JP5263523B2 - Positive photosensitive resin composition containing polyhydroxyurea resin - Google Patents

Description

The present invention relates to a positive photosensitive resin composition containing a polyhydroxyurea resin synthesized from diisocyanate and diamine and a photoacid generator.
The positive photosensitive resin composition of the present invention is suitable as a photosensitive material suitable for surface protective films, interlayer insulating films, passivation films, electrode protective layers, etc. for electrical / electronic devices, particularly semiconductor devices and display devices. .

The photosensitive resin insulation film made from photosensitive resin represented by photosensitive polyimide resin with excellent mechanical properties and high heat resistance has expanded its use, and has begun to spread not only to the semiconductor field but also to the display field. Therefore, there has been a demand for reliability with respect to an insulating film, which has never existed before.
Many of the positive type photosensitive resin compositions currently used are produced by adding a photosensitive dissolution inhibitor (DNQ: diazonaphthoquinone) to a base polymer. After producing a coating film from this resin composition, it is exposed through a mask, and a positive pattern is obtained by dissolving the exposed portion in tetramethylammonium hydroxide (TMAH), which is a typical water-soluble alkaline developer. It is done.
The typical polyimide-based positive photosensitive resin compositions that have been used so far have too high solubility in TMAH, so recently, basic acid compounds such as triethylamine are used to reduce the acidity of the polyamic acid. A polyimide-based positive tourism resin composition that suppresses the dissolution rate in an alkali developer has been proposed (Patent Document 1).

On the other hand, since polyhydroxyamide resin has moderate solubility in TMAH, it has been reported that it can be suitably used as a positive photosensitive resin composition (for example, Patent Document 2).
The characteristics required for a positive photosensitive resin composition using a polyhydroxyamide resin are excellent in film properties such as electrical insulation, heat resistance, mechanical strength, etc., as with a polyimide positive photosensitive resin composition. And that a high-resolution circuit pattern can be formed. In recent years, the characteristics required for these positive photosensitive resin compositions have become increasingly severe.

Usually, polyhydroxyamide resin is synthesize | combined on basic conditions using dicarboxylic acid chloride and dihydroxyamine (nonpatent literature 1). However, in the above method, since inorganic ions such as chloride ions are present in the reaction solution, the polymer must be isolated and purified after the completion of the reaction. Moreover, there is a possibility that a small amount of inorganic ions may be mixed in the positive photosensitive resin composition obtained using the polymer, which may cause corrosion when used in the field of electronic materials.
In order to solve these problems, a technique for synthesizing polyhydroxyamide using a carboxylic acid derivative obtained from the reaction of 1-hydroxybenzotriazole and dicarboxylic acid has been reported (Patent Document 3).

On the other hand, polyurea resin is easily synthesized from diisocyanate and diamine, and has been used for vibration damping resin compositions and the like (Patent Document 4).
U.S. Pat. No. 4,880,722 JP-A-9-183846 JP 2003-302761 A JP 2004-143324 A Polymer Letter. , Vol. 2, pp655-659 (1964)

Since the positive photosensitive resin composition using the polyhydroxyamide resin proposed in Patent Document 1 contains a small amount of impurities (inorganic ions), the composition is used as a material for a cured film such as an element. However, this left problems in various performances including electrical characteristics.
Further, even in Patent Document 2 in which the above problem is solved, a condensing agent is used in the synthesis of the carboxylic acid derivative, so that a by-product removal step is required, and it is difficult to obtain high-purity polyhydroxyamide. It was.
Furthermore, since polyurea resin cannot be dissolved in TMAH, it has been difficult to impart photosensitive characteristics.

  The present invention has been made in view of the above circumstances, and does not contain chlorides or low molecular compounds that adversely affect semiconductor elements and electronic / electrical circuits, and can be manufactured at low cost. Is excellent in electrical insulation, mechanical strength, etc. and can form high-resolution patterns, especially polyhydroxy which can form a cured film useful as a protective film or insulating film for circuit boards such as semiconductors or printed boards. It is an object to provide a urea resin composition.

  As a result of intensive investigations to achieve the above object, the present inventor has obtained an electrical insulating property by using a positive photosensitive resin composition containing a polyhydroxyurea resin produced from diisocyanate and diamine. The inventors have found that the film has excellent film properties in terms of mechanical strength and the like, and further enables the formation of a fine pattern, thereby completing the present invention.

  That is, as a first aspect, as the component (A), at least one polyhydroxyurea resin containing a structural unit represented by the following formula (1) and having a weight average molecular weight of 3,000 to 200,000, (B) It is related with the positive photosensitive resin composition characterized by including the compound which generate | occur | produces an acid by light as a component.

(Wherein X represents a divalent aliphatic group, alicyclic group or aromatic group,
Y represents a divalent organic group containing an aromatic group substituted with at least one hydroxy group;
Ra, Rb, Rc and Rd each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. )
As a second aspect, the X represents an aliphatic group having 1 to 13 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an aromatic group having 4 to 20 carbon atoms. To a positive photosensitive resin composition.
As a third aspect, the present invention relates to the positive photosensitive resin composition according to the first aspect or the second aspect, wherein Y has a structure represented by the following formula (2).

(In the formula (2),
R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, a phenyl group which may be substituted with W ^1, W ¹ with an optionally substituted naphthyl group, optionally substituted by W ¹ Represents a thienyl group which may be substituted or a furyl group which may be substituted with W ¹ , and W ¹ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms,
Represents an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group;
Z ¹ represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ² , —C (O) O—, —C (O) NH—, —O—, —S—, —S (O) ₂ — or —C (O) —, and W ² represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy having 1 to 10 carbon atoms. Represents a group. )
As a fourth aspect, in any one of the first to third aspects, the polyhydroxyurea resin of the component (A) further includes at least one structural unit represented by the following formula (3): It relates to the positive photosensitive resin composition described.

(In the formula, X, Ra, Rb, Rc and Rd represent the same meaning as defined in the formula (1), and Q represents a divalent organic group.)
As a fifth aspect, the present invention relates to the positive photosensitive resin composition according to the fourth aspect, wherein Q has a structure represented by the following formulas (4) to (7).

