TWI437025B - An alkali-soluble polymer, a photosensitive resin composition comprising the same, and a use thereof - Google Patents

Description

Alkali-soluble polymer, photosensitive resin composition containing the same, and use thereof

The present invention relates to a photosensitive resin composition which is used as a heat-resistant resin precursor for a surface protective film of a semiconductor device and an interlayer insulating film, and a cured resin pattern having heat resistance using the photosensitive resin composition. A method and a semiconductor device having the hardened concave-convex pattern.

A polyimide resin having excellent heat resistance, electrical properties, mechanical properties, and the like is widely used for a surface protective film of a semiconductor device and an interlayer insulating film. Currently, most of the polyimine resin is provided in the form of a photosensitive polyimide intermediate composition. In the process of manufacturing a semiconductor device, the precursor composition is applied to a substrate such as a germanium wafer, patterned by active light, developed, and subjected to thermal imidization treatment, thereby easily A surface protective film, an interlayer insulating film, or the like which is a part of the semiconductor device is formed. That is, a manufacturing process of a semiconductor device using a photosensitive polyimide precursor composition and a prior use non-photosensitive polyimide precursor composition which is required to be patterned by a lithography method after forming a surface protective film or the like Compared with the manufacturing process of the object, the steps can be greatly shortened.

However, in the development step of the photosensitive polyimide intermediate composition, it is necessary to use an organic solvent such as N-methyl-2-pyrrolidone as a developing solution, and it is required to remove organic solvents due to an increase in environmental problems in recent years. . In response to this demand, various heat-resistant photosensitive resin materials which can be developed with an alkaline aqueous solution in the same manner as the photoresist have recently been proposed.

In the following Patent Documents 1 and 2, there is disclosed a method in which a hydroxypolyamine which is soluble in an alkaline aqueous solution of a heat resistant resin after curing, for example, polybenzoic acid is disclosed. A PBO precursor composition obtained by mixing a azole (hereinafter also referred to as "PBO") precursor with a photoacid generator such as a naphthoquinone diazide compound is used as the photosensitive resin composition.

The developing mechanism of the photosensitive resin composition utilizes a mechanism in which the dissolution rate of the naphthoquinonediazide compound and the PBO precursor in the unexposed portion is small in an alkaline aqueous solution, whereas the photosensitive property is exposed by exposure. The chemical change of the diazonium compound is a hydrazine carboxylic acid compound, so that the dissolution rate of the exposed portion in the alkaline aqueous solution is increased. A concave-convex pattern including an unexposed portion can be produced by using a difference between the exposure portion and the unexposed portion with respect to the dissolution rate of the developer.

The PBO precursor composition can form a positive concavo-convex pattern by development using exposure and an aqueous alkaline solution. Generated by heat The azole ring, the hardened PBO film has the same thermosetting film characteristics as the polyimide film, and therefore the PBO precursor composition attracts attention as a promising substitute material for the organic solvent-developed polyimide intermediate composition. .

Similarly, in the following Patent Documents 3 and 4, a photosensitive resin composition containing polyamic acid, a polyphthalate, and a naphthoquinonediazide compound which can be subjected to alkaline development is disclosed.

Further, in the following Patent Document 5, a photosensitive resin containing a phenolic hydroxyl group-containing solvent-soluble polyimine (hereinafter also referred to as "soluble PI") and a naphthoquinonediazide compound capable of performing alkaline development is proposed. combination.

Further, in the following Patent Documents 6 and 7, a PBO precursor resin in which a crosslinking group is introduced into a branch by using a carboxylic acid derivative is disclosed. Further, in the following Patent Document 8, it is proposed to use an amine compound derivative in a branch. A PI precursor resin composition into which a crosslinking group is introduced.

Further, Patent Document 9 below proposes a photosensitive resin composition comprising a PBO precursor polymer containing an ester bond and a naphthoquinonediazide compound.

[previous technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 01-046862

[Patent Document 2] Japanese Patent Laid-Open Publication No. SHO 63-096162

[Patent Document 3] Japanese Patent Laid-Open No. 52-013315

[Patent Document 4] Japanese Patent Laid-Open No. 02-181149

[Patent Document 5] International Publication No. 07/029614

[Patent Document 6] International Publication No. 05/068535

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2002-167435

[Patent Document 8] Japanese Patent Laid-Open No. Hei 11-024268

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2007-171945

The prior art described in the above documents has room for improvement in the following aspects.

The surface protective film and the interlayer insulating film of the conventional semiconductor element have a problem in that, compared with the surface protective film and the interlayer insulating film containing the photosensitive polyimide precursor composition, the sensitivity is caused by the problem of the absorption wavelength accompanying the photosensitizer. Lower; and in the PBO precursor and PI precursor accompanying cyclization, the hardening shrinkage caused by cyclization is large, and the glass transition temperature before cyclization is lower, so the concave and convex pattern obtained after development is heated. In the processing (hereinafter referred to as "hardening"), the taper angle is low. Therefore, in the manufacturing process of the semiconductor device, metal wiring or the like is exposed, and the reliability of the semiconductor package is lowered.

Further, in the alkali-soluble polymer shown in Patent Document 6 in which the branched chain contains a crosslinking group, the amine derivative derived from the skeleton is used as a crosslinking group, and therefore, the i-line of the alkali-soluble polymer (365 nm) The permeability decreases and the sensitivity decreases. The alkali-soluble polymer shown in Patent Document 7 in which the branched chain contains a crosslinking group is a non-photosensitive polybenzoic acid. Oxazole.

In the alkali-soluble polymer shown in Patent Document 8, a crosslinking group is introduced into a branch by linking with an ethylene glycol chain, but the ethylene glycol chain is decomposed during hardening, and the crosslinking group is partially detached. Therefore, it is considered that There is an inhibitory effect of hardening shrinkage at the time of cyclization.

Therefore, the problem to be solved by the present invention is to provide an alkali-soluble polymer having a low curing shrinkage (high residual film ratio at the time of curing) and a photosensitive resin composition excellent in pattern shape after curing, and using the composition A method for producing a cured concave-convex pattern, and a semiconductor device and a light-emitting device having the cured concave-convex pattern.

The present inventors have made an effort to study and repeat the experiment in view of the problems of the prior art described above, and as a result, it has been found that a polymer and a photosensitive resin composition which solve the above problems can be obtained by forming an alkali-soluble polymer having a specific structure, thereby completing this invention.

That is, the present invention is as follows.

[1] an alkali-soluble polymer having a structure synthesized from at least one carboxylic acid compound selected from the group consisting of polycarboxylic acids and derivatives thereof and a polyamine compound; and derived from having a crosslinking group And a structure containing a crosslinking group of a compound which can react with the above polycarboxylic acid or a derivative thereof.

[2] The alkali-soluble polymer according to [1] above, wherein the structure containing the crosslinking group is a structure represented by the following formula (1):

[Chemical 1]

In the formula, R ₁ and R ₂ are each independently at least one group selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from a hydroxyl group, an alkoxy group, and an alkene group. a group of at least one of a group consisting of a group consisting of an epoxy group and an oxetane group, and W ₁ is an organic group having a (n ₁ + 2) valence of 1 to 30, and m ₁ is An integer from 1 to 500, and n ₁ is an integer from 1 to 12.

