranilic acid) , pyromellitic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1- Bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis (2,3-dicarboxyphenyl)methane dianhydride, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid -1,4-phenylene ester, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10- Perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoro Propane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzoyloxy)phenyl)hexafluoropropane dianhydride, 2,2'-bis(trifluoromethyl)-4,4'-bis (3,4-dicarboxyphenoxy)biphenyl dianhydride, cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclo hexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and the like. These tetracarboxylic dianhydrides may be used alone. Alternatively, a mixture of two or more of these can be used.

Among these tetracarboxylic dianhydrides, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester is preferred.

Examples of diamine compounds containing carboxyl groups include methylenebisaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-(3,3'-dicarboxy) diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminodiphenyl ether and the like. These carboxyl group-containing diamine compounds may be used alone. Alternatively, a mixture of two or more of these can be used.

Among these carboxyl group-containing diamine compounds, methylenebisaminobenzoic acid is preferred.

Examples of diamine compounds containing phenolic hydroxyl groups include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'- dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, bis(3-amino-4-hydroxyphenyl)methane, 2, 2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl) hexafluoropropane, bis(4-amino-3-hydroxyphenyl)methane, 2,2-bis(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3 , 3′-diamino-4,4′-dihydroxybenzophenone, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino- 2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like. These diamine compounds containing phenolic hydroxyl groups may be used alone. Alternatively, two or more of these can be mixed and used.

Among these diamine compounds containing phenolic hydroxyl groups, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane is preferred, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro Propane is more preferred.

For the purpose of improving heat resistance and/or chemical resistance and adjusting development performance, the polyimide resin and the like may optionally have other repeating units. Any such repeating units may be formed from other diamine compounds that do not contain carboxyl groups and phenolic hydroxyl groups. Such other diamine compounds include, for example, 4,4'-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3' -diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2, 2-di(3-aminophenyl)propane, 2,2-di(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2,2-di(3 -aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-di(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2 -(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,1-di(3-aminophenyl)-1-phenylethane, 1,1-di(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane, 1,3-bis(3-aminophenoxy ) benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3- aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, 1,4-bis(4-aminobenzoyl)benzene, 1,3-bis( 3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene , 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,3-bis(4-amino -α,α-ditrifluoromethylbene dyl)benzene, 1,4-bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene, 2,6- Bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy)pyridine, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl , bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4- aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]ether, bis [4-(4-aminophenoxy)phenyl]ether, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2 , 2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1 , 1,1,3,3,3-hexafluoropropane, 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene , 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(3-aminophenoxy) )-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-aminophenoxy)- α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 4,4′-bis[4-(4-aminophenoxy)benzoyl] Diphenyl ether, 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy] diphenyl sulfone, 4,4'-bis[4-(4-aminophenoxy) phenoxy]diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3 , 3′-diamino-4-biphenoxybenzophenone, 5-amino-2-(p-aminophenyl)benzoxazole, 2,2′-di(p-aminophenyl)-6,6′-bisbenzoxazole, 2 -(4-aminophenyl)-6-aminobenzoxazole, N-(4-aminophenyl)-4-aminobenzamide, N,N'-bis(4-aminophenyl)terephthalamide, 4-aminophenyl-4- Aminobenzoate, 2,2'-dimethylbiphenyl-4,4'-diamine and the like can be mentioned. These other diamine compounds may be used alone. Alternatively, two or more of these may be combined.

In method A (method of imidating a polyimide precursor), the method of synthesizing the polyimide precursor is not particularly limited. A known method can be adopted as a method for synthesizing the polyimide precursor.

For example, first, a diamine compound containing a carboxyl group and a diamine compound containing a phenolic hydroxyl group are dissolved in a solvent. If desired, other diamine compounds that do not contain carboxyl groups and phenolic hydroxyl groups may be dissolved in the solvent as well. Stir the solution. To this solution is gradually added a tetracarboxylic dianhydride in an amount substantially equivalent to the diamine compound used. A polyimide precursor solution can be obtained by allowing the reaction to proceed while stirring is continued. The monomer concentration at this time is not particularly limited. The monomer concentration is preferably 5% by mass or more and 50% by mass or less. The monomer concentration is more preferably 10% by mass or more and 40% by mass or less.

The solvent used in synthesizing the polyimide precursor is not particularly limited as long as it sufficiently dissolves the monomer and polyimide precursor. For example, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, hexamethylphosphoric triamide; sulfolane, dimethylsulfoxide, dimethylsulfone, tetramethylene sulfur-containing solvents such as sulfone and dimethyltetramethylene sulfone; phenolic solvents such as cresol, phenol and xylenol; diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), diglyme solvents such as tetraglyme; Lactone solvents such as γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone; ketone solvents such as isophorone, cyclopentanone, cyclohexanone, 3,3,5-trimethylcyclohexanone; benzene, toluene, xylene and other solvents such as pyridine, ethylene glycol, dioxane, and tetramethylurea; and the like. These solvents may be used alone. Alternatively, two or more of these may be mixed or used.

The reaction temperature is not particularly limited. For example, the reaction temperature is -10°C or higher and 80°C or lower. The reaction temperature is more preferably 0°C or higher and 40°C or lower. As an example, the reaction temperature can be room temperature. Also, the reaction time is not particularly limited. For example, the reaction time is 0.5 hours or more and 150 hours or less. The reaction time is more preferably 3 hours or more and 24 hours or less.

The concentration of the solution may be adjusted without isolating the polyimide precursor from the obtained polyimide precursor solution. The solution can then be subjected to the following imidization reaction. Alternatively, the polyimide precursor solution may be dropped into a large amount of water or a poor solvent such as methanol. Thereby, a polyimide precursor can be deposited. The polyimide precursor can also be isolated by filtering, washing and drying this.

The method for imidizing the polyimide precursor is not particularly limited. For example, a known chemical imidization method or thermal imidization method can be employed. Among them, the chemical imidization method is preferably used. The chemical imidization method does not include an excessive heating step and can suppress the reduction in the molecular weight of the polyimide resin.

In the chemical imidization method, for example, a polyimide precursor solution is stirred and an organic acid anhydride and an organic base are added dropwise. As the solvent for the solution of the polyimide precursor, the same solvents as those shown as the solvent for synthesizing the polyimide precursor can be used. Examples of organic acid anhydrides include acetic anhydride, propionic anhydride, maleic anhydride, and phthalic anhydride. Among them, acetic anhydride is preferably used because it is easy to remove after the reaction and from the viewpoint of cost. The amount of organic acid anhydride used is not particularly limited. For example, the amount used is preferably 1 equivalent or more and 10 equivalents or less, more preferably 2 equivalents or more and 5 equivalents or less, of the theoretical amount of dehydration of the polyimide precursor.