(In Formula (4)-Formula (7),
R ^{7 to} R ⁴⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, a cyano group, a carboxyl group, a phospho group, substituted by a sulfo group, W a phenyl group optionally substituted by ^3, which may be substituted naphthyl group in W ^3, W ³ Represents a thienyl group or a furyl group optionally substituted by W ³ ,
W ³ is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms,
Represents an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group;
Z ^{2 to} Z ¹⁰ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ⁴ , —C (O) O—, —C (O) NH—, -O-, -S-, -S (O) _2- or -C (O)-
W ⁴ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. )
As a sixth aspect, the polyhydroxyurea resin of the component (A) comprises a structural unit represented by the above formula (1) and a structural unit represented by the formula (3) in a molar ratio of the above formula (1). The positive photosensitive resin composition according to the fourth aspect or the fifth aspect, which is contained at a ratio of the structural unit represented by: the structural unit represented by the formula (3) = 70: 30 to 99: 1.
As a seventh aspect, the present invention relates to the positive photosensitive resin composition according to any one of the first to sixth aspects, wherein the component (B) is a naphthoquinone diazide sulfonic acid ester compound.
As an eighth aspect, according to any one of the first aspect to the seventh aspect, containing 0.01 to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A). The present invention relates to a positive photosensitive resin composition.
As a ninth aspect, the present invention relates to the positive photosensitive resin composition according to any one of the first aspect to the eighth aspect, which further contains a crosslinkable compound as the component (C).
As a 10th viewpoint, it is related with the positive photosensitive resin composition as described in a 9th viewpoint containing 5 thru | or 100 mass parts (C) component based on 100 mass parts of said (A) component.
As a eleventh aspect, a positive photosensitive resin, wherein the positive photosensitive resin composition according to any one of the first to tenth aspects is dissolved in at least one solvent. It relates to a composition-containing varnish.
As a 12th viewpoint, it is related with the cured film produced using the positive photosensitive resin composition as described in any one of a 1st viewpoint thru | or a 10th viewpoint.
As a 13th viewpoint, it is related with the cured film produced using the positive photosensitive resin composition containing varnish as described in an 11th viewpoint.
As a 14th viewpoint, it is related with a structure provided with at least one layer which consists of a cured film as described in a 12th viewpoint or a 13th viewpoint on a board | substrate.
The fifteenth aspect relates to a polyhydroxyurea compound containing the structural unit represented by the formula (1) described in the first aspect and having a weight average molecular weight of 3,000 to 200,000.

  The positive photosensitive resin composition of the present invention can form a fine pattern with excellent resolution without causing film loss in unexposed areas, which becomes a problem during development.

[Positive photosensitive resin composition]
Hereinafter, the present invention will be described in more detail.
The positive-type photosensitive resin composition according to the present invention includes at least one kind of poly (ethylene) having a structural unit represented by the formula (1) as the component (A) and having a weight average molecular weight of 3,000 to 200,000. It contains a hydroxyurea resin and a compound that generates an acid by light as component (B).

<(A) component: polyhydroxyurea resin>
The polyhydroxyurea resin of component (A) used in the present invention contains a structural unit represented by the following formula (1).
The weight average molecular weight of the polyhydroxyurea resin is 3,000 to 200,000, and preferably 5,000 to 150,000 from the viewpoint of development time, pattern characteristics, and residue.
The present invention also includes a polyhydroxyurea compound containing a structural unit represented by the following formula (1) and having a weight average molecular weight of 3,000 to 200,000.

In the formula (1), X represents a divalent aliphatic group, alicyclic group or aromatic group, and Y represents a divalent organic group containing an aromatic group substituted with at least one hydroxy group. Represents a group, and Ra, Rb, Rc and Rd each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

  In the formula (1), X is preferably an aliphatic group having 1 to 13 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an aromatic group having 4 to 20 carbon atoms.

Specific examples of the aliphatic group having 1 to 13 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, ethenyl, propenyl, butenyl, pentenyl, Hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecinyl, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl Methyl, heptyloxymethyl, octyloxymethyl, nonyloxymethyl, decyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, pliers Oxyethyl, hexyloxyethyl, heptyloxyethyl, octyloxyethyl, nonyloxyethyl, decyloxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, pentyloxypropyl, hexyloxypropyl, heptyloxypropyl, octyloxypropyl, Nonyloxypropyl, decyloxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, butoxybutyl, pentyloxybutyl, hexyloxybutyl, heptyloxybutyl, octyloxybutyl, nonyloxybutyl, decyloxybutyl, methoxypentyl, ethoxypentyl, Propoxypentyl, butoxypentyl, pentyloxypentyl, hexyloxypentyl, heptyloxy Pentyl, octyloxy, nonyl oxy pentyl, decyl oxy pentyl, 2-methylpropyl, 2-methylbutyl, 3-methylbutyl, 3-methylpentyl, and the like.
Specific examples of the alicyclic group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-butylcyclohexyl, and 4-pentyl. Examples include cyclohexyl, 4-hexylcyclohexyl, 4-heptylcyclohexyl, 4-octylcyclohexyl, 4-nonylcyclohexyl, 4-decylcyclohexyl, 4-propylcyclohexenyl, 3,5,5-trimethylcyclohexyl and the like.
Specific examples of the aromatic group having 4 to 20 carbon atoms include phenyl, naphthyl, biphenyl, anthracenyl, thiophenyl, anilyl, 4,4′-benzophenyl, 4,4′-etherphenyl, 4,4′-carboxy. Examples include phenyl and 4,4′-sulfonylphenyl.

  In the formula (1), Y is preferably a structure represented by the following formula (2), for example.

In the above formula (2), R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy having 1 to 10 carbon atoms. group, hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, a phenyl group optionally be substituted with W ^1, which may be substituted naphthyl group in W ^1, optionally substituted by also thienyl group or W ¹ optionally substituted with W ¹ represents an furyl group.
W ¹ is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group Represents a group, a phospho group or a sulfo group.
Z ¹ represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ² , —C (O) O—, —C (O) NH—, —O—, —S—, —S (O) ₂ — or —C (O) — is represented.
W ² represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

In the above formula (2), Z ¹ is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C (O) NH—, —O—, It is desirable that it is —S (O) ₂ — or —C (O) —.