[3] An alkali-soluble polymer having at least one selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (4):

[Chemical 2]

In the formula, X ₁ , Y ₁ and Y ₂ are each independently a 2 to 4 valent organic group having at least 2 carbon atoms, and Z ₁ has a structure represented by the following formula (3):

[Chemical 3]

(wherein R ₁ and R ₂ are each independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from the group consisting of a hydroxyl group, an alkoxy group, and an alkene group; a group of at least one group of a group consisting of a group, an epoxy group, and an oxetane group, and W ₂ is an organic group having a (n ₁ + 2) valence of 1 to 30, and B is selected a radical in the group consisting of -NH-, -O-, and -S-, and n ₁ is an integer from 1 to 12), and R ₄ to R ₆ are each independently a hydrogen atom or have a carbon number of 1 to 10; The hydrocarbon group, m ₂ is an integer from 1 to 1000, and m ₃ is an integer from 1 to 500, where m ₂ /(m ₂ +m ₃ )=0.05 to 0.99, and n ₂ to n ₇ are independently 0 to 2 An integer, n ₂ + n ₃ + n ₄ + n ₅ + n ₆ + n ₇ > 0, here, m ₂ units including X ₁ and Y ₁ , and m ₃ units including Z ₁ and Y ₂ The order of arrangement is not limited};

[Chemical 4]

In the formula, Y ₃ is a tetravalent organic group having at least 2 carbon atoms, and X ₂ and Y ₄ are each independently a 2 to 4 valent organic group having at least 2 carbon atoms, and Z ₁ has the following formula (3) The structure represented:

[Chemical 5]

(wherein R ₁ and R ₂ are each independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from the group consisting of a hydroxyl group, an alkoxy group, and an alkene group; a group of at least one group of a group consisting of a group, an epoxy group, and an oxetane group, and W ₂ is an organic group having a (n ₁ + 2) valence of 1 to 30, and B is selected a radical in the group consisting of -NH-, -O-, and -S-, and n ₁ is an integer from 1 to 12), and R ₇ and R ₈ are each independently a hydrogen atom or have a carbon number of 1 to 10; The hydrocarbon group, m ₄ is an integer from 1 to 1000, and m ₅ is an integer from 1 to 500, where m ₄ /(m ₄ +m ₅ )=0.05 to 0.99, and n ₈ to n ₁₁ are integers of 0 to 2, _{n 8 + n 9 + n 10} + n 11> 0, where, X ₂ is not limited to the order comprises Y m ₃ and the unit _4, and comprising Z ₁ and Y m ₄ of the _five units}.

[4] A method for producing an alkali-soluble polymer, which comprises the steps of: reacting a polyvalent carboxylic acid or a derivative thereof with a compound having a crosslinking group to synthesize a cross-linking compound having a carboxylic acid or a derivative thereof; A compound having a structure of a bond; a compound having a structure having a crosslink group having a carboxylic acid or a derivative thereof at both ends and a polyamine compound is polycondensed.

[5] A photosensitive resin composition comprising the photoacid generator (B) in an amount of from 1 to 50 by weight based on 100 parts by weight of the alkali-soluble polymer (A) according to any one of the above [1] to [3] Share.

[6] The photosensitive resin composition according to the above [5], wherein the organic hydrazine compound (C) is further contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the alkali-soluble polymer (A).

[7] The photosensitive resin composition of the above [5] or [6] wherein the photoacid generator (B) is a naphthoquinonediazide compound, and 100 parts by weight of the alkali-soluble polymer (A), Further, the monocarboxylic acid compound (D) is contained in an amount of from 1 to 40 parts by weight.

[8] The photosensitive resin composition according to any one of the above [5] to [7], wherein the phenol compound (E) is further contained in an amount of from 1 to 100 parts by weight based on 100 parts by weight of the alkali-soluble polymer (A). .

The photosensitive resin composition of any one of the above-mentioned [5] to [8], wherein the compound containing a crosslinking reaction by heat is contained with respect to 100 parts by weight of the above-mentioned alkali-soluble polymer (A). (F) 1 to 50 parts by weight.

[10] The photosensitive resin composition according to any one of [5] to [9] wherein the compound (F) which is crosslinked by heat is selected from the group consisting of an epoxy compound and an oxetane. a compound, a melamine compound, an alkenyl compound, a structure represented by the following formula (5), a structure represented by the following formula (6), and a group represented by the following formula (7) At least one of:

[Chemical 6]

In the formula, R ₉ is a hydrogen atom or a monovalent group selected from the group consisting of methyl, ethyl, n-propyl, and isopropyl, and R ₁₀ is selected from a hydrogen atom, a hydroxyl group, and a carbon atom. a monovalent group of at least one of a group consisting of an alkyl group having 1 to 6, an alkoxy group, an ester group having 2 to 10 carbon atoms, and an amine group having 2 to 10 carbon atoms, n ₁₂ is an integer from 1 to 5, and n ₁₃ is an integer from 0 to 4, where n ₁₂ + n ₁₃ = 5, m ₆ is an integer from 1 to 4, and Z ₂ is CH ₂ OR when m ₆ =1. ₉ or R ₁₀ , when m ₆ = 2~4, is a single bond or a 2 to 4 valence organic group, where R ₉ and R ₁₀ are each other when a plurality of CH ₂ OR ₉ and R ₁₀ are present. The same or different};

[Chemistry 7]

Wherein R ₁₁ and R ₁₂ are each independently a hydrogen atom or a hydrocarbon group selected from the group consisting of 1 to 10 carbon atoms and R ₁₃ CO- (wherein R ₁₃ is a hydrocarbon group having 1 to 10 carbon atoms) The base of the group of members};

[化8]

In the formula, D ₁ is a functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an organic group capable of crosslinking, and M ₁ is selected from -CH ₂ -, a group in the group consisting of -O-, and -S-, Z ₃ is a divalent organic group, and n ₁₄ is an integer of 0 to 4. When there are a plurality of D ₁ , a plurality of D ₁ may be the same Can also be different}.

[11] The photosensitive resin composition according to any one of the above [5] to [10], wherein the compound (G) which generates an acid by heat is contained in an amount of 100 parts by weight based on the alkali-soluble polymer (A). ) 0.1 to 30 parts by weight.

[12] A photosensitive resin composition comprising 0.5 to 30 parts by weight of the photoacid generator (B), based on 100 parts by weight of the alkali-soluble polymer (A) according to any one of the above [1] to [3] And a compound (H) which can be crosslinked by the action of an acid, 1 to 50 parts by weight.

[13] The photosensitive resin composition according to [12] above, wherein the compound (H) which can be crosslinked by the action of an acid is a compound having a methylol group or an alkoxymethyl group in the molecule.

[14] The photosensitive resin composition of the above [12] or [13], wherein the compound (1) which is a sensitizer is further contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble polymer (A). .

[15] The photosensitive resin composition solution according to any one of the above [5] to [14], further comprising an organic solvent (J).

[16] A method of manufacturing a hardened concave-convex pattern, comprising the steps of:

(1) A step of forming a photosensitive resin layer obtained by applying the photosensitive resin composition according to any one of the above [5] to [14] or the photosensitive resin composition solution of the above [15] on the substrate ;

(2) an exposure step;

(3) developing step;

(4) A step of heat-treating the obtained concave-convex pattern.

[17] A semiconductor device comprising: a semiconductor substrate; a semiconductor element provided on the semiconductor substrate; and an insulating film provided on an upper portion of the semiconductor element; and the insulating film is manufactured by the above [16] The hardened concave-convex pattern obtained by the method.

[18] A light-emitting device comprising: a display element substrate; an insulating film covering a surface of the substrate; and a display element provided on an upper portion of the display element substrate; and the insulating film is as described above [ 16] The hardened concave-convex pattern obtained by the manufacturing method.

According to the present invention, it is possible to provide an alkali-soluble polymer which is characterized in that the curing shrinkage is low (the residual film ratio is high at the time of curing), the ductility of the cured film is excellent, and the photosensitive resin composition having excellent pattern shape after curing, A method of producing a cured concave-convex pattern of the positive photosensitive resin composition, and a semiconductor device having the cured uneven pattern.