Examples of organic bases include heterocyclic compounds such as pyridine and picoline; tertiary amines such as triethylamine and N,N-dimethylaniline; and the like. The amount of organic base used is not particularly limited. For example, the amount to be used is preferably 0.1 equivalent or more and 2 equivalent or less relative to the organic acid anhydride. The amount used is more preferably 0.2 equivalents or more and 1.5 equivalents or less.

The reaction temperature in the chemical imidization method is not particularly limited. For example, the reaction temperature is 0° C. or higher and 130° C. or lower. More preferably, the reaction temperature is 20°C or higher and 110°C or lower. The reaction time is also not particularly limited. For example, the reaction time is 0.5 hours or more and 48 hours or less. More preferably, the reaction time is 1 hour or more and 24 hours or less.

In the thermal imidization method, for example, a polyimide precursor solution is heated to a temperature at which a dehydration ring-closing reaction occurs. As a heating method, either a method of raising the temperature to the maximum temperature in one step or a method of raising the temperature in multiple steps is adopted.

As the solvent for the solution of the polyimide precursor, the same solvent as the solvent for synthesizing the polyimide precursor may be used. In the thermal imidization method, the reaction temperature is not particularly limited. For example, the reaction temperature is 130° C. or higher and 450° C. or lower. More preferably, the reaction temperature is 300°C or higher and 400°C or lower. The reaction time is also not particularly limited. For example, the reaction time is preferably 0.1 hour or more and 24 hours or less. More preferably, the reaction time is 0.5 hours or more and 5 hours or less.

The reaction can be carried out in vacuum, in an inert gas such as nitrogen or argon, or in air. An organic base such as γ-picoline may be added to the reaction system as a catalyst. Toluene, xylene, or the like may be added to the reaction system in order to azeotropically distill off water, which is a by-product.

Alternatively, the isolated polyimide precursor can be heated as it is for thermal imidization. The reaction temperature is not particularly limited. For example, the reaction temperature is 200° C. or higher and 400° C. or lower. More preferably, the reaction temperature is 250°C or higher and 300°C or lower. The reaction time is also not particularly limited. For example, the reaction time is 0.5 hours or more and 48 hours or less. More preferably, the reaction time is 1 hour or more and 24 hours or less.

The reaction can be carried out in vacuum, in an inert gas such as nitrogen, argon, or in air. It is preferable to carry out the reaction in vacuum or in an inert gas, as this can prevent coloration.

A case of synthesizing a polyimide by method B (a method of synthesizing a polyimide directly from a tetracarboxylic dianhydride and a diamine) will be described. The reaction conditions for Method B may differ from the reaction conditions for the method for synthesizing the polyimide precursor in Method A, for example.

As the solvent used for the reaction, the same solvents as those shown as the solvent for synthesizing the polyimide precursor can be used. Among them, amide-based solvents and phenol-based solvents are preferred. The reaction temperature is not particularly limited. For example, the reaction temperature may be 130° C. or higher and 250° C. or lower. More preferably, the reaction temperature is 140°C or higher and 200°C or lower. The reaction time is also not particularly limited. For example, the reaction time may be from 0.5 hours to 48 hours. More preferably, the reaction time is 1 hour or more and 24 hours or less. An organic base such as γ-picoline may be added to the reaction system as a catalyst. Toluene, xylene, or the like may be added to the reaction system in order to azeotropically distill off water, which is a by-product.

Polyimides may be obtained by the reaction of Method A or Method B above. The resulting polyimide solution may be added dropwise into a large amount of poor solvent. Polyimide is thereby deposited. Further, the precipitated polyimide may be filtered, washed, dried, and the like. Thus, polyimide powder can be obtained.

As the poor solvent, a solvent that does not dissolve polyimide is used. For example, water; alcohol solvents such as methanol, ethanol, n-propanol and isopropanol; ketone solvents such as acetone; ester solvents such as ethyl acetate; These poor solvents have high affinity with reaction solvents and chemical imidizing agents. Moreover, these poor solvents are efficiently removed by drying.

The weight average molecular weight (Mw) of the polyimide resin, etc. is not particularly limited. For example, from the viewpoint of ensuring mechanical properties, it is preferably 40,000 or more. More preferably, the weight average molecular weight is 45,000 or more. Moreover, the upper limit of the weight average molecular weight of the polyimide resin or the like is not particularly limited. For example, it is preferably 80,000 or less.

The molecular weight distribution (Mw/Mn) of the polyimide resin or the like is preferably 1.5 or more and 5 or less.

The weight average molecular weight and molecular weight distribution of polyimide resins and the like can be controlled, for example, by changing the type and composition of monomers, conditions during synthesis, and the like. In addition, a weight average molecular weight and molecular weight distribution are polystyrene conversion values. A polystyrene conversion value is obtained by a gel permeation chromatography method. More specifically, the weight average molecular weight and molecular weight distribution can be measured by the methods described in Examples.

[1.1.2] Novolak resin As a binder component, a novolak resin may be included in addition to the above-described polyimide resin and the like. Thereby, developability and resolution can be improved.

As the novolak resin, a known novolak resin can be appropriately selected and used. Specifically, for example, phenol novolak resin, cresol novolak resin, t-butylphenol novolak resin, dicyclopentadiene cresol novolak resin, dicyclopentadiene phenol novolak resin, xylylene-modified phenol novolak resin, tetrakisphenol novolak resin, bisphenol A novolak resin. , poly-p-vinylphenol resin and the like.

These novolac resins can be used alone or in combination of two or more. Moreover, a commercial product and/or a synthetic product may be used as the novolac resin. Examples of commercially available products include TR4020G and TR4080G (these are cresol novolac resins manufactured by Asahi Organic Chemicals Industry Co., Ltd.). The content of the novolac resin in the composition is preferably 5 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the polyimide resin or the like as the binder component. More preferably, the content of the novolak resin is 10 parts by mass or more and 40 parts by mass or less.

At least part of the resin of the binder component described above may be synthesized before cross-linking with the first cross-linking agent or the like. Alternatively, polymerization and crosslinking of the binder component may proceed in parallel, as described below.

[1.2] First Crosslinking Agent The first crosslinking agent has a slide ring structure. The first cross-linking agent cross-links at least part of the resin of the binder component. For example, the first cross-linking agent may cross-link at least a polyimide resin or the like. The slide ring structure is, for example, a structure in which a molecule having a linear structure penetrates a ring of molecules having a ring structure. Here, the ring-structured molecule may be capable of moving (sliding) on the chain of the linear-structured molecule. A stopper molecule may be arranged at one end or both ends of the linear molecule to prevent the ring structure molecule from falling off.