In addition to the structural unit represented by the above formula (1), the polyhydroxyurea resin as the component (A) may further contain at least one structural unit represented by the following formula (3).
In addition, when including at least one type of structural unit represented by the following formula (3), the mole of the structural unit represented by the above formula (1) and at least one type of structural unit represented by the following formula (3): The ratio is in the range of a molar ratio of the structural unit represented by the formula (1): at least one structural unit represented by the following formula (3) = 70: 30 to 99: 1, from the viewpoint of the photosensitive properties. More preferably, the ratio is in the range of 80:20 to 95: 5.

  In formula (3), X, Ra, Rb, Rc and Rd represent the same meaning as defined in formula (1), and Q represents a divalent organic group.

  In formula (3), Q preferably has a structure represented by the following formula (4) to formula (7).

In the formulas (4) to (7), R ^{7 to} R ⁴⁶ are each independently a hydrogen atom or a carbon atom number of 1
An alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, W ³ optionally substituted by a phenyl group, a W ³ at a naphthyl group which may be substituted, W ³ optionally substituted by at thienyl group, or W ³ optionally substituted furyl group.
W ³ is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group Represents a group, a phospho group or a sulfo group.
Z ^{2 to} Z ¹⁰ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ⁴ , —C (O) O—, —C (O) NH—, —O—, —S—, —S (O) ₂ — or —C (O) — is represented.
W ⁴ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

In the above formulas (4) to (6), Z ^{2 to} Z ⁷ are a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —.
, —C (CF ₃ ) ₂ —, —C (O) NH—, —O—, —S (O) ₂ — or —C (O) — is desirable.
Also in the above formula (7), R ⁴³ to R ⁴⁶ represent a methyl group, Z ⁹ represents -O-, Z ⁸ and Z ¹⁰ are preferably represents a propylene group.

[Production method of polyhydroxyurea]
The (A) component polyhydroxyurea used in the positive photosensitive resin composition of the present invention is a polyhydroxyurea obtained by polymerizing a diisocyanate component and a diamine component.

<Diisocyanate component>
The diisocyanate component that is one component of the monomer constituting the polyhydroxyurea used in the positive photosensitive resin composition of the present invention is not particularly limited, and is an aromatic diisocyanate, aliphatic diisocyanate, or fat. Cyclic isocyanates or mixtures thereof can be used. Preferably, an aliphatic diisocyanate or an alicyclic diisocyanate is used.

Aliphatic diisocyanates include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, hexamethylene diisocyanate, 2, 2,4-trimethylhexamethylene diisocyanate 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, decamethylene diisocyanate Examples thereof include, but are not limited to, nate and lysine diisocyanate.
Examples of the alicyclic diisocyanate include isophorone diisocyanate, cyclohexane-1,4-diisocyanate, norbornane diisocyanate methyl, bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanate methyl). ) Cyclohexane, methylcyclohexane diisocyanate and the like, but are not limited thereto.

<Diamine component>
The diamine component which is one component of the monomer constituting the polyhydroxyurea used in the positive photosensitive resin composition of the present invention is a compound having a structure represented by the following general formula (8), Y represents a divalent organic group containing an aromatic group substituted with at least one hydroxy group, and preferably a divalent organic group containing two or more benzene rings substituted with at least one hydroxy group. These structures are not particularly limited as long as they are divalent organic groups including an aromatic group substituted with at least one OH group.
Moreover, in manufacture of the polyhydroxy urea resin used for this invention, diamine may use 1 type of compounds which have a structure represented by a following formula, or multiple types may be used for it.

Specific examples of the diamine having an aromatic group substituted with at least one OH group represented by the above formula (8) include 2,4-diaminophenol, 3,5-diaminophenol, and 2,5-diaminophenol. 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, 3,3′-dihydroxybenzidine (3BP), 3,3′-diamino-4,4′-dihydroxybiphenyl (4BP), 3,3′-diamino -2,2'-dihydroxybiphenyl (2BP), bis (3-amino-4-hydroxyphenyl) methane (BAPF), bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5 -Dihydroxyphenyl) methane, 2,2'-bis (3-amino-4-hydroxyphenyl) propane (BAPA), 2,2'-bis ( 4-amino-3-hydroxyphenyl) propane, 2,2′-bis (4-amino-3,5-dihydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane ( BAHF), 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 2,2-bis [4 -(3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane, (3-amino-4-hydroxy) phenyl (3-amino-4-hydroxy) anilide (AHPA), bis (3-amino-4-hydroxyphenyl) ) Ether (AHPE), bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-) 3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) sulfide (BSDA), bis (4-amino-3-hydroxyphenyl) sulfide, bis (4-amino-3,5-dihydroxyphenyl) ) Sulfide, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 3,3′-diamino -4,4'-dihydroxybenzophenone (AHPK), 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5, 5′-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis 3-amino-4-hydroxyphenoxy) benzene, 1,4-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- ( 3-amino-4-hydroxyphenoxy) phenyl] sulfone, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2-amino-4- (3- (4-amino-3-hydroxyphenoxy) Phenoxy) phenol, 5,5 ′-(1,3-phenylenebis (oxy)) bis (2-aminophenol), 5,5 ′-(1,4-phenylenebis (oxy)) bis (2-aminophenol) ), 2-amino-4- (4- (4-amino-3-hydroxyphenoxy) phenoxy) phenol, 2-amino-4- (3- (3- (4-amino-3- Hydroxyphenoxy) phenoxy) phenoxy) phenol, 5,5 ′-(3,3′-oxybis (3,1-phenylene) bis (oxy)) bis (2-aminophenol), 4,4 ′-(4,1 '-Oxybis (4,1-phenylene) bis (oxy)) bis (2-aminophenol), 2-amino-4- (4- (4- (4-amino-3-hydroxyphenoxy) phenoxy) phenoxy) phenol However, it is not limited to these.
In particular, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) may be mentioned as a more suitable compound from the viewpoint of the solubility of the polymer obtained and the photosensitive properties.