<Photosensitive Resin Composition>

Hereinafter, the alkali-soluble polymer of the present invention and each component constituting the photosensitive resin composition containing the alkali-soluble polymer will be specifically described.

Alkali soluble polymer (A)

The alkali-soluble polymer of the present invention has a structure in which a structure synthesized from at least one carboxylic acid compound selected from the group consisting of a polyvalent carboxylic acid and a derivative thereof and a polyamine compound; and a structure having a crosslinking group and capable of A structure containing a crosslinking group of a compound which reacts with the above polycarboxylic acid or a derivative thereof. The alkali-soluble polymer (A) is a base polymer of a photosensitive resin composition to be described later.

Here, examples of the polyvalent carboxylic acid and the derivative thereof include a dicarboxylic acid, a tricarboxylic acid, these chlorochemical compounds, an acid anhydride compound, and tetracarboxylic dianhydride. Further, examples of the polyvalent amine compound include compounds having at least two amine groups, and specifically, diamines such as diaminobenzoic acid, diaminophenol, and bis(aminophenol). These compounds can also be substituted.

The structure of the crosslinking group is not particularly limited, and it means that the crosslinking reaction occurs in the range of 150 to 350 ° C, and the crosslinking reaction occurs in the heat treatment step after patterning by development.

The compound capable of reacting with a polyvalent carboxylic acid or a derivative thereof is a compound capable of undergoing a condensation reaction with a carboxylic acid or a derivative thereof, and specific examples thereof include a hydroxy compound, a thiol compound, a thiophenol compound, an amine compound, and hydrazine. Amine compounds and the like. The hydroxy compound referred to herein means a phenol compound or an alcohol compound.

That is, the alkali-soluble polymer (A) is characterized by having a structure selected from a compound derived from a dicarboxylic acid or a derivative thereof and a bis(aminophenol), and a structure containing a crosslinking group. Polyamine having a phenol group, particularly preferably a polyamine which is a PBO precursor having a phenol group in the ortho position of a guanamine bond; derived from a tetracarboxylic dianhydride and a bis(aminophenol), having a phenolic hydroxyl group Alkali-soluble polyimine; a poly-proline which is derived from a tetracarboxylic dianhydride and a diamine as a polyimine precursor having a carboxyl group at the ortho position of the indoleamine bond; and a moiety partially capping the above carboxyl group Polyphthalate. The alkali-soluble polymer (A) has a structure containing a cross-linking group, and the cross-linking group also reacts at a low temperature to become a resin having a small hardening shrinkage.

First, a structural portion containing a crosslinking group (hereinafter also referred to as "structure containing a crosslinking group") will be described.

The structure containing the crosslinking group is preferably at least one selected from the group consisting of structures represented by the following general formula (1) from the viewpoint of reactivity at the time of heat treatment:

[Chemistry 9]

In the formula, R ₁ and R ₂ are each independently at least one group selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from a hydroxyl group, an alkoxy group, and an alkene group. a group of at least one of a group consisting of a group consisting of an epoxy group and an oxetane group, and W ₁ is an organic group having a (n ₁ + 2) valence of 1 to 30, and m ₁ is An integer from 1 to 500, and n ₁ is an integer from 1 to 12.

The organic group having a (n ₁ + 2) valence of 1 to 30 carbon atoms represented by W ₁ in the above formula (1) is not particularly limited, and examples thereof include a hydrocarbon having 1 to 30 carbon atoms. The structure and the fluorine-containing structure or a structure containing at least one selected from the group consisting of a mercapto group, an ether group, and an ester group. As a structural example, the following general formula (8) is mentioned.

[化10]

In the formula, R ₁ and R ₂ are each independently at least one group selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from a hydroxyl group, an alkoxy group, and an alkene group. a group of at least one group consisting of a group consisting of a group consisting of an epoxy group and an oxetanyl group; W ₃ is a hydrocarbon group having 1 to 10 carbon atoms, and A ₁ is selected from a single bond and having a carbon number of a hydrocarbon group of 1 to 13, and having the following formula (9):

[11]

At least one of the groups consisting of the structures represented, m ₇ is an integer from 1 to 500, and n ₁₅ is an integer from 1 to 4, and n ₁₆ is an integer from 0 to 3. Here, in the case where there are a plurality of W ₃ and A ₁ , the same may be the same or different}.

In the above formula (8), W _{3 is} preferably an aromatic group from the viewpoint of solvent resistance. Further, from the viewpoint of heat resistance, in the above formula (8), W _{3 is} preferably a benzene ring, and in the above formula (8), A _{1 is} preferably selected from a single bond and the following structure:

[化12]

The crosslinking group contained in the structure containing a crosslinking group (for example, (CR ₁ R ₂ R ₃ ) in the formula (1)) preferably contains: from the viewpoint of reactivity at the time of heat treatment: At least one group selected from the group consisting of a methylol group, an alkoxymethyl group, an alkenyl group, an epoxy group, and an oxetane group. Here, the alkenyl group means an unsaturated double bond group such as a (meth) acrylate group, an allyl group or a vinyl group. In the present specification, the (meth) acrylate group means a methacrylate group or an acrylate group.

In the structure containing a crosslinking group represented by the above formula (1), from the viewpoint of storage stability, a methylol group, an alkoxymethyl group and derivatives thereof are preferable, and among them, an alkane is more preferable. Oxymethyl group. The hydroxymethyl group and the alkoxymethyl group derivative are equivalent to the following: in the structure containing the crosslinking group represented by the above formula (1), R ₁ and R ₂ have at least one selected from the group consisting of methyl group and ethyl group. A group of a group consisting of a group, a n-propyl group, and an isopropyl group, and R ₃ is -OR, and here, R is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.

Further, the alkali-soluble polymer (A) may be a resin having at least one structure selected from the group consisting of a structure represented by the following general formula (2) and a structure represented by the general formula (4):

[Chemistry 13]

In the formula, X ₁ , Y ₁ and Y ₂ are each independently a 2 to 4 valent organic group having at least 2 carbon atoms, and Z ₁ has a structure represented by the following formula (3):

[Chemistry 14]

(wherein R ₁ and R ₂ are each independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from the group consisting of a hydroxyl group, an alkoxy group, and an alkene group; a group of at least one group of a group consisting of a group, an epoxy group, and an oxetane group, and W ₂ is an organic group having a (n ₁ + 2) valence of 1 to 30, and B is selected a radical in the group consisting of -NH-, -O-, and -S-, and n ₁ is an integer from 1 to 12), and R ₄ to R ₆ are each independently a hydrogen atom or have a carbon number of 1 to 10; The hydrocarbon group, m ₂ is an integer from 1 to 1000, and m ₃ is an integer from 1 to 500, where m ₂ /(m ₂ +m ₃ )=0.05 to 0.99, and n ₂ to n ₇ are independently 0 to 2 An integer, n ₂ + n ₃ + n ₄ + n ₅ + n ₆ + n ₇ > 0, here, m ₂ units including X ₁ and Y ₁ , and m ₃ units including Z ₁ and Y ₂ The order of arrangement is not limited};

[化15]

In the formula, Y ₃ is a tetravalent organic group having at least 2 carbon atoms, and X ₂ and Y ₄ are each independently a 2 to 4 valent organic group having at least 2 carbon atoms, and Z ₁ has the following formula (3) The structure represented:

[Chemistry 16]

(wherein R ₁ and R ₂ are each independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from the group consisting of a hydroxyl group, an alkoxy group, and an alkene group; a group of at least one group of a group consisting of a group, an epoxy group, and an oxetane group, and W ₂ is an organic group having a (n ₁ + 2) valence of 1 to 30, and B is selected a radical in the group consisting of -NH-, -O-, and -S-, and n ₁ is an integer from 1 to 12), and R ₇ and R ₈ are each independently a hydrogen atom or have a carbon number of 1 to 10; The hydrocarbon group, m ₄ is an integer from 1 to 1000, and m ₅ is an integer from 1 to 500, where m ₄ /(m ₄ +m ₅ )=0.05 to 0.99, and n ₈ to n ₁₁ are integers of 0 to 2, _{n 8 + n 9 + n 10} + n 11> 0, where, X ₂ is not limited to the order comprises Y m ₃ and the unit _4, and comprising Z ₁ and Y m ₄ of the _five units}.