A straight-chain polymer can be preferably used as the molecule having a straight-chain structure. A molecule having a linear structure may be partially branched. Polyethylene glycol is preferably used as the linear polymer.

A molecule having a ring structure may be a molecule having a ring structure large enough to move (slid) on a molecule having a linear structure. A structure containing, for example, cyclodextrin is preferably used as the ring structure molecule. One or a plurality of ring structure molecules may be provided for one linear structure molecule.

The ring-structured molecule may have one or more functional groups that can serve as cross-linking points for cross-linking the binder component. For example, in a molecule with a ring structure, functional groups that can serve as cross-linking points may be attached directly to the ring structure. In the ring-structure molecule, the functional group that can serve as a cross-linking point may be bound to the ring structure via the chain-structure molecule. The first cross-linking agent may cross-link the binder component at a plurality of cross-linking points of one ring structure. and/or the first cross-linking agent may cross-link the binder component at multiple cross-linking points across multiple ring structures.

Such chain structure molecules may be various linear polymers. A chain structure molecule may be, for example, polycaprolactone. Examples of functional groups that can serve as cross-linking points include, for example, a hydroxycarbonyl group, a hydroxycarbonylethyl group, a hydroxyl group, a methacryl group, and/or an acryl group.

The stopper molecule may be a bulky molecule to the extent that the ring structure molecule does not fall off from the linear structure molecule. For example, the stopper molecule may be adamantane, a derivative thereof, or the like (adamantanamine as an example).

…（化学式６）
化学式６において太線楕円は、スライドリング構造におけるリング構造の分子に対応する。太線楕円は、下記化学式７で示される構造を有してよい。ここで、ｌは１以上の整数から選択される数である。ｐは単分子中に存在するリング構造の分子の数であり、１以上の整数から選択される。 As a specific example, the first cross-linking agent may have a structure represented by Formula 6 below.

... (chemical formula 6)
In Chemical formula 6, the bold ellipse corresponds to the ring structure molecule in the slide ring structure. A thick ellipse may have a structure represented by Formula 7 below. Here, l is a number selected from integers of 1 or more. p is the number of ring-structured molecules present in a single molecule, and is selected from an integer of 1 or more.

…（化学式７）
化学式７において太線矩形はシクロデキストリンを示す。スライドリング構造における鎖部分が、当該シクロデキストリンの中空部分を貫通する。ｍ及びｎは１以上の整数から選択される数である。Ｘはそれぞれ独立に水素原子、ヒドロキシカルボニル基、ヒドロキシカルボニルエチル基、メタクリル基、アクリル基から選択される。

... (chemical formula 7)
In chemical formula 7, a thick rectangle indicates cyclodextrin. The chain portion in the slide ring structure penetrates the hollow portion of the cyclodextrin. m and n are numbers selected from integers of 1 or more. Each X is independently selected from a hydrogen atom, a hydroxycarbonyl group, a hydroxycarbonylethyl group, a methacryl group and an acryl group.

…（化学式８）
化学式８において太線矩形はシクロデキストリンを示す。スライドリング構造における直鎖状構造の分子部分が、当該シクロデキストリンの中空部分を貫通する。ｍ及びｎはそれぞれ独立に１以上の整数から選択される数である。 For example, the ring structure molecule in the slide ring structure of Chemical Formula 6 may have a structure represented by Chemical Formula 8 below.

... (chemical formula 8)
In chemical formula 8, a thick rectangle indicates cyclodextrin. The molecular portion of the linear structure in the slide ring structure penetrates the hollow portion of the cyclodextrin. m and n are numbers independently selected from integers of 1 or more.

In Chemical Formulas 6-8, preferably p is 1-2300, l is 8-2300, n is 1-1100, and m is 1-1100.

…（化学式９）
化学式９において、ヒドロキシ基のうちの１か所又は２か所以上が鎖構造分子とエーテル結合する。さらにｎは、１以上の整数であってよい。例えばｎは、１～３から選択される。ヒドロキシ基のうちの少なくとも一部は置換されていてよい。ヒドロキシ基のうちの少なくとも一部は、保護基で保護されていてもよい。 An example of the structure of cyclodextrin in chemical formulas 7 and 8 is shown in chemical formula 9 below.

... (chemical formula 9)
In Chemical Formula 9, one or more of the hydroxy groups are ether-bonded to the chain structure molecule. Furthermore, n may be an integer of 1 or more. For example, n is selected from 1-3. At least some of the hydroxy groups may be substituted. At least part of the hydroxy groups may be protected with a protecting group.

A commercially available product and/or a synthetic product may be used as the first cross-linking agent having a slide ring structure. As a commercially available product, a compound sold as polyrotaxane may be used. For example, as the first cross-linking agent, Selm Super Polymer manufactured by Advanced Soft Materials Co., Ltd. (product code: SH3400P, SH2400P, SH1310P, SM3403P, SM1313P, SA3403P, SA2403P, SA1313P), Selmky Mixture (product code: SM3400C, SA3400C, SA2400C) and/or Serum elastomer (product code: SH3400M), etc. may be used.

During the production of the positive photosensitive composition, the first cross-linking agent added cross-links the binder component. Here, at least part of the first cross-linking agent may exist in an unreacted and free state in the positive photosensitive composition. The content of the first cross-linking agent in the positive photosensitive composition is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder component or the polyamideimide resin and/or polyimide resin of the binder component. As for content of a 1st crosslinking agent, 2.5 to 10 mass parts is more preferable.

[1.3] Second Cross-Linking Agent The second cross-linking agent is an optional component that cross-links the resin that becomes the binder component together with the first cross-linking agent. The second cross-linking agent does not have a slide ring structure. The second cross-linking agent may be a compound having a methylol group and/or an alkoxymethyl group, an allyl compound, or the like. For example, the second cross-linking agent includes an aromatic compound having a methylol group and/or an alkoxymethyl group, or a compound substituted with a methylol group and/or an alkoxymethyl group at the N-position. Among the compounds, compounds in which the N-position is substituted with a methylol group and/or an alkoxymethyl group can be preferably used as the second cross-linking agent. Thereby, the chemical resistance after thermosetting can be improved.

As compounds substituted with methylol groups and/or alkoxymethyl groups at the N-position, more specifically, melamine resins, benzoguanamine resins, glycoluril resins, hydroxyethylene urea resins, urea resins, glycolurea resins, alkoxymethylated melamine Resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, alkoxymethylated urea resins can be mentioned.