In addition to the diamine containing an aromatic group substituted with at least one OH group as described above, other diamines can also be used.
Although it does not specifically limit as another diamine component, Preferably it is a diamine containing an aromatic group, especially a diamine containing one or more benzene rings or a siloxane-containing diamine.
When the other diamine component is used, the diamine component containing the aromatic group substituted with the at least one OH group: the other diamine component has a molar ratio of 70:30 to 99: 1, and is photosensitive. From the viewpoint of characteristics, it is more preferable to use in the range of 80:20 to 95: 5.

Examples of the diamine containing an aromatic group include 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane or 2,2-bis (3-amino-4-toluyl) hexafluoropropane, p-phenylenediamine M-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4-methylene-
Bis (2-methylaniline), 4,4′-methylene-bis (2,6-dimethylaniline), 4,4-methylene-bis (2,6-diethylaniline), 4,4′-methylene-bis ( 2-
(Isopropyl-6-methylaniline) 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine, m- Tolidine, 3,3 ′, 5,5′-tetramethylbenzidine, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3- Benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4 -Amino-3-carboxyphenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3 ' Dicarboxylate biphenyl, 4,4'-diamino -3
, 3′-dicarboxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethoxybiphenyl, 1,4-bis (4-amino-3- Carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4-amino-3) -Carboxyphenoxy) phenyl] propane and the like, but is not limited thereto. In addition, from the viewpoint of the solubility and photosensitive properties of the resulting polymer, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4′-diaminodiphenyl ether, and 4,4′-diaminodiphenylmethane are desirable.

Siloxane-containing diamines are suitable for use as other diamines because they can improve the adhesion of the coating film made of polyhydroxyurea resin to the substrate.
As such a siloxane-containing diamine, for example, bis (3-aminoalkyl) -1,1,3,3-tetramethyldisiloxane is desirable. From the viewpoint of adhesion to the substrate and solubility, bis (3-amino Propyl) -1,1,3,3-tetramethyldisiloxane (APDS) is more preferred.

<Production method of polyhydroxyurea>
The polyhydroxyurea of the component (A) of the present invention can be produced by reacting the diisocyanate component and the diamine component at -78 to 150 ° C, preferably -5 to 100 ° C for 1 to 24 hours.
In addition, the molar ratio of the diisocyanate component and the diamine component used at the time of production is such that if the diamine component is too much, the molecular weight will not increase, and if it is too little, gelation will occur and it will become insoluble, so the diisocyanate component: Diamine component is preferably 1: 0.5 to 3.0 (molar ratio), more preferably diisocyanate component: diamine component = 1: 0.8 to 2.0 (molar ratio), It is most preferable to use the isocyanate component: diamine component = 1: 1.0 to 1.2 (molar ratio).

The solvent used in the production of the above polyhydroxyurea is not particularly limited. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone can be used because the resulting polymer has high solubility. N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, γ-butyrolactone and the like are preferable.
Further, if the concentration of the monomer component is too high at the time of polymerization, the handleability is deteriorated, and if it is too low, the molecular weight of the polymer to be produced may not increase, so preferably 1 to 50% by mass, more preferably 5 to 40%. It is produced at a concentration of the monomer components (total) of 8% by weight, particularly preferably 8-30% by weight.

Moreover, you may add other solvents, for example, poor solvents, such as butyl cellosolve, toluene, and methanol, within the range which a polymer melt | dissolves.
Further, in order to make the molecular weight of the polymer appropriate, the reaction system may be placed in a nitrogen atmosphere, or the reaction may be performed while bubbling nitrogen through a solvent in the reaction system.

<(B) component: Photoacid generator>
The compound (photoacid generator) that generates an acid by the light of the component (B) generates an acid directly or jointly by irradiation of light used for exposure or the like, and dissolves the light irradiated portion in an alkali developer. The type and structure are not particularly limited as long as they have a function of enhancing the properties. Moreover, a photo-acid generator can also be used 1 type or in combination of 2 or more types.

  As the photoacid generator of the component (B), any of the conventionally known photoacid generators can be applied, and specific examples thereof include o-quinonediazide compounds, allyldiazonium salts, diallyliodonium salts, triallylsulfonium. Examples thereof include salts, o-nitrobenzyl esters, p-nitrobenzyl esters, trihalomethyl group-substituted s-triazine derivatives, and imide sulfonate derivatives.

  Moreover, a sensitizer can be used together with the photo-acid generator of (B) component as needed. Examples of such sensitizers include, but are not limited to, perylene, anthracene, thioxanthone, Michler ketone, benzophenone, fluorene, and the like.

Among the photoacid generators of the component (B), an o-quinonediazide compound is desirable from the viewpoint that high sensitivity and high resolution can be obtained in a coating film obtained using a positive photosensitive resin composition.
The o-quinonediazide compound is usually obtained by a condensation reaction of o-quinonediazidesulfonyl chloride with a compound having at least one group selected from a hydroxy group and an amino group in the presence of a basic catalyst. Obtained as an acid ester or o-quinonediazidesulfonamide.

  Examples of the o-quinonediazide sulfonic acid component constituting the o-quinonediazidesulfonyl chloride include 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2-naphthoquinone-2-diazide-5-sulfonic acid. 1,2-naphthoquinone-2-diazide-6-sulfonic acid and the like.

Specific examples of the compound having a hydroxy group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, o-methoxyphenol, 4,4-isopropylidenediphenol, 1,1- Bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4 ′, 4 ″ -trihydroxytriphenylmethane, 1,1,1- Tris (4-hydroxyphenyl) ethane, 4,4 ′-[1
-[4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, methyl 3,4,5-trihydroxybenzoate, propyl 3,4,5-trihydroxybenzoate, 3 , 4,5-trihydroxybenzoic acid isoamyl ester, 3,4,5-trihydroxybenzoic acid-2-ethylbutyl ester, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ′ , 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, phenol compounds such as 2,3,4,2 ', 4'-pentahydroxybenzophenone, ethanol, 2-propanol, 4, -Butanol, cyclohexanol, ethylene glycol, propylene glycol, polyethylene Glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, include aliphatic alcohols such as butyl lactate.