The organic group having a (n ₁ + 2) valence of 1 to 30 carbon atoms represented by W ₂ in the above formula (3) is not particularly limited, and examples thereof include a hydrocarbon having 1 to 30 carbon atoms. The structure and the fluorine-containing structure or a structure containing at least one selected from the group consisting of a mercapto group, an ether group, and an ester group. As a structural example, the following general formula (10) is mentioned:

[化17]

In the formula, R ₁ and R ₂ are each independently at least one group selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from a hydroxyl group, an alkoxy group, and an alkene group. a group of at least one of a group consisting of a group consisting of an epoxy group and an oxetane group; W ₄ is a hydrocarbon group having 1 to 10 carbon atoms, and B is selected from the group consisting of -NH-, -O- and a group in the group consisting of -S-, and A ₁ is a hydrocarbon group selected from a single bond, having 1 to 13 carbon atoms, and the following formula (9):

[化18]

At least one of the groups consisting of the structures represented, and n ₁₅ is an integer from 1 to 4, and n ₁₆ is an integer from 0 to 3. Here, in the case where there are a plurality of W ₄ and A ₁ , the same may be the same or different}.

The preferred structure of the above formula (10) is the same as the preferred structure of the above formula (8). In the case where W ₄ is an aromatic group, it is preferred that the group represented by CR ₁ R ₂ R ₃ is substituted with a group represented by B at any of the ortho or para position.

Further, the alkali-soluble polymer (A) is represented by the above formula (3) and the above formula (10) represented by Z ₁ in the above formula (2) and the above formula (4) from the viewpoint of sensitivity. B is preferably -O-, and R _{3 is} preferably a structure represented by the following formula (11):

[Chemistry 19]

(wherein R ₁₃ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms).

In the alkali-soluble polymer (A) selected from the above formula (2) or formula (4), B is -NH-, -O- or -S-, but compared with the case where B is -NH- More preferably, B is -O- or -S-. The reason for this is that, in the case of introducing an ester bond or a thioester bond, the hydrogen bond derived from the guanamine group is reduced as compared with the case of the guanamine bond, and thus it is considered that the alkali-soluble polymer has a reduced interaction with each other, and the ester The segments adjacent to the bond or thioester bond are liable to rotate with each other, and the resulting cured film has good ductility in the case where the alkali-soluble polymer forms a crosslinked structure upon hardening.

Further, when an ester bond or a thioester bond is introduced, the hydrophobicity of the alkali-soluble polymer is improved as compared with the case of the guanamine bond, and therefore, the solubility of the unexposed portion in the alkaline aqueous solution is suppressed, and The contrast of the exposure section is increased.

The alkali-soluble polymer (A) selected from the above formulas (2) and (4) is preferably produced by a method described later.

In the structure containing a crosslinking group represented by the above formula (11), from the viewpoint of storage stability, a crosslinking group having a methylol group, an alkoxymethyl group or the like is preferable. The structure. The hydroxymethyl group and the alkoxymethyl group derivative are equivalent to the following: in the structure containing a crosslinking group represented by the above formula (10), R ₁ and R ₂ are selected from a methyl group and an ethyl group. A group of a group consisting of n-propyl and isopropyl, R ₃ is -OR ₁₃ , and R ₁₃ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. The structure containing a crosslinking group which has a methylol group, an alkoxymethyl group, and these derivatives is the following structure.

[Chemistry 20]

(wherein R _{14 is} each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms).

The method for producing the alkali-soluble polymer (A) includes a method of polycondensing a compound containing a crosslinking group described below with a polyvalent carboxylic acid, and then polycondensing the polyamine compound. Examples of the compound containing a crosslinking group include an alcohol having a crosslinking group, a phenol having a crosslinking group, a thiol having a crosslinking group, a thiophenol having a crosslinking group, and an amine having a crosslinking group.

The compound containing a crosslinking group is obtained by the following synthesis method. In other words, the raw material described below is reacted with formaldehyde in the presence of a base catalyst, whereby methylolation is carried out, and the corresponding halide or alcohol is reacted to obtain a compound containing a crosslinking group.

Examples of the compound of the raw material of the compound containing a crosslinking group include a hydroxy compound, a thiophenol compound, and an amine compound. Specific examples thereof include 1,4-bis(2-hydroxyethyl)benzene and 2- (4-hydroxyphenyl)ethanol, hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 4,4'-ethylene double Phenol, 4,4'-dihydroxydiphenylpropane, TM124 (Degussa Japan: trade name), 2,2-bis(4-hydroxyphenyl)butane, 4,4'-(1,3-dimethyl Butyl butyl) diphenol, 4,4'-(2-ethylhexylene) diphenol, hexestrol, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4' -(α-methylbenzylidene)bisphenol, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 9,9-bis(4-hydroxyphenyl)fluorene, 4,4'-dihydroxytetraphenylmethane, 4,4'-dihydroxydiphenylhexafluoropropane, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 1 , 3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenylanthracene, bis(4-hydroxyphenyl) sulfide, bisphenolic acid, 1,4-benzenedithiol, 4,4'-biphenyldithiol, 4,4'-thiobisbenzenethiol, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiyl Methane, 4,4'-ethylenediphenylamine, 1,1-bis(4-aminophenyl)cyclohexane, 4,4"-diamino-p-triphenyl, α,α'-double (4 -aminophenyl)-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)hexafluoropropane, 4 , 4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amino group Phenoxy)benzene, bis(4-aminophenyl)anthracene, bis(4-aminophenyl) sulfide, and the like.

Among these compounds, from the viewpoint of mechanical properties, a compound having a structure selected from the following is preferable:

[Chem. 21]

In the case of a phenol compound and a thiophenol compound, a hydroxymethyl-substituted compound is synthesized by the following method.

In the presence of an alkaline catalyst, in an aqueous solvent or a mixed solvent of water and an organic solvent, 4 mol of formaldehyde, preferably 5-10 mol, and 1 mol of the above-mentioned compound containing a crosslinking group are used. After the reaction, the resulting reaction product is neutralized, whereby a hydroxymethyl-substituted compound can be obtained.

In the above production method, as the formaldehyde, in addition to the commercially available, for example, 35% of the aqueous solution of the formalin, in the presence of water, the paraformaldehyde or the like which acts in the same manner as the formaldehyde may be used. Among the alkane, among them, it is preferred to use formalin.

Examples of the basic catalyst include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, calcium hydroxide, and the like, and inorganic strong bases such as sodium hydroxide or potassium hydroxide are preferably used. An organic strong base such as methyl ammonium hydroxide, wherein an aqueous solution of 10 to 40% by weight of such a strong base is preferably used. The basic catalyst is used in an amount of from 0.5 to 5 equivalents based on the hydroxyl group of the raw material of the compound containing a crosslinking group, and is preferably used in the range of from 0.8 to 3 equivalents. The amount of the solvent is usually from 1 to 5 times the weight ratio of the raw material of the compound containing the crosslinking group, and is preferably used in the range of about 2 to 3 times. The organic solvent may be, for example, methanol, ethanol or n-propanol, insofar as it does not impair the solubility of the alkaline catalyst and the phenol compound as the raw material or the aqueous solvent mixture of the thiophenol compound. Alcohols such as isopropanol, n-butanol, ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol, carbitol, aromatic hydrocarbons such as toluene and xylene, and dimethyl hydrazine, N a water-soluble aprotic polar solvent such as methylpyrrolidone or dimethylformamide.