Alkoxymethylated melamine resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins are prepared by replacing the methylol groups of known methylolated melamine resins, methylolated benzoguanamine resins, or methylolated urea resins with alkoxymethyl groups. can be obtained by converting to Types of this alkoxymethyl group include, for example, methoxymethyl group, ethoxymethyl group, propoxymethyl group, and butoxymethyl group.

Examples of commercially available compounds in which the N-position is substituted with a methylol group and/or an alkoxymethyl group include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238 , 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Nippon Cytec Industries Co., Ltd.), Nikalac (registered trademark) MX-270, -279, -280, -290, Nikalac MS-11, Nikalac MW-30, -100, -300, -390, -750, DM-BIPC-F (manufactured by Sanwa Chemical Co., Ltd.), EX-411, EX314 (Nagase Chemtech Co., Ltd.), NC -3000-L, EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), Licaresin HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.), EXA-850CRP (manufactured by DIC Corporation), MeDAIC, DA-MGIC, MA-DGIC, and CIC acid (manufactured by Shikoku Kasei Co., Ltd.).

Also, an epoxy resin may be used as the second cross-linking agent. Examples of such epoxy resins include Celoxide 2021P (manufactured by Daicel), PB3600 (manufactured by Daicel), PB4700 (manufactured by Daicel), Epiclon HP-7200 (manufactured by DIC), HP-7200L (manufactured by DIC), and/or HP -7200H (manufactured by DIC) or the like may be used.

Moreover, when an epoxy resin is used as the second cross-linking agent, the positive photosensitive composition may further contain a thermal acid generator or a thermal base generator as a curing accelerator. As a thermal acid generator, for example, WPAG-370 (manufactured by Wako Pure Chemical Industries) may be used. Further, as a thermal base generator, for example, WPBG-300 (manufactured by Wako Pure Chemical Industries), WPBG-345 (manufactured by Wako Pure Chemical Industries), or NISCURE TIC-188 (manufactured by Nippon Soda) may be used. By using such a combination, the properties of the positive photosensitive composition can be further improved. For example, by combining the above epoxy resin with a thermal acid generator or a thermal base generator, mechanical properties such as toughness of the cured film can be greatly improved.

During the production of the positive photosensitive composition, the second cross-linking agent cross-links the binder component. Here, at least part of the second cross-linking agent may exist in an unreacted and free state in the positive photosensitive composition. The content of the second cross-linking agent in the positive photosensitive composition is preferably 5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the binder component or the polyimide resin of the binder component. As for content of a 2nd crosslinking agent, 7 mass parts or more and 20 mass parts or less are more preferable.

[1.4] Photoacid Generator Examples of photoacid generators include quinonediazide compounds, onium salts, and halogen-containing compounds. Among them, quinonediazide compounds are preferred from the viewpoint of solvent solubility, storage stability, high sensitivity, and the like. A photo-acid generator may be used individually or in combination of 2 or more types.

Examples of the onium salts include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts and the like. Among them, onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts and trialkylsulfonium salts are preferred.

Examples of the halogen-containing compounds include haloalkyl group-containing hydrocarbon compounds. From the viewpoint of high sensitivity, trichloromethyltriazine is preferably used as the halogen-containing compound.

As the quinonediazide compound, a naphthoquinonediazide compound (hereinafter also referred to as “NQD compound”) is preferable. Among them, compounds having a 1,2-naphthoquinone diazide structure are preferred. The compound having a 1,2-naphthoquinonediazide structure comprises a 1,2-naphthoquinonediazide-4-sulfonate ester of a polyhydroxy compound and a 1,2-naphthoquinonediazide-5-sulfonate ester of the polyhydroxy compound. It is preferably at least one compound selected from the group.

A commercially available NQD compound may be used, or a synthetic product may be used. When synthesizing, a commonly used method may be followed. For example, a naphthoquinonediazide sulfonic acid compound is converted to a sulfonyl chloride with chlorosulfonic acid or thionyl chloride. The obtained naphthoquinonediazide sulfonyl chloride and the polyhydroxy compound may be subjected to a condensation reaction. For example, a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride are mixed in a solvent such as dioxane, acetone, tetrahydrofuran, or the like in a solvent such as triethylamine. Esterification is carried out by reaction in the presence of a basic catalyst. The NQD compound can be obtained by washing the resulting product with water and drying it.

…（化学式１０）

…（化学式１１）

…（化学式１２）

…（化学式１３）

…（化学式１４）

…（化学式１５） From the viewpoint of ensuring contrast in i-line exposure, the preferred photoacid generator is at least one selected from the group consisting of compounds represented by chemical formulas 10 to 15 below.

... (chemical formula 10)

... (chemical formula 11)

... (chemical formula 12)

... (chemical formula 13)

... (chemical formula 14)

... (chemical formula 15)

…（化学式１６）

…（化学式１７） In Chemical Formulas 10 to 15 above, each R is independently a hydrogen atom, a group represented by Chemical Formula 16 below, or a group represented by Chemical Formula 17 below.

... (chemical formula 16)

... (chemical formula 17)

The content of the photoacid generator in the positive photosensitive composition is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the binder component or the polyamideimide resin and/or polyimide resin of the binder component. preferable. More preferably, the content of the photoacid generator is 5 parts by mass or more and 40 parts by mass or less. Within this range, both contrast during development and good mechanical properties can be achieved.

[1.5] Surfactant The positive photosensitive composition may contain a surfactant. This can improve the applicability of the composition and the in-plane uniformity and smoothness of the coating film. A nonionic surfactant can be preferably used as the surfactant.

Examples of nonionic surfactants include fluorine-based surfactants such as perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorine-containing organosiloxane compounds. Examples of commercially available products include Florard (registered trademark) “FC-430”, “FC-431”, “FC-4430” (manufactured by Sumitomo 3M Limited), Surflon (registered trademark) “S-141”, "S-145", "KH-10", "KH-20", "KH-30", "KH-40" (manufactured by AGC Seimi Chemical Co., Ltd.), Unidyne "DS-401", "DS- 4031", "DS-451" (manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) "F-8151" (manufactured by DIC Corporation), "X-70-092", "X-70 -093” (manufactured by Shin-Etsu Chemical Co., Ltd.).

The amount of the surfactant to be added is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the binder component or the polyamide-imide resin and/or the polyimide resin of the binder component. More preferably, the added amount of the surfactant is 0.1 parts by mass or more and 3 parts by mass or less.