Examples of the compound having an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, Examples thereof include anilines such as 4,4′-diaminodiphenylmethane and 4,4′-diaminodiphenyl ether, and aminocyclohexane.

  Furthermore, specific examples of the compound having both a hydroxy group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, and 2,4-diamino. Phenol, 4,4′-diamino-4 ″ -hydroxytriphenylmethane, 4-amino-4 ′, 4 ″ -dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether Bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, bis (4-amino-3-carboxy-5-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-carboxy-5) -Hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) Sulfonyl) amino phenols such as hexafluoropropane, 2-aminoethanol, 3-aminopropanol, mention may be made of alkanolamines, such as 4-amino-cyclohexanol.

  When the o-quinonediazidosulfonyl chloride and a compound having at least one selected from a hydroxy group and an amino group are subjected to a condensation reaction, a part or all of the hydroxy group or amino group of the compound is o-quinonediazidesulfonyl chloride o-quinonediazide A disubstituted, trisubstituted, tetrasubstituted or pentasubstituted o-quinonediazide compound substituted with a sulfonyl group is obtained. When such an o-quinonediazide compound is used as one component of a positive photosensitive resin composition, the above-mentioned polysubstituted o-quinonediazide compound alone or two or more polysubstituted selected from the above polysubstituted products is used. Generally used as a mixture of bodies.

  Among the o-quinonediazide compounds described above, the coating residue obtained using the positive photosensitive resin composition has a good balance of difference in development solubility between the exposed and unexposed areas, and the development residue at the bottom of the pattern during development From the viewpoint that there is no (residue at the pattern edge part), o-quinonediazide sulfonic acid ester of p-cresol, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] Phenyl] ethylidene] bisphenol o-quinonediazide sulfonate, methyl 3,4,5-trihydroxybenzoate o-quinonediazide sulfonate, 2,3,4-trihydroxybenzophenone o-quinonediazide sulfonate, or O-Quinonediazi of 2,3,4,4'-tetrahydroxybenzophenone Sulfonic acid ester is preferable, be used those compounds singly, or may be mixed and used as the two or more selected arbitrarily from these compounds.

  The content of the photoacid generator as the component (B) used in the present invention is 0.01 to 100 parts by mass based on 100 parts by mass of the component (A). In the coating film obtained from the positive photosensitive resin composition of the present invention, the balance of the developer solubility difference between the exposed area and the unexposed area is improved, and further, the sensitivity of the coating film and the coating film obtained from the coating film are obtained. From the viewpoint of the mechanical properties of the cured film to be obtained, the content of the photoacid generator as the component (B) is particularly preferably 50 parts by mass or less, and more preferably 30 parts by mass or less.

<(C) component: crosslinkable compound>
The positive photosensitive resin composition of the present invention can contain a crosslinkable compound as the component (C). The crosslinkable compound of component (C) is a component of component (A) in the step of converting a coating film obtained using the positive photosensitive resin composition of the present invention into a cured film (hereinafter referred to as final curing). A compound having a group capable of reacting with an organic group contained in a polyhydroxyurea resin, and being soluble in an alkaline developer in a coating step obtained by using the positive photosensitive resin composition If it is, it will not be specifically limited.

Examples of such a crosslinkable compound (C) include a maleimide compound. The structure of the maleimide compound is not particularly limited as long as the maleimide moiety is directly connected to an aromatic ring and a hydrogen atom is directly connected to an adjacent aromatic carbon.
Examples of the maleimide compound having a structure in which a maleimide moiety is directly connected to an aromatic ring and a hydrogen atom is directly connected to an adjacent aromatic carbon include a compound represented by the following formula (9).

In the above formula (9), R ⁴⁷ represents a divalent group, and R ^{48 to} R ⁵⁷ each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms.

Among these, in the formula (9), a maleimide compound in which R ⁴⁷ has a structure represented by the following formula (10) is desirable.

In the above formula (10), h and i each independently represent 0 or 1, and R ^{58 to} R ⁶⁰ each independently represent an organic group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, or nitrogen. Represents a divalent group having an atom.
In particular, in the formula (10), it is desirable that h and i are 1, R ⁵⁸ and R ⁶⁰ are oxygen atoms, and R ⁵⁹ represents a dimethylmethylene group.

Specific examples of the maleimide compound represented by the above formula (9) include 2,2-bis (3-amino-4-maleimide) hexafluoropropane, 4,4′-dimaleimide diphenyl ether, and 3,4′-dimaleimide. Diphenyl ether, 3,3′-dimaleimide diphenyl ether, 4,4′-dimaleimide diphenyl sulfide, 4,4′-dimaleimide diphenylmethane, 3,4′-dimaleimide diphenylmethane, 3,3′-dimaleimide diphenylmethane, 4, 4-methylene-bis (2-methylmaleimide), 4,4′-dimaleimidodiphenylsulfone, 3,3′-dimaleimidodiphenylsulfone, 1,4′-bis (4-maleimidophenoxy) benzene, 1,3 ′ -Bis (4-maleimidophenoxy) benzene, 1,3'-bis (4-maleimidopheno) ) Benzene, bis [4- (4-maleimide phenoxy) phenyl] sulfone, bis [4- (3-maleimido phenoxy) phenyl] sulfone, bis [3- (4-maleimido phenoxy) phenyl] sulfone, bis [
Such as 3- (3-maleimidophenoxy) phenyl] sulfone, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, etc. Examples include, but are not limited to, compounds.
Of the above compounds, 4,4′-dimaleimidodiphenylmethane and 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane are desirable from the viewpoint of easy availability, and further from the viewpoint of photosensitive properties. 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane is more preferable.

The maleimide compound of the crosslinkable compound (C) in the present invention can be used alone or in combination of two or more.
In addition, the content of the crosslinkable compound (C) in the positive photosensitive resin composition of the present invention is not particularly limited, but is 5 to 100 parts by mass based on 100 parts by mass of the polyhydroxyurea resin of component (A). Yes, more preferably 5 to 20 parts by mass.