The reaction is usually carried out at a temperature of from 0 to 60 ° C, preferably from 20 to 50 ° C, usually for from 1 to 72 hours, preferably from about 4 to 16 hours. When the temperature of the reaction is higher than 60 ° C, a high molecular weight substance or various undesired by-products are formed in a large amount, which is not preferable. After the reaction of the phenol compound or the thiophenol compound as the above-mentioned raw material with formaldehyde is completed in the presence of a basic catalyst, the target reaction product is separated and recovered from the obtained reaction mixture, and the reaction is completed after the reaction is completed. An acid such as sulfuric acid is added to the mixture to neutralize the alkali salt and the base catalyst of the target. Then, in order to separate and remove the water layer, a solvent capable of separating from water such as toluene, xylene, methyl isobutyl ketone or ether is added as needed, and then the aqueous layer is separated. After the obtained oil layer is washed with water, the aqueous layer is separated, and a solvent or a low boiling point compound such as formaldehyde is distilled off from the obtained oil layer, and then a crystallization solvent such as an aromatic hydrocarbon such as toluene, ethylbenzene or cumene is added thereto. An aliphatic ketone such as methyl ethyl ketone or methyl isobutyl ketone, or an aliphatic hydrocarbon such as cyclohexane, n-hexane or n-heptane, dissolved, cooled, crystallized, and then filtered. Thus, the crystal of the target can be obtained in high yield with good yield.

Examples of the acid used for the neutralization treatment include organic acids such as formic acid, acetic acid, propionic acid, and oxalic acid, and inorganic acids such as sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, and hydrochloric acid. Among these, hydrochloric acid, sulfuric acid, and acetic acid are preferably used in terms of economy or operability.

Then, using the hydroxymethyl-substituted compound obtained by the above production method, an alkoxymethyl-substituted compound was synthesized by the following method.

The hydroxymethyl substituted compound obtained by the above production method is used as a raw material, and reacted with a saturated aliphatic alcohol having 1 to 4 carbon atoms in the presence of an acid catalyst, whereby an alkoxymethyl substituted compound can be obtained. . Here, the lower aliphatic alcohol serves as a reaction raw material of a reaction solvent. As the acid catalyst, concentrated sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, cation exchange resin (acid type), oxalic acid or the like is preferably used. More preferably, it is a strong inorganic acid such as concentrated sulfuric acid. Further, the acid catalyst is usually used in an amount of from 0.1 to 100 parts by weight, preferably from 0.5 to 30 parts by weight, based on 100 parts by weight of the hydroxymethyl-substituted compound of the starting material.

The lower aliphatic alcohol is a saturated aliphatic alcohol having 1 to 4 carbon atoms, and specifically, methanol, ethanol, n-propanol, isopropanol or n-butanol can be used. It is preferably a primary or secondary alcohol, and more preferably a primary alcohol. Such a lower aliphatic alcohol is usually used as a reaction solvent in excess, and is used in excess with respect to the hydroxymethyl-substituted compound of the starting material. The amount to be used is not particularly limited, and is usually used in the range of 200 to 4000 parts by weight, preferably 500 to 1500 parts by weight, based on 100 parts by weight of the hydroxymethyl-substituted compound of the starting material.

Further, the reaction temperature is usually in the range of 0 to 80 ° C, preferably 40 to 60 ° C. After completion of the reaction, the target alkoxymethyl-substituted compound can be isolated from the obtained reaction mixture according to a usual method. For example, after the reaction is completed, the obtained reaction mixture is neutralized with a base such as an aqueous sodium hydroxide solution, and an excess of the lower aliphatic alcohol which also serves as a reaction solvent is removed by distillation or the like as needed, and then formed by neutralization. The salt is separated by filtration to obtain a crude product of the target. If necessary, the crude product is dissolved in a solvent such as toluene, xylene, methyl isobutyl ketone or ether, washed with water, and the aqueous layer is separated, and the obtained oil layer is cooled, crystallized, and then filtered. Thereby, crystals of the target substance can be obtained in high purity with good yield.

In a compound containing a crosslinking group containing an alkenyl group, an epoxy group, and an oxetanyl group, a hydroxymethyl group-substituted compound is used as a raw material to react with methacrylic acid, epichlorohydrin, and halo The oxetane compound or the like is reacted, whereby an alkoxymethyl substituted compound can be obtained.

In the case of an amine-based compound, the amine group is subjected to a decane treatment, and a methylol-substituted compound and an alkoxymethyl-substituted compound are synthesized by the same method.

As a method for synthesizing the alkali-soluble polymer (A) having a structure of a PBO precursor and a cross-linking group, it may be in the presence of a base catalyst such as pyridine, triethylamine or benzyltriethylamine chloride. The excess dicarboxylic acid or a derivative thereof is reacted with a compound containing a crosslinking group obtained by the above production method in the range of -10 ° C to 40 ° C to synthesize a cross-linking of a carboxylic acid or a derivative thereof at both ends. a structure in which the above-mentioned both ends are a crosslinkable group of a carboxylic acid or a derivative thereof, and a polyamine compound such as bis(aminophenol) is condensed in a range of from -15 ° C to 10 ° C, whereby The PBO precursor containing a crosslinking group can be synthesized. Examples of the derivative of the dicarboxylic acid include those in which the dicarboxylic acid is ruthenium chloride by sulfinium chloride. Specific examples of the synthesis method of ruthenium chloride include a method in which a dicarboxylic acid and an excess amount are present in the presence of a catalyst such as N,N-dimethylformamide, pyridine or benzyltriethylamine chloride. The sulfoxide is reacted, and excess sulfinium chloride is distilled off by heating and depressurization; the residue of the reaction solution can be obtained by recrystallization using a solvent such as hexane or toluene, or may be omitted. It is used for the polymerization of resins. Further, a catalyst which forms a HOBT active ester body by using a dehydration condensing agent such as dicyclohexylcarbodiimide to form a HOBT active ester with a dicarboxylic acid and N-hydroxybenzotriazole (hereinafter also referred to as "HOBT") can also be used.

In the alkali-soluble polymer (A) having a structure of a PBO precursor and a crosslinking group, the repeating unit having a structure containing a crosslinking group, that is, m ₃ in the above formula (2), is subjected to alkaline development. The solubility in the liquid and the mechanical properties of the obtained resin film are preferably from 1 to 500, more preferably from 2 to 100, more preferably from 3 to 50, most preferably from 4 to 30. The integer. Further, as for the ratio of the structure containing a crosslinking group in the present polymer, that is, m ₂ /(m ₂ +m ₃ ) in the above formula (2), the solubility in an alkaline developing solution and the obtained The viewpoint of the mechanical properties of the resin film is from 0.05 to 0.99, more preferably from 0.10 to 0.50, particularly preferably from 0.15 to 0.40, in the case of a positive photosensitive resin composition, in the negative photosensitive resin composition. In the case of 0.20 to 0.80, it is preferably 0.30 to 0.60.

As a method for synthesizing an alkali-soluble polymer (A) having a soluble polyimine (PI) or a PI precursor and a structure containing a crosslinking group, it can be used in pyridine, triethylamine, benzyltriethylamine chloride In the presence of an alkali catalyst, the trimellitic chloride is reacted with a compound containing a crosslinking group obtained by the above production method at a temperature of from -10 ° C to 25 ° C to synthesize a cross-linking group having an acid anhydride at both ends. a structure in which the structure of the cross-linking group having an acid anhydride at both ends is polycondensed with a polyamine compound such as a diamine or a bis(aminophenol) at a temperature of from 25 ° C to 60 ° C, and thereafter, a quinone imine is carried out. Thereby, a soluble PI containing a crosslinking group and a PI precursor containing a crosslinking group can be synthesized.