[1.6] Other components The positive photosensitive composition may contain colorants, fillers, photosensitizers, alkali dissolution accelerators, adhesion aids, antifoaming agents, if necessary, to the extent that the photosensitive characteristics are not affected. It may optionally have other additives such as agents, leveling agents and the like.

[2] Method for producing positive photosensitive composition The method for producing the positive photosensitive composition is not particularly limited, and various methods can be employed. For example, a positive photosensitive composition can be obtained by mixing each component.

[2.1] Adjustment method As an example, a binder component and a first cross-linking agent, and optionally at least one of a photoacid generator, a second cross-linking agent, a surfactant, and other additives are stirred and mixed, A positive-acting photosensitive composition may be obtained (referred to as Method C). Various methods can be used as the mixing method. For example, in a room shielded from ultraviolet light, the components may be thoroughly stirred and mixed at room temperature or at a constant temperature (for example, 20° C. or higher and 40° C. or lower) until the mixture becomes uniform. When stirring and mixing, an organic solvent may be used together. After stirring and mixing, filtration may be performed.

Alternatively, only the binder component and the first cross-linking agent are mixed first, then a weak acid (eg, 3-methylsalicylic acid) is added and heated (eg, 145° C.). Thereby, at least a part of the binder component (for example, polyimide resin, etc.) is crosslinked by the first crosslinker before the other components are mixed. The crosslinked binder component and other components may then be mixed (referred to as Method D).

Alternatively, cross-linking with the first cross-linking agent may proceed in parallel with the synthesis of the polyimide resin or the like of the binder component (referred to as method E). For example, in Method A, a tetracarboxylic dianhydride, a diamine compound containing a carboxyl group, and a diamine compound containing a phenolic hydroxyl group are mixed in a solvent and reacted at room temperature. Synthesis of the polyimide precursor by this reaction is performed as the first reaction step. Thereafter, as a second reaction step, the imidization reaction may proceed by further adding the first cross-linking agent. Here, the imidization reaction may be carried out by the method described in Method A. Especially in the thermal imidization process, an azeotropic solvent with water and a weak acid may be added to cause an azeotropic dehydration reaction under heating conditions. Thereby, the synthesis of the polyimide resin or the like by dehydration reaction and the cross-linking reaction by the first cross-linking agent may proceed at the same time. According to Method E, the synthesis and cross-linking of the binder component can be completed in one step.

In method E, the degree of dispersion of the first cross-linking agent in the binder component can be increased compared to other methods. Therefore, method E can provide a tougher film than other methods. On the other hand, in methods C and D, compared to method E, the degree of dispersion of the first cross-linking agent in the binder component may be lower. Therefore, in Methods CD, it is desirable to use a surfactant to improve dispersibility.

Organic acids can be used as weak acids. For example, 3-methylsalicylic acid, 4-hydroxyphenylacetic acid, hydroxybenzoic acid can be used as weak acids. The azeotropic solvent with water may be any solvent that azeotropes with water with a sufficiently low azeotropic point (eg, less than 100°C, preferably less than 80°C). For example, toluene and xylene can be used.

As the tetracarboxylic dianhydride, the diamine compound containing a carboxyl group, and the diamine compound containing a phenolic hydroxyl group, those described in Method A may be used. As an example, a tetracarboxylic dianhydride, a diamine compound containing a carboxyl group, and a diamine compound containing a phenolic hydroxyl group are each 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic-1 ,4-phenylene ester, methylenebisaminobenzoic acid, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

In the first reaction step, the molar mixing ratio of the carboxyl group-containing diamine compound and the phenolic hydroxyl group-containing diamine compound may be 5:95 to 20:80. Also, in method E, if a second cross-linking agent is added, further cross-linking with the second cross-linking agent may be performed after the second reaction step.

In Method D and Method E, the binder component that has completed crosslinking may be purified and then mixed with other components to obtain a positive photosensitive composition. For example, after the second reaction step of Method E, the purified crosslinked binder component may be mixed with a photoacid generator and/or other ingredients.

Various organic solvents may be used in the final mixing in Methods CE. For example, organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol 1-monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol. Ethers such as dibutyl ether and tetrahydrofuran, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (propylene glycol 1-monomethyl ether 2-acetate), propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3- Acetates such as methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate and butyl lactate; Alcohols such as ketones, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol, N-methyl -2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone and the like.

Among them, from the viewpoint of solubility, it is selected from the group consisting of propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, cyclohexanone, 1-methoxy-2-propanol, γ-butyrolactone, and N-methyl-2-pyrrolidone. at least one is preferred.

The amount of the organic solvent to be added is not particularly limited as long as it is an amount that allows each component to be uniformly dispersed or dissolved. Moreover, the amount to be added may be such that the positive photosensitive composition exhibits a liquid state or a paste state suitable for each application. Generally, it is preferable that the amount of solid content (all components other than the solvent) in the positive photosensitive composition is 10% by mass or more and 90% by mass.

[2.2] Formation of Cured Film A cured film can be produced using the positive photosensitive composition. For example, a hardened film is formed by the following steps (i) to (ii).
(i) A step of applying a positive photosensitive composition onto a substrate and drying it to form a resin film.
(ii) a step of heat-treating the obtained resin film;

As an example, a cured film can be formed by a method including the following steps.
(a) forming a photosensitive resin layer made of a positive photosensitive composition on a substrate;
(b) exposing the photosensitive resin layer;
(c) removing the exposed portion with a developer to obtain a pattern; and (d) heating the pattern.

This method will be described below.

(a) Step of Forming Photosensitive Resin Layer on Substrate In this step, a positive photosensitive composition is applied onto the substrate. For example, spin coating using a spin coater may be performed. Alternatively, a coater such as a die coater or a roll coater may be used. The solvent is then removed by drying using an oven or hot plate. Drying is preferably carried out at a temperature of 50°C or higher and 140°C or lower. This forms a photosensitive resin layer. From the viewpoint of obtaining a coating film having a uniform thickness, a spin coating method using a spin coater is preferable.

The substrate is at least one material selected from the group consisting of copper, aluminum, titanium nitride, tantalum, tantalum nitride, silicon, silicon nitride, liquid crystal polymer, polyimide, epoxy resin, polyphenylene sulfide, and polyvinylidene chloride. A substrate comprising The substrate may have a single-layer structure or a multi-layer structure of two or more layers.

(b) Step of exposing the photosensitive resin layer Next, the photosensitive resin layer obtained above is exposed through a photomask. Exposure may be performed using a mask aligner or stepper. For example, exposure may be performed by directly irradiating active energy rays such as ultraviolet rays (i-ray (wavelength: 365 nm), h-ray (wavelength: 405 nm), g-ray (wavelength: 436 nm), etc.), X-rays, electron beams, and the like. The photomask may be hollowed out in a desired pattern.