<Other additives>
Furthermore, as long as the positive photosensitive resin composition of the present invention does not impair the effects of the present invention, a surfactant, a rheology modifier, an adhesion aid such as an organic silane compound or an aluminum chelate compound, if necessary, Pigments, dyes, storage stabilizers, antifoaming agents, or dissolution accelerators such as polyphenols and polycarboxylic acids can be contained.

<Adhesion aid (compound for enhancing adhesion)>
The positive photosensitive resin composition of the present invention can contain an organosilane compound or an aluminum chelate compound in order to enhance the adhesion between the coating film and cured film obtained using the composition and the substrate. As such an organic silane compound and an aluminum chelate compound, for example, commercially available products such as those manufactured by GE Toshiba Silicone Co., Ltd. and Shin-Etsu Chemical Co., Ltd. can be used, and these are more preferable because they can be easily obtained.
Examples of the organic silane compound include vinyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldiethoxyethylsilane, 3-glycidoxypropylethoxydiethylsilane, and 3-glycidoxypropyl. Trimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylmethoxydimethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethoxydimethylsilane, 3-methacryloxypropyldimethoxymethylsilane 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropylmethoxydimethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyldisilane Butoxyethyl silane, and 3-aminopropyl ethoxy diethyl silane.
Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like.
In this invention, 1 type chosen from an organosilane compound and an aluminum chelate compound can be used individually or in combination of 2 or more types.
Among these, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-aminopropyltriethoxysilane are more preferable.
The content of the compound selected from the organic silane compound and the aluminum chelate compound in the positive photosensitive resin composition of the present invention is not particularly limited, but the coating film obtained by using the positive photosensitive resin composition and curing From the point which can fully improve the adhesiveness of a film | membrane and a board | substrate, Preferably it is 0.1 mass part or more with respect to 100 mass parts of polyhydroxyurea resin (A), More preferably, it is 0.5 mass part or more. When the content of the compound selected from the organic silane compound and the aluminum chelate compound is 30 parts by mass or less, the storage stability of the positive photosensitive resin composition is good and the composition is obtained using the composition. Since there is no residue at the bottom of the pattern, it is preferable, and the content is more preferably 20 parts by mass or less.

<Surfactant>
The positive photosensitive resin composition of the present invention may further contain a surfactant in order to improve its coating property and to improve the uniformity of the coated film surface. The surfactant used for this purpose is not particularly limited, and a fluorine-based surfactant, a silicon-based surfactant, a nonionic surfactant, and the like can be used. As this type of surfactant, for example, commercially available products such as those manufactured by Sumitomo 3M Co., Ltd., Dainippon Ink Chemical Co., Ltd., or Asahi Glass Co., Ltd. can be easily obtained. is there.
Among these, a fluorosurfactant is preferable because it has a high effect of improving applicability. More preferable specific examples include F-top EF301, EF303, EF352 (manufactured by Gemco), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 ( Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), FTX-206D, FTX-212D, FTX-218, FTX- Fluorosurfactants such as 220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, etc., and other surfactant series (manufactured by Neos Co., Ltd.).
The said surfactant can be used individually by 1 type or in combination of 2 or more types.
Moreover, when surfactant is used, the content is 0.2 mass% or less normally in 100 mass% of positive photosensitive resin compositions, Preferably it is 0.1 mass% or less. Even if the amount of the surfactant used is set to an amount exceeding 0.2% by mass, the effect of improving the coating property becomes dull and not economical.

<Organic solvent>
The positive photosensitive resin composition of the present invention is usually used in the form of a varnish after being dissolved in an organic solvent as a solvent. As the organic solvent used in the positive photosensitive resin composition-containing varnish of the present invention, the (A) component polyhydroxyurea resin and the (B) component compound that generates acid by light, and optionally (C ) Component cross-linking compound and other additives (adhesive adjuvant, surfactant, etc.) can be uniformly dissolved, and the components are not particularly limited as long as these components are compatible with each other.

Specific examples of the organic solvent include, for example, acetone, methanol, ethanol, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, and ethyl cellosolve. , Butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, butyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol , Propylene glycol monoacetate, propylene glycol Monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol-tert-butyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monopropyl ether acetate, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl Ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone N-vinylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, n-hexane, n-pentane, n-octane, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, diethyl ether, cyclohexanone, methyl lactate, lactic acid Ethyl, butyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3- Methyl Tokishipuropion acid, 3-methoxy ethyl propionate, 3-ethoxy propionate, 3-methoxy propionic acid, 3-methoxy propionic acid propyl, 3-methoxy propionic acid butyl, and the like diglyme.

These organic solvents may be used alone or in combination of two or more.
Among these, the organic solvent includes methyl ethyl ketone, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, N, N-dimethyl, because it is easy to handle in the positive photosensitive resin composition. One or a mixture of two or more selected from acetamide, N-2-methylpyrrolidone, γ-butyrolactone, ethyl lactate and butyl lactate is preferred.

<Positive photosensitive resin composition>
The positive photosensitive resin composition of the present invention contains (A) component polyhydroxyurea resin, (B) component photoacid generator, and optionally (C) crosslinkable compound and surfactant. It is a composition which can further contain one or more of the other additives.

Among these, preferred examples of the positive photosensitive resin composition of the present invention are as follows.
[1]: A positive photosensitive resin composition containing 0.01 to 100 parts by mass of component (B) based on 100 parts by mass of component (A).
[2]: A positive photosensitive resin composition further containing 5 to 100 parts by mass of component (C) based on 100 parts by mass of component (A) in the composition of [1] above.

  The method for obtaining the positive photosensitive resin composition of the present invention is not particularly limited. Since this type of composition is usually used in the form of a varnish, the positive photosensitive resin composition of the present invention generally generates an acid by (A) component polyhydroxyurea resin and (B) component light. It is prepared by dissolving the generated compound and other components such as the crosslinking compound of component (C) in the organic solvent as desired.