In the alkali-soluble polymer (A) having a structure of a soluble polyimine (PI) or PI precursor and a crosslinking group, as for a repeating unit having a structure of a crosslinking group, that is, in the above formula (4) The m ₅ is preferably an integer of 1 to 500, more preferably an integer of 3 to 200, and more preferably 5 to 5, from the viewpoint of the solubility in the alkaline developer and the mechanical properties of the obtained resin film. An integer of 100, preferably an integer from 10 to 60. Further, as for the pyridyl compound having a structure in which the polyamine compound is synthesized from at least one carboxylic acid compound selected from the group consisting of polyvalent carboxylic acids and derivatives thereof, and the polyamine compound, that is, m in the above formula (4) ₄ / (m ₄ + m ₅ ), from the viewpoint of the solubility in the alkaline developing solution and the mechanical properties of the obtained resin film, preferably from 0.05 to 0.99, in the case of a positive photosensitive resin composition More preferably, it is 0.10 to 0.70, and particularly preferably 0.20 to 0.60. In the case of a negative photosensitive resin composition, it is preferably 0.30 to 0.90, and particularly preferably 0.40 to 0.60.

Next, it is explained that (A) in the structure represented by the above formula (2), other than the structure containing a crosslinking group, has X ₁ (NH ₂ ) ₂ (OH) _{n 2} (COOR ₄ ) _{n 3} and Y _{1 (COOH) 2 (OH) n4} (COOR 5) n5, or _{Y 2 (COOH) 2 (OH} ) n6 PBO precursor structure unit (COOR _{6) n7} and of precursors of PI.

The compound represented by Y ₂ (COOH) ₂ (OH) _n6 (COOR ₆ ) _n7 may also be the same as the compound represented by Y ₁ (COOH) ₂ (OH) _{n 2} (COOR ₅ ) _n3 , represented by n ₄ The value represents the same range as the value represented by n ₆ , and the value expressed by n _{5 and} the value represented by n _{7 are} also the same.

First, the structure having the PBO precursor will be described. The PBO precursor corresponds to a hydroxypolyamine having a structure in which (1) X ₁ (NH ₂ ) ₂ (OH) _{n2 in} the structure represented by the above formula (2) ( COOR ₄ ) _n3 , Y ₁ (COOH) ₂ (OH) _n4 (COOR ₅ ) _n5 has X ₁ (NH ₂ ) ₂ when n ₂ = 2, n ₃ =0, n ₄ =0 and n ₅ =0 A structure in which a polyaminophenol having a structure of (OH) ₂ and a dicarboxylic acid having a structure of Y ₁ (COOH) _{2 are} polycondensed. The two groups of amine groups and hydroxyl groups of the bisaminophenol are in the ortho position to each other. Dihydroxydiamine (hydroxypolyamine) is ring-closed by heating to about 250-400 ° C and converted into polybenzoate as a heat resistant resin. Oxazole. From the viewpoint of the solubility in the alkaline developing solution and the heat resistance of the obtained resin film, X ₁ is preferably a tetravalent organic group having two or more and 30 or less carbon atoms. Y ₁ is preferably a divalent organic group having two or more and 30 or less carbon atoms from the viewpoint of the solubility in the alkaline developing solution and the heat resistance of the obtained resin film. m ₂ is preferably an integer of 1 to 1000, more preferably an integer of 2 to 200, and particularly preferably 2 to 100, from the viewpoint of the solubility in the alkaline developer and the mechanical properties of the obtained resin film. Integer, the best is an integer from 3 to 60.

As the above bisaminophenol having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , for example, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′- Dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylanthracene, 4,4'- Diamino-3,3'-dihydroxydiphenylanthracene, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl) Propane, 3,3'-diamino-4,4'-dihydroxytetraphenylmethane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-double -(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, and 1,3-diamino-4,6-dihydroxybenzene, bis(3-amino-4-hydroxyphenyl) sulfide, etc. . These bisaminophenols may be used singly or in combination of two or more.

Among the bisaminophenols having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , particularly preferred are diaminophenols having an X ₁ group selected from the following aromatic groups:

[化22]

The combination of the following bisphenols with respect to the bonding of the benzene rings to each other may be an amino group in the meta position, a hydroxyl group in the para position, or a hydroxyl group in the meta position, and an amino group in the para position, dissolved in a solvent. From the viewpoint of the nature, it is preferred that the meta position is an amine group and the para position is a hydroxyl group.

In the structure represented by the above formula (2), X ₁ (NH ₂ ) ₂ (OH) ₂ may also have X ₃ (NH ₂ ) ₂ (OH), X ₃ (NH ₂ ) ₂ as needed. Structure of the diamine polycondensation structure.

In the structure represented by the above formula (2), the higher the ratio of the above dihydroxydiamine unit, the higher the solubility in the alkaline aqueous solution used as the developer, so [X ₁ (NH ₂ ) ₂ The value of (OH) ₂ ] / [X ₁ (NH ₂ ) ₂ (OH) ₂ + X ₃ (NH ₂ ) ₂ ] is preferably 0.5 or more, more preferably 0.7 or more, and most preferably 0.8 or more. X ₃ represents a divalent organic group represented by X ₁ (NH ₂ ) ₂ (OH) ₂ , and X _{1 has the} same meaning as X ₁ in the above formula (2).

Further, as a compound having a structure of X ₃ (NH ₂ ) ₂ , a diamine having two groups of amidoxime bonds and a phenolic hydroxyl group in the ortho position in the molecule (hereinafter referred to as "the PBO precursor in the molecule" may be used. Diamine of the structure"). For example, it is obtained by reacting two molecules of nitrobenzoic acid with the above-described bisaminophenol having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ to be represented by the following formula (12). Diamine:

[化23]

(wherein X ₄ represents a tetravalent organic group having at least 2 carbon atoms).

X ₄ is preferably selected from the group consisting of organic groups as the preferred of those organic group represented by X ₁ and on the composition of the set forth in the at least one organic group, X ₁ and X ₁ in the general formula (2) in the Synonymous.

As another method for obtaining a diamine having a PBO precursor structure in a molecule, there is also a method of reacting two molecules of nitroaminophenol with dichlorobenzene having a structure of Y ₅ (COCl) ₂ for reduction. And a diamine represented by the following formula (13) is obtained:

[Chem. 24]

(wherein, Y ₅ is a divalent organic group having at least 2 carbon atoms).

Y ₅ is preferably selected from the group consisting of those preferred as the organic group to the sum Y ₁ represents an organic group and to set forth the group consisting of at least one organic group, Y ₁ and Y ₁ in the general formula (2) in the Synonymous.

Examples of the diamine having a structure of X ₃ (NH ₂ ) ₂ include an aromatic diamine, decanediamine, and the like.

In addition, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 3,3'-diaminodiphenyl ether, and 3,4'-diamino group. Diphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,4'-diamino Diphenylanthracene, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-di Aminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2' - bis(4-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4-methyl-2,4-bis(4-aminophenyl)-1-pentyl Alkene, 4-methyl-2,4-bis(4-aminophenyl)-2-pentene, 1,4-bis(α,α-dimethyl-4-aminobenzyl)benzene, sub Amino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis(4-aminophenyl)pentane, 5 (or 6)-amino-1-(4-aminophenyl)-1,3,3-trimethylhydrazine, bis(p-aminophenyl)phosphine oxide, 4,4'-diamineyl couple Nitrobenzene, 4 , 4'-diaminodiphenylurea, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl] Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]benzophenone 4,4'-bis(4-aminophenoxy)diphenylanthracene, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy] Benzophenone, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy]diphenylanthracene, 4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, benzoquinone diamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4, 4'-diaminobiphenyl, o-toluidine oxime, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)anthracene, bis (4 -aminophenoxyphenyl) sulfide, 1,4-(4-aminophenoxyphenyl)benzene, 1,3-(4-aminophenoxyphenyl)benzene, 9,9- Bis(4-aminophenyl)anthracene, 4,4'-di-(3-aminophenoxy)diphenylanthracene, and 4,4'-diaminobenzimidamide, and the like, and the like The hydrogen atom of the aromatic nucleus of the aromatic diamine is selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group. At least one compound from the group or atom.