The wavelength of the active energy ray used for exposure is preferably 190 nm or more and 500 nm or less. Further, the dose of active energy rays is preferably 100 mJ/cm ² or more and 3,000 mJ/cm ² or less.

Further, heat treatment (post-exposure baking) may be performed after exposure. By performing post-exposure baking, the curing reaction by the acid generated from the photoacid generator can be accelerated. The post-exposure baking conditions vary depending on the composition of the composition, the content of each component, the thickness of the photosensitive resin layer, and the like. For example, it is preferable to heat at 70° C. or higher and 150° C. or lower for about 1 minute or longer and 60 minutes or shorter.

(c) Step of removing the exposed portion with a developer to obtain a pattern Next, development can be performed by selecting from methods such as the dipping method, the puddle method, and the rotary spray method. By development, the uncured composition is eluted and removed from the photosensitive resin layer, and a pattern can be obtained. Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia; organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine; tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Aqueous solutions of quaternary ammonium salts, etc., and if necessary, aqueous solutions to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant has been added can be used. Among these, tetramethylammonium hydroxide aqueous solution is preferable. The concentration of the tetramethylammonium hydroxide aqueous solution is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 5% by mass or less.

After development, the pattern may be washed with pure water or the like.

(d) Heating Step Subsequently, the obtained pattern is cured by heating. Thereby, a cured film having a pattern is formed. Heating can increase the crosslink density of the composition and remove remaining volatile components. As a result, adhesion to the substrate, heat resistance, strength, etc. can be improved. As a heating device, an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven, or the like can be used. As a heating method, heating by hot air, infrared rays, electromagnetic induction, or the like may be used. The heating temperature is preferably 280° C. or lower. The heating temperature is more preferably 120° C. or higher and 280° C. or lower. The heating temperature is more preferably 160° C. or higher and 250° C. or lower. The heating time is preferably 15 minutes or more and 8 hours or less. The heating time is more preferably 15 minutes or more and 4 hours or less. In addition, the atmosphere of the heat treatment process can be selected from either the air or an inert atmosphere such as nitrogen.

The cured film thus obtained contains a cured product of the positive photosensitive composition of the present embodiment. The glass transition point of the cured product is preferably 200° C. or higher and 350° C. or lower. This can ensure the shape stability of the material during the solder reflow process and ensure flexibility at room temperature. The glass transition point can be controlled by the composition of the polyimide resin or the like, the composition of the positive photosensitive composition, and the like. Moreover, the glass transition point of the cured product can be measured by the method described in Examples.

Moreover, the film thickness of the cured film is preferably 5 μm or more and 20 μm or less.

Thus, at least one selected from the group consisting of copper, aluminum, titanium nitride, tantalum, tantalum nitride, silicon, silicon nitride, liquid crystal polymer, polyimide, epoxy resin, polyphenylene sulfide, and polyvinylidene chloride A printed wiring board can be provided comprising a substrate comprising a material and a patterned cured film of a positive photosensitive composition.

[3] Method of using the positive photosensitive composition The positive photosensitive composition can be used in the production of various electronic components. Any electronic component may be used as long as it can utilize a pattern formed by a positive photosensitive composition. Examples of electronic components include semiconductor devices, multilayer wiring boards, and various electronic devices. The positive photosensitive composition may be used particularly for forming insulating layers of printed wiring boards. A cured film obtained from a positive photosensitive composition can be used as a surface protective film or an interlayer insulating film for electronic parts such as semiconductor devices, an interlayer insulating film for multilayer wiring boards, and the like.

Electronic components are not particularly limited other than those described above, and can be used in various structures, applications, and structures. For example, it can also be used for patterns included in MEMS, flexible substrates, and the like.

The positive photosensitive composition of this embodiment is excellent in resolution and toughness. In particular, a binder component having a polyimide structure or the like is combined with a slide ring structure. As a result, the resolution as a photosensitive material, the insulation as an insulating material, and the mechanical strength (thermal expansion and toughness) as a permanent film can all be achieved at high levels.

Thereby, according to the positive photosensitive composition of the present embodiment, it is possible to maintain high resolution in the photo process. Furthermore, it can withstand warpage caused by the difference in coefficient of linear expansion between constituent materials in the product. Moreover, the cured film obtained from the positive photosensitive composition of this embodiment has a low dielectric loss tangent. As a result, it is possible to improve the propagation speed of the interlayer insulating material in the electronic component and reduce the transmission loss, thereby improving the performance of the electronic component.

As described above, the positive photosensitive composition of the present embodiment contains a binder component crosslinked by at least part of the first crosslinking agent and/or the second crosslinking agent. In addition, in the modified example, the binder component can be crosslinked by the first crosslinking agent and/or the second crosslinking agent, but may be in a state where it is not yet crosslinked.

[4] Examples Hereinafter, embodiments of the present invention will be described using examples.

[4.1] Synthesis Example [4.1.1] Synthesis Example 1
The following composition 1 was added to a separable flask equipped with a water content receiver connected to a reflux condenser, a thermometer and a stirrer, and reacted at room temperature for 20 hours.
[Composition 1]
67.4 g (50 mol %) of 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic-1,4-phenylene ester,
4.2 g (5 mol %) of methylenebisaminobenzoic acid,
2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 48.4 g (45 mol%),
540 g of N-methylpyrrolidone

Further, 6 g of polyrotaxane compound A, 3.5 g of 3-methylsalicylic acid, and 200 g of toluene were added to the reaction solution. Using an oil bath, the mixture was heated until the internal temperature reached 145° C., and the toluene-water azeotropic dehydration reaction was carried out for 5 hours. As the polyrotaxane compound A, a compound using a molecule represented by Chemical Formula 6 (in Chemical Formula 6, l is 454 and the ring structure molecule is represented by Chemical Formula 8) was used. In addition, in the molecule of the ring structure represented by Chemical Formula 7 in Chemical Formula 6, X is a hydroxycarbonylethyl group. For example, as polyrotaxane compound A, SA-SH2405P (molecular weight 350,000, oxidation: 3 to 10 mmgKOH/g) available from Advanced Softmaterials may be used.

The polyimide reaction solution thus obtained was reprecipitated in a methanol solvent and filtered to obtain a white solid. By drying the white solid at 60° C. for 10 hours under reduced pressure, 108 g of polymer compound 1 was obtained. The molecular weight was measured by high performance liquid chromatography (HLC-8120FPC manufactured by Tosoh). As a result, in terms of polystyrene, the weight average molecular weight (Mw) was 13,500, the number average molecular weight (Mn) was 12,700, and Mw/Mn was 10.6.