In preparing the positive photosensitive resin composition of the present invention, the polyhydroxyurea resin of component (A) is produced, that is, a diisocyanate component and a diamine component are polymerized in an organic solvent. The obtained reaction solution can also be used as it is. In addition, as said organic solvent used at this time, said organic solvent is mentioned. In this case, when the component (B) is added to the reaction solution of the component (A) to obtain a uniform varnish, the organic solvent may be additionally added for the purpose of adjusting the concentration. At this time, the organic solvent used at the time of manufacture of (A) component and the organic solvent used for density | concentration adjustment may be the same, and may differ.
Moreover, when using a plurality of types of organic solvents, not only a plurality of types of organic solvents are mixed and used first, but also a plurality of types of organic solvents can be added separately.
Thus, the prepared positive photosensitive resin composition solution is preferably used after being filtered using a filter having a pore diameter of about 0.2 μm.

The solid content concentration of the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved. In general, when a solution of a positive photosensitive resin composition having a solid content concentration arbitrarily selected from the range of a solid content concentration of 1 to 50% by mass is used, a coating film can be easily formed. Here, solid content means the thing remove | excluding the organic solvent from all the components of the positive photosensitive resin composition.

<Coating film and cured film>
In general, for example, the positive photosensitive resin composition of the present invention is made of an ITO substrate, a silicon wafer, a glass plate, a ceramic substrate, an oxide film, a nitride film, or the like by a known method such as spin coating, dipping, or printing. A coating film made of the positive photosensitive resin composition of the present invention can be formed by coating on the material and then preliminary drying at a temperature of 60 ° C. to 160 ° C., preferably 70 ° C. to 130 ° C.

  After the coating film is formed, the coating film is exposed using a mask having a predetermined pattern, for example, with ultraviolet light, and developed with an alkali developer, whereby the exposed portion is washed away, thereby sharpening the end face (clear) A relief pattern is formed on the substrate.

The alkaline developer used here is not particularly limited as long as it is an alkaline aqueous solution. For example, an aqueous solution of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, tetramethylammonium hydroxide, or the like. And aqueous solutions of quaternary ammonium hydroxides such as tetraethylammonium hydroxide and choline, and aqueous amine solutions such as ethanolamine, propylamine and ethylenediamine.
The concentration of the alkaline developer is generally 10% by mass or less, and an industrial aqueous solution of 0.1 to 3.0% by mass is used industrially. The alkaline developer can also contain alcohols or surfactants, and these are preferably contained in an amount of about 0.05 to 10% by mass.

  In the development step, the temperature of the alkali developer can be arbitrarily selected. However, when the positive photosensitive resin composition of the present invention is used, the exposed portion is highly soluble, so that the alkali development can be easily performed at room temperature. Development with a liquid can be performed.

  A relief pattern having low water absorption, excellent electrical characteristics, and good heat resistance and chemical resistance by heat-treating (baking) the substrate having the relief pattern thus obtained at a temperature of 180 ° C. to 400 ° C. The cured film which has can be obtained.

  Since the cured film obtained from the positive photosensitive resin composition of the present invention has such excellent effects, it can be used for electric / electronic devices, semiconductor devices, display devices, and the like. In particular, a cured film obtained from the positive photosensitive resin composition of the present invention has a characteristic effect that the reliability of an organic EL element (a kind of LED (Light-Emitting Diode) element) is high, and thus a light-emitting element It is very useful as an insulating film and partition material for organic EL elements, where damage to the metal is a major problem, or for buffer coating where the ion migration of copper wiring is greatly affected by the water absorption of the insulating film in semiconductor packages. is there.

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

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Diamine component>
BAHF: 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane APDS: bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane <diisocyanate component>
HMDI: hexamethylene diisocyanate IPDI: isophorone diisocyanate BIMB: 1,3-bis (isocyanatomethyl) benzene BICH: 1,3-bis (isocyanatomethyl) cyclohexane PDI: 1,4-phenylene diisocyanate MDDI : Methylenediphenyl diisocyanate <organic solvent>
GBL: γ-butyrolactone NMP: N-2-methylpyrrolidone <photoacid generator>
P200: manufactured by Toyo Gosei Kogyo Co., Ltd. P-200 (trade name) 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol 1 mol and 1 , 2-naphthoquinone-2-diazide-5-sulfonyl chloride A photosensitizer synthesized by a condensation reaction <surfactant>
Megafuck R-30: manufactured by Dainippon Ink & Chemicals, Inc.

[Measurement of number average molecular weight and weight average molecular weight]
In accordance with the following synthesis examples, the weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of the polymer were measured using GPC apparatus (Shodex (registered trademark) columns KF803L and KF805L) manufactured by JASCO Corporation and dimethylformamide as the elution solvent. The measurement was performed under the condition that the column was eluted at a flow rate of 1 ml / min (column temperature: 50 ° C.). Mw is expressed in terms of polystyrene.

[Measurement of coating film component analysis]
For component analysis of the coating film, GC-MS (JMS-700T (registered trademark) column TC-WAX) manufactured by JEOL Ltd. was used. 10 mg was weighed as a sample from various coating films, the initial temperature and the final temperature were 60 ° C. and 220 ° C. (temperature increase 10 / min), respectively, and the resulting components were detected.

[Production example]
<Production Example 1: Production of polyhydroxyurea (P1)>
13.0 g (0.0358 mol) of BAHF and 0.98 g (0.0039 mol) of ADPS were dissolved in 70 g of GBL, and 10 g of GBL in which 5.98 g (0.0395 mol) of HMDI was dissolved was added. The reaction was performed at 23 ° C. for 24 hours.
Mw of the obtained polymer was 49,800 and molecular weight distribution was 2.25.
In addition, solid content was computed from the preparation ratio of each component.

<Production Examples 2 to 7: Production of various polyhydroxyureas (P2-P7)>
Polymers were produced in the same manner as in Production Example 1 using various diamines and diisocyanates in various solvents. Table 1 shows the diamine and diisocyanate used at this time, the type and amount of solvent used, the Mw and molecular weight distribution of the polymer obtained, and the solid content of the polymer solution obtained.
In addition, solid content was computed from the preparation ratio of each component.