In order to improve the adhesion to the substrate, a part or all of the diamine having a structure of X ₃ (NH ₂ ) ₂ may be selected from the group. Examples of the stilbene diamine include bis(4-aminophenyl)dimethyl decane, bis(4-aminophenyl)tetramethyl decane, and bis(4-aminophenyl)tetra. Methyldioxane, bis(γ-aminopropyl)tetramethyldioxane, 1,4-bis(γ-aminopropyldimethylbenzyl)benzene, bis(4-amine Butyl) tetramethyldioxane, bis(γ-aminopropyl)tetraphenyldioxane, and the like.

Examples of the dicarboxylic acid having a structure of Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ include a dicarboxylic acid having an aromatic group or an aliphatic group selected from Y ₁ :

[化25]

(wherein A ₂ represents a group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and a single bond. a divalent group in the group, L ₁ represents a hydrogen atom, a halogen atom, an alkyl group or an unsaturated group, and k is an integer of 0 to 4);

[Chem. 26]

(wherein, L ₂ , L ₃ and L ₄ are each independently a hydrogen atom or a methyl group, and L ₅ is a hydrogen atom, a methyl group or a hydroxyl group).

In the structure represented by the above formula (2), in the case of the PBO precursor structure, it is preferable to include a structure represented by the following formula (14) from the viewpoint of transparency of the i-line region. :

[化27]

In the formula, X ₅ is selected from the group consisting of the following formula (15):

[化28]

At least one of the groups consisting of the structures represented, L ₆ , L ₇ , and L ₈ each independently represent a hydrogen atom or a methyl group, L ₉ represents a hydrogen atom, a methyl group or a hydroxyl group, and m ₂ is 1 to 1000. The integer}.

The above bisaminophenol compound may be a compound in which a benzene ring is bonded to each other, and may be an amino group in the meta position, a hydroxyl group in the para position, or a hydroxyl group in the meta position, and an amino group in the para position, dissolved in a solvent. From the viewpoint of the nature, it is preferred that the meta position is an amine group and the para position is a hydroxyl group.

Further, the tricyclodecane moiety in the structure represented by the above formula (14) is further preferably at least one selected from the group consisting of the following formula (16):

[化29]

Among them, from the viewpoint of satisfactory mechanical properties of the obtained resin film, the following formula (17) is more preferable:

[化30]

As a representative compound of the dicarboxylic acid having a tricyclodecane skeleton, bis(carboxy)tricyclo[5,2,1,0 ^2,6 ]decane can be mentioned. The compound can be synthesized according to the production method of the production example A of the Japanese Patent Laid-Open Publication No. SHO-58-110538, or the synthesis method of the first embodiment of the Japanese Patent Publication No. 2002-504891, or the Japanese Patent Laid-Open No. 09-15846 It was obtained by the synthesis method of Synthesis Example 2. However, heavy metals are used as the oxidizing agent in these methods, and therefore, the following production method is more preferable in that heavy metals are not used. Namely, tricyclo(5,2,1,0)decane dimethanol (manufactured by Tokyo Chemical Industry Co., Ltd., catalog No. T0850) was dissolved in acetonitrile or the like, and 2,2,6,6-tetramethylpiperidine-1 was added. - Catalyst such as oxygen radical (hereinafter also referred to as "TEMPO"), pH is adjusted by using disodium hydrogen phosphate or sodium dihydrogen phosphate, and sodium chlorite or sodium hypochlorite is added for oxidation and purification. Bis(carboxy)tricyclo[5,2,1,0 ^2,6 ]decane was produced as the target compound.

Further, a dicarboxylic acid compound having a structure represented by the structural group of the above formula (16) other than the above compound can be obtained, for example, by the following method. Namely, methylcyclopentadiene dimer (manufactured by Tokyo Chemical Industry Co., Ltd., catalog No. M0920), 1-methyldicyclopentadiene (manufactured by Tokyo Chemical Industry Co., Ltd., catalog No. M0910) or 1-hydroxybicyclo Pentadiene (manufactured by Tokyo Chemical Industry Co., Ltd., catalog No. H0684) as a raw material, hydrogen bromide or hydrogen chloride is added to the above raw materials by a method known from J. Org. Chem., 45, 3527 (1980) After saturating the bond sites, carbon monoxide and water are added according to the method known from J. Am. Chem. Soc., 95, 249 (1973), whereby tricyclic [5, ^{2, 1, 0 2, 6} ] 癸 can be obtained. Two hydroxymethyl groups were introduced into the skeleton of the alkane. As a method of synthesizing a dihydroxymethyl group, 9-boron bicyclo(3,3,1)decane may be additionally added by a method known from J. Am. Chem. Soc., 91, 2150 (1969). After the intermediate material is formed in the unsaturated bond site of the above-mentioned raw material, carbon monoxide is further reacted and reduced by LiAlH(OCH ₃ ) ₃ to produce a dimethylol group. According to the method described for obtaining bis(carboxy)tricyclo[5,2,1,0 ^2,6 ]nonane, the dimethylol group of the dihydroxymethyl group obtained in the above manner is similarly oxidized. The target dicarboxylic acid is obtained.

Further, a derivative of 5-aminoisophthalic acid may be used as part or all of the dicarboxylic acid having a structure of Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ . Specific examples of the reaction with 5-aminoisophthalic acid for obtaining the derivative include 5-norbornene-2,3-dicarboxylic anhydride and external 3,6-epoxy-1,2. ,3,6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene -1,2-Dicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, A Benicene methyltetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, allyl succinic anhydride, isocyanatoethyl methacrylate, 3-isopropenyl-α, α-dimethyl Benzyl isocyanate, 3-cyclohexene-1-methyl chloroform, 2-chloro chloro, croton chloro, cinnamyl chloride, methacryl chloro, propylene chloro, propyl chloride, butyne chloro, Thiophene 2-acetamidine chloride, p-styrenesulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, isopropyl chloroformate, Isobutyl chloroformate, 2-ethoxylate chloroformate, second butyl chloroformate, benzyl chloroformate 2-ethylhexyl chloroformate, allyl chloroformate, phenyl chloroformate, 2,2,2-trichloroethyl chloroformate, 2-butoxyethyl chloroformate, chloroformic acid-p-nitro Benzyl ester, chloroformic acid-p-methoxybenzyl ester, isobornyl chloroformate, chloroformic acid-p-phenylisopropyl benzyl ester, 2-tert-butoxycarbonyl-oxyimine-2-phenylacetonitrile , S-tert-butoxycarbonyl-4,6-dimethyl-decylpyrimidine, di-t-butyl dicarbonate, N-ethoxycarbonylphthalimide, ethyldithiocarbamidine, Formamidine, benzamidine chloride, p-toluenesulfonium chloride, methanesulfonium chloride, ethyl chloroform, triphenylchloromethane, trimethylchlorodecane, hexamethyldioxane, N, O-double (three Methyl decyl) acetamide, bis(trimethyldecyl)trifluoroacetamide, (N,N-dimethylamino)trimethyldecane, (dimethylamino)trimethyldecane , trimethyldecyl diphenylurea, bis(trimethyldecyl)urea, phenyl isocyanate, n-butyl isocyanate, n-octadecyl isocyanate, o-cresyl isocyanate 1,2-phthalic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, glutaric anhydride.