[4.1.2] Synthesis Example 2
The same procedure as in Synthesis Example 1 was performed, except that 0.12 g of F-563 as a surfactant was added together with the polyrotaxane compound A and the like to carry out a dehydration-crosslinking reaction. Polymer compound 2 was thus obtained.

[4.1.3] Synthesis Example 3
4,4′-oxydiphthalic anhydride (ODPA-C) 50 in place of 50 mol % 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic-1,4-phenylene ester in composition 1 The procedure was carried out in the same manner as in Synthesis Example 2, except that mol % was used. Thus, polymer compound 3 was obtained.

[4.1.4] Synthesis Example 4
The same operation as in Synthesis Example 2 was performed except that Composition 4 below was used instead of Composition 1. Thus, polymer compound 4 was obtained.
[Composition 4]
45.5 g (50 mol %) of 4,4′-oxydiphthalic anhydride (ODPA-C),
2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHP-HFM) 40.4 g (37.5 mol%),
8.58 g (10 mol %) of 1,3-bis(4-aminophenoxy)benzene (TPE-R),
2.1 g (2.5 mol%) of methylenebisaminobenzoic acid (MBAA)
540 g of N-methylpyrrolidone

[4.1.5] Synthesis Example 5
The binder component was polymerized using composition 1 without cross-linking with the polyrotaxane compound A. Thus, polymer compound 5 was obtained.

[4.2] Preparation of composition [4.2.1] Example 1
A positive photosensitive composition was prepared using the polymer compound 1 synthesized above. For preparation, polymer compound 1 (3 g) was added with 4,4′-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene)bisphenol as a photoacid generator. -diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid ester (0.75 g) and cyclopentane (7 g) were added. After stirring and mixing this at 25° C. for 6 hours, it was filtered through a filtration membrane having a pore size of 5 μm. Composition 1 was thus obtained.

[4.2.2] Example 2
6-diazo- of 4,4′-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene)bisphenol as a photoacid generator in polymer compound 2 (3 g) 5,6-Dihydro-5-oxo-1-naphthalenesulfonic acid ester (0.75 g), MX-270 (0.3 g) as a second cross-linking agent, and cyclopentane (7 g) were added. After stirring and mixing this at 25° C. for 6 hours, it was filtered through a filtration membrane having a pore size of 5 μm. Composition 2 was thus obtained.

[4.2.3] Example 3
The same operation as in Example 2 was performed except that polymer compound 3 was used instead of polymer compound 1. Composition 3 was thus obtained.

[4.2.4] Example 4
The same operation as in Example 2 was performed except that polymer compound 4 was used instead of polymer compound 1. Composition 4 was thus obtained.

[4.2.5] Example 5
To 100 parts by weight of polymer compound 5, 5 parts by weight of polyrotaxane compound A and 25 parts by weight of the same photoacid generator as in Example 1 were added. Composition 5 was thus obtained.

[4.2.6] Comparative Example 1
The same operation as in Example 5 was performed except that the polyrotaxane compound A was not added. Composition 6 was thus obtained.

[4.2.7] Comparative Example 2
5 parts by weight of polyrotaxane compound A and 25 parts by weight of the same photoacid generator as in Example 1 were added to 100 parts by weight of meta-, para-cresol novolak resin TR-4020-C (manufactured by Asahi Organic Chemicals Industry Co., Ltd.). Composition 7 was thus obtained.

[4.3] Preparation of cured film for measuring elongation at break, toughness, coefficient of linear expansion, and glass transition point Compositions 1 to 7 were each applied onto a polytetrafluoroethylene (PTFE) film having a thickness of 50 μm. It was dried on a hot plate at 80°C for 30 minutes and in an oven at 130°C air environment for 5 minutes. After that, heat treatment was performed at 200° C. for 1 hour in an inert oven with an oxygen concentration of 10 ppm or less. As a result, cured films (thickness: 15 μm) of Compositions 1 to 7 were obtained.

[4.4] Measurement of elongation at break and toughness The cured film obtained above was cut into strips having a width of 5 mm. On the other hand, a tensile test was performed using a universal testing machine (texture analyzer TA.TXplus manufactured by Stable Micro System) with a chuck width of 20 mm and a speed of 0.1 mm/sec. The elongation to break (elongation at break) and the area under the stress-strain curve were measured. The area under the stress-strain curve is defined as toughness in this specification. The elongation at break is preferably 12% or more and 30% or less. Further, the toughness is preferably 10 mJ/mm ³ or more and 30 mJ/mm ³ or less.

[4.5] Linear expansion coefficient measurement of cured film The film obtained by preparing the cured film is treated with TMA (manufactured by Seiko Instruments, EXSTAR6000TMA / SS6100) at a temperature increase rate of 10 ° C./min from room temperature to 200 ° C. went on a cycle. The coefficient of linear expansion was calculated from the TMA curve in the region of 50°C or higher and 100°C or lower in the second cycle.

[4.6] Dielectric Properties of Cured Film The dielectric loss tangent of the film obtained by producing the cured film was evaluated using a cylindrical cavity resonator manufactured by AET. The evaluation conformed to JIS2565 micro wave ferrite magnetic core test method. Permittivity and dissipation factor (Df) at 10 GHz were evaluated.

Table 1 shows the evaluation results for each example and comparative example. Cured films obtained from the positive photosensitive compositions prepared according to the examples exhibited excellent toughness and dielectric properties.

[4.7] Observation of Cured Film Using Composition 1 of Example 1, exposure and development were performed to form a pattern. A cross section of the obtained pattern was observed by SEM. As shown in FIG. 1, the pattern formed with composition 1 exhibited good pattern resolution.

[4.8] Comparison of toughness in Example 2, Example 5, and Comparative Example 1 The results of measuring the stress-strain curves in Example 2 (dotted line), Example 5 (solid line), and Comparative Example 1 (dashed line) are shown in the figure. 2. As shown in the figure, in Example 2 and Example 5, the area under the stress-strain curve is smaller than the result of Comparative Example 1. Also, in Example 2, the area under the stress-strain curve is slightly smaller than in Example 5.

The present invention has been described above using the embodiments. The technical scope of the present invention is not limited to the scope described in the above embodiments. It is obvious to those skilled in the art that various modifications and improvements can be made to the above embodiments. It is clear from the description of the scope of claims that forms with such modifications or improvements can also be included in the technical scope of the present invention.