<Comparative Production Example 1: Production of polyhydroxyurea (H1)>
13.9 g (0.0380 mol) of BAHF was dissolved in 80 g of NMP, where PDI was dissolved.
6.08 g (0.0380 mol) was added and reacted at 23 ° C. for 24 hours. However, PDI did not react and the desired polymer was not obtained.
Next, this solution was reacted at 90 ° C. for 24 hours, but PDI did not react and the desired polymer could not be obtained.

<Comparative Production Example 2: Production of polyhydroxyurea (H2)>
BAHF 11.9g (0.0324mol) was melt | dissolved in NMP 80g, MDDI 8.11g (0.0324mol) was added here, and it was made to react at 23 degreeC. Ten minutes after the start of the reaction, the solution gelled and the desired polymer was not obtained.

[Examples 1 to 7: Preparation of positive photosensitive resin composition]
Using the polymer solutions obtained in the above Production Examples 1 to 7, according to the composition shown in Table 2, the solution of (A) component (polymer solution), (B) component (photoacid generator), additive solvent and fluorine 0.0002 g of a surfactant (Megafac R-30) is mixed at a predetermined ratio, and stirred at room temperature for 3 hours or more to obtain a uniform solution. Varnish) was prepared.

[Photosensitive characteristic evaluation: Examples 1 to 7]
About each obtained positive photosensitive resin composition of Example 1 thru | or 7, the photosensitive characteristic was evaluated with the following method. The obtained results are shown in Table 3.

<1. Film thickness before development>
The positive photosensitive resin composition is applied onto an ITO substrate having a level difference of 50 mm × 50 mm using a spin coater and then pre-baked on a hot plate at a temperature of 130 ° C. for 120 seconds. A film was formed. The film thickness was measured using a contact-type film thickness measuring device (Dektak 3ST manufactured by ULVAC).

<2. Development time, film thickness after development, resolution (line width)>
Ultraviolet light was applied to the obtained coating film for 16 seconds (100 mJ / cm ² ) by means of an ultraviolet irradiation device PLA-600 manufactured by Canon Inc. through a line / space mask of 1/1 (μm) to 100/100 (μm). Irradiated. After exposure, the film was immersed in a 23 ° C. aqueous tetramethylammonium hydroxide solution (2.38 mass%) for the development time shown in Table 3 for development, then washed pure for 20 seconds, and then the film thickness after development. Was measured.
Moreover, the coating film after image development was observed with the optical microscope, and the minimum line | wire width in which the line / space was formed without pattern peeling was made into the resolution.

  As shown in Table 3, the cured films obtained from the positive photosensitive resin compositions of Examples 1 to 7 had a small film loss in the unexposed areas, and a positive pattern was obtained with a resolution of 20 μm or less.

Claims (15)

As component (A), at least one polyhydroxyurea resin containing a structural unit represented by the following formula (1) and having a weight average molecular weight of 3,000 to 200,000, and component (B) A positive photosensitive resin composition comprising a compound capable of generating an acid by heating.

(Wherein X represents a divalent aliphatic group, alicyclic group or aromatic group,
Y represents a divalent organic group containing an aromatic group substituted with at least one hydroxy group;
Ra, Rb, Rc and Rd each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ) The positive photosensitive resin according to claim 1, wherein X represents an aliphatic group having 1 to 13 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an aromatic group having 4 to 20 carbon atoms. Resin composition. The positive photosensitive resin composition according to claim 1 or 2, wherein Y has a structure represented by the following formula (2).

(In the formula (2),
R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, a phenyl group which may be substituted with W ^1, W ¹ with an optionally substituted naphthyl group, optionally substituted by W ¹ Represents a thienyl group which may be substituted or a furyl group which may be substituted with W ¹ , and W ¹ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms,
Represents an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group;
Z ¹ represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ² , —C (O) O—, —C (O) NH—, —O—, —S—, —S (O) ₂ — or —C (O) —, and W ² represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy having 1 to 10 carbon atoms. Represents a group. ) The positive photosensitive resin according to any one of claims 1 to 3, wherein the polyhydroxyurea resin as the component (A) further contains at least one structural unit represented by the following formula (3). Resin composition.

(In the formula, X, Ra, Rb, Rc and Rd represent the same meaning as defined in the formula (1), and Q represents a divalent organic group.) The positive photosensitive resin composition according to claim 4, wherein the Q has a structure represented by the following formulas (4) to (7).

(In Formula (4)-Formula (7),
R ^{7 to} R ⁴⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, a cyano group, a carboxyl group, a phospho group, substituted by a sulfo group, W a phenyl group optionally substituted by ^3, which may be substituted naphthyl group in W ^3, W ³ Represents a thienyl group or a furyl group optionally substituted by W ³ ,
W ³ is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms,
Represents an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group;
Z ^{2 to} Z ¹⁰ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with W ⁴ , —C (O) O—, —C (O) NH—, -O-, -S-, -S (O) _2- or -C (O)-
W ⁴ represents an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. ) The polyhydroxyurea resin of the component (A) is a structure represented by the above formula (1) in a molar ratio between the structural unit represented by the above formula (1) and the structural unit represented by the formula (3). 6. The positive photosensitive resin composition according to claim 4, wherein the positive photosensitive resin composition is contained at a ratio of unit: structural unit represented by formula (3) = 70: 30 to 99: 1. The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the component (B) is a naphthoquinonediazide sulfonic acid ester compound. The positive photosensitive resin according to any one of claims 1 to 7, comprising 0.01 to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A). Composition. Furthermore, the positive photosensitive resin composition as described in any one of Claims 1 thru | or 8 which contains a crosslinkable compound as (C) component. The positive photosensitive resin composition according to claim 9, comprising 5 to 100 parts by mass of the component (C) based on 100 parts by mass of the component (A). A positive photosensitive resin composition-containing varnish, wherein the positive photosensitive resin composition according to any one of claims 1 to 10 is dissolved in at least one kind of solvent. The cured film produced using the positive photosensitive resin composition as described in any one of Claims 1 thru | or 10. The cured film produced using the positive photosensitive resin composition containing varnish of Claim 11. A structure comprising at least one layer made of the cured film according to claim 12 or 13 on a substrate. A polyhydroxyurea compound comprising the structural unit represented by the formula (1) according to claim 1 and having a weight average molecular weight of 3,000 to 200,000.