The execution order of each process such as actions, procedures, steps, and stages in the processes and methods shown in the claims, the specification, and the drawings is specified as "before", "before", etc. , and can be implemented in any order, as long as the output of a previous process is not used in a later process. Regarding the operation flow in the claims, the specification, and the drawings, even if the description is made using "first," "next," etc. for the sake of convenience, it means that it is essential to carry out in this order. not a thing

Claims (18)

A binder component having an alkali-soluble group has a structure crosslinked to a first crosslinking agent having a slide ring structure ,
The first cross-linking agent is a positive photosensitive composition having a structure represented by Chemical Formula 1 below.

... (chemical formula 1)
(The bold ellipse in Chemical Formula 1 corresponds to the ring structure in the slide ring structure.
A thick ellipse has a structure represented by Chemical Formula 2 below.
l is a number selected from integers of 1 or more.
p is the number of ring structures present in a single molecule and is selected from integers of 1 or more.

... (chemical formula 2)
In chemical formula 2, a thick rectangle indicates cyclodextrin.
The chain portion in the slide ring structure penetrates the hollow portion of the cyclodextrin.
m and n are numbers selected from integers of 1 or more.
Each X is independently selected from a hydrogen atom, a hydroxycarbonyl group, a hydroxycarbonylethyl group, a methacryl group and an acryl group. ) removing the areas exposed by the actinic radiation with a developer to obtain a pattern;
Claim 1positive typephotosensitive composition. The positive photosensitive composition according to claim 1 or 2, wherein the thick ellipse in Chemical Formula 1 corresponds to the ring structure in the slide ring structure and has a structure represented by Chemical Formula 3 below:

... (chemical formula 3)
(In chemical formula 3, the bold rectangle indicates cyclodextrin.
The chain portion in the slide ring structure penetrates the hollow portion of the cyclodextrin.
m and n are numbers independently selected from integers of 1 or more. ) 4. The positive photosensitive composition according to any one of claims 1 to 3, wherein the binder component contains a polyamideimide structure and/or a polyimide structure. 5. The positive photosensitive composition according to claim 4, wherein the binder component contains 80 mol % or more of repeating units containing a phenolic hydroxyl group in all repeating units. The positive photosensitive composition according to claim 5, wherein the repeating unit containing the phenolic hydroxyl group has a structure represented by the following chemical formula 4:

... (chemical formula 4)
(In chemical formula 4, R ₁ is
(A) a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, or
(B) an arylene group having 6 to 20 carbon atoms;
(A) The alkylene group may contain a fluorine atom, an ether bond or an ester bond. (B) The arylene group may contain an ether bond or an ester bond. ) 7. The positive photosensitive composition according to claim 5, wherein the binder component contains 5 mol % or more of repeating units containing a carboxyl group in all repeating units. The positive photosensitive composition according to claim 7, wherein the repeating unit containing a carboxyl group has a structure represented by the following chemical formula 5:

... (chemical formula 5)
(In chemical formula 5, R ₂ is
(A) a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, or
(B) an arylene group having 6 to 20 carbon atoms;
(A) The alkylene group may contain a fluorine atom, an ether bond or an ester bond. (B) The arylene group may contain an ether bond or an ester bond. ) 9. The positive photosensitive composition according to any one of claims 1 to 8, wherein the binder component has a structure further crosslinked by a second crosslinking agent that does not have the slide ring structure. The second cross-linking agent contains a compound having a methylol group and/or an alkoxymethyl group, an allyl compound, and/or an epoxy resin,
The positive photosensitive composition according to claim 9. 11. The positive photosensitive composition according to any one of claims 1 to 10, further comprising a photoacid generator. The positive photosensitive composition for forming an insulating layer of a printed wiring board according to any one of claims 1 to 11. A first reaction step in which a tetracarboxylic dianhydride, a diamine compound containing a carboxyl group, and a diamine compound containing a phenolic hydroxyl group are mixed in a solvent and reacted at room temperature.
A second reaction step in which the first cross-linking agent having a slide ring structure, a weak acid, and an azeotropic solvent with water are further added to cause dehydration and cross-linking reactions under heating conditions.
including a third reaction step of purifying a binder component having an alkali-soluble group that has been crosslinked and mixing a photoacid generator;
A method for producing a photosensitive composition, wherein the first cross-linking agent has a structure represented by the following chemical formula 7:

... (chemical formula 7)
(The bold ellipse in Chemical Formula 7 corresponds to the ring structure in the slide ring structure.
The thick ellipse of Chemical Formula 7 has a structure represented by Chemical Formula 8 below.
l is a number selected from integers of 1 or more.
p is the number of ring structures present in a single molecule and is selected from integers of 1 or more.

... (chemical formula 8)
In chemical formula 8, a thick rectangle indicates cyclodextrin.
The chain portion in the slide ring structure penetrates the hollow portion of the cyclodextrin.
m and n are numbers selected from integers of 1 or more.
Each X is independently selected from a hydrogen atom, a hydroxycarbonyl group, a hydroxycarbonylethyl group, a methacryl group and an acryl group. ) The tetracarboxylic dianhydride is a compound represented by the following chemical formula 6,
The diamine compound containing a carboxyl group is methylenebisaminobenzoic acid,
The diamine compound containing a phenolic hydroxyl group is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane,
The azeotropic solvent with water is toluene.
A method for producing a photosensitive composition according to claim 13:

... (chemical formula 6)
₍ where R3 is
(A) a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, or (B) an arylene group having 6 to 20 carbon atoms.
(A) The alkylene group may contain a fluorine atom, an ether bond or an ester bond.
(B) The arylene group may contain an ether bond or an ester bond. ) 15. The method for producing a photosensitive composition according to claim 13 or 14 , wherein the thick ellipse in chemical formula 7 corresponds to the ring structure in the slide ring structure and has a structure represented by chemical formula 9 below:

... (chemical formula 9)
(In chemical formula 9, the bold rectangle indicates cyclodextrin.
The chain portion in the slide ring structure penetrates the hollow portion of the cyclodextrin.
m and n are numbers independently selected from integers of 1 or more. ) 16. The method according to any one of claims 13 to 15 , wherein the molar mixing ratio of the carboxyl group-containing diamine compound and the phenolic hydroxyl group-containing diamine compound is 5:95 to 20:80 in the first reaction step. A method for producing a photosensitive composition according to 15. The method of claim 14, wherein the compound represented by Formula 6 is 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic-1,4-phenylene ester. After the second reaction step, further comprising a cross-linking step of performing cross-linking with a second cross-linking agent that does not have the slide ring structure.
A method for producing a photosensitive composition according to any one of claims 13 to 17 .

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