As a polycondensation method of the above dicarboxylic acid and bisaminophenol (diamine) for synthesizing dihydroxydiamine as a hydroxypolyamine, a dicarboxylic acid and a sulfinium chloride are used to obtain a dioxime. After chlorine, a method of reacting with a bisaminophenol (diamine); a method of polycondensing a dicarboxylic acid with a bisaminophenol (diamine) by dicyclohexylcarbodiimide, and the like. In the method of using dicyclohexylcarbodiimide, it is also possible to simultaneously act with hydroxybenzotriazole.

Further, it is also preferred that the PBO precursor having the repeating unit represented by the above formula (2) is used by blocking an end group thereof with an organic group (hereinafter also referred to as "blocking group"). For example, in the case of polycondensation of hydroxypolyamine, it is preferred to use an amine group when the dicarboxylic acid component is used in excess of the molar amount compared to the sum of the bisaminophenol component and the diamine component. Or a hydroxyl group as a terminal group compound. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate. A nitrogen-containing cyclic compound such as 2-aminobenzotriazole, benzothiadiazole or tetrazole.

On the other hand, when the sum of the bisaminophenol component and the diamine component is used in excess of the molar amount of the dicarboxylic acid component, it is preferred to use an acid anhydride or a carboxylic acid as the compound having a terminal group. A compound such as chloro, isocyanate or the like. Examples of the compound include benzamidine chloride, norbornene dicarboxylic anhydride, norbornenecarboxylic acid, 5-benzimidazolecarboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, and maleic anhydride. , phthalic anhydride, cyclohexanedicarboxylic anhydride, methylcyclohexanedicarboxylic anhydride, cyclohexene dicarboxylic anhydride, methacryloxyethyl methacrylate, phenyl isocyanate, methyl sulfonate醯 chloro, p-toluene sulfonium chloride, etc., wherein a preferred terminal group is selected from the group consisting of a nitrogen-containing cyclic compound such as 5-benzimidazolecarboxylic acid and a terminal group represented by the following formula (18); At least one terminal group in the group:

[化31]

(wherein L ₁₀ represents -CH ₂ -, -O- or -S-, and L ₁₁ represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 6 carbon atoms).

Next, the structure having the PI precursor will be described.

The PI precursor is a poly-proline or polyphthalate having a structure such that X ₁ (NH ₂ ) ₂ (OH) _n 2 in the structure represented by the above formula (2) (COOR ₄ ) _n3 and Y ₁ (COOH) ₂ (OH) _n4 (COOR ₅ ) _n5 when n2=0~2, n ₃ =0 or 1, n ₄ =0~2, n ₅ =1 or 2 The diamine and diamine derivatives are formed by polycondensation of a tricarboxylic acid and the above-described ruthenium chloride compound, acid anhydride compound or tetracarboxylic dianhydride. These poly-proline and polyphthalate may also contain a hydroxyl group in order to improve solubility in an alkaline aqueous solution.

Even if the polyglycolic acid and the polyamidamide are heat-treated at 250 ° C or lower, the dehydration cyclization reaction can be carried out by 90% or more to form a polyimine resin, so that low-temperature cyclization can be achieved.

From the viewpoint of the solubility in the alkaline developing solution and the heat resistance of the obtained resin film, X ₁ is preferably a tetravalent organic group having two or more and 30 or less carbon atoms. Y ₁ is preferably a divalent organic group having two or more and 36 or less carbon atoms from the viewpoint of solubility in an alkaline developer and good heat resistance of the obtained resin film. m ₂ is preferably an integer of 1 to 1000, more preferably an integer of 2 to 200, and particularly preferably 2 to 100, from the viewpoint of the solubility in the alkaline developer and the mechanical properties of the obtained resin film. Integer, the best is an integer from 3 to 60.

As a constituent (COOR ₄₎ of the diamine of Example _n3, to n ₂ = 0, and the case where n ₃ = _{(NH 2) 2 (OH)} n2 of 0 or ₁ X 1, include: 3,5-diamine A benzoic acid, an aromatic diamine or a quinone diamine used for the above PBO precursor.

In the case of n ₂ =1 or 2 and n ₃ =0 or 1, a bisphenol which is used for the above PBO precursor, represented by the above formula (12) and the above formula (13) The "diamine having a PBO precursor structure in the molecule" and the like.

As an example of the carboxylic acid constituting Y ₁ (COOH) ₂ (OH) _n4 (COOR ₅ ) _n5 , in the case of n ₄ =0 and n ₅ =1 or 2, trimellitic anhydride and benzene may be cited. Trimethic anhydride ruthenium chloride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, 4-chloroformylcyclohexanehydride, tetracarboxylic dianhydride. The tetracarboxylic dianhydride is preferably selected from the group consisting of aromatic tetracarboxylic dianhydride having a carbon number of 8 to 36 and carbon from the viewpoints of solubility in a solvent and solubility in an aqueous alkaline solution. A compound of 6 to 34 alicyclic tetracarboxylic dianhydride.

Specific examples thereof include 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2, 3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3, 3',4,4'-biphenyltetracarboxylic dianhydride, 3,3",4,4"-tert-phenyl tetracarboxylic dianhydride, 3,3"',4,4"'- Quatern-phenyl tetracarboxylic dianhydride, 3,3"", 4,4""-quinac-phenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl Tetracarboxylic acid dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2,2-propylene -4,4'-diphthalic dianhydride, 1,2-extended ethyl-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-di-ortho Phthalic anhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, Bis(3,4-dicarboxyphenyl)ether dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1, 3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxybenzene) Phthalic anhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxybenzene) Bis-propyl]benzene phthalic anhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)benzene Methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy) Phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethyl phthalane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3 -tetramethyldioxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dihydride, 3,4,9,10-tetracarboxylic acid dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,7,8-phenanthrenecarboxylic acid dianhydride, ethylene tetracarboxylic dianhydride 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane-1,2,3, 4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexanetetracarboxylic dianhydride, carbonyl-4,4'- Bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-extended ethyl-4 , 4'-bis (cyclohexane-1, 2 -dicarboxylic acid)dianhydride, 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-double (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-double (ring Hexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7- Alkene-2,3,5,6-tetracarboxylic dianhydride, endo-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6- Spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2- Dicarboxylic anhydride, ethylene glycol-bis(3,4-dicarboxylic anhydride phenyl) ether, and the like.

Among them, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, bis(3,4-dicarboxyphenyl) is preferred. Ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy) bis(phthalic anhydride), wherein It is more preferably 5-(2,5-dioxotetrahydro-3-furanyl)-3- from the viewpoint of transparency of the i-line of the mercury lamp, solubility in an alkaline aqueous solution, and photosensitivity. Methyl-cyclohexene-1,2-dicarboxylic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride. The resulting carboxylic acid residue is esterified by a monool depending on the solubility of the base.

In the case where n ₄ =1 or 2 and n ₅ = 2, an acid anhydride having two groups of amidoxime bond and a phenolic hydroxyl group which are adjacent to each other in the molecule may be used, and the acid anhydride may be used as follows. The structure represented by the formula (19) has two groups of structures in which the indole bond and the phenolic hydroxyl group are located adjacent to each other:

[化32]

In the formula, X ₆ represents a trivalent or tetravalent organic group having at least 2 carbon atoms, R ₅ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n ₁₇ represents an integer of 1 or 2.

X ₆ contains the organic group described above as the preferred _one of the organic group represented by X ₁ .

Further, it is also preferred that the end of the PI precursor having the repeating unit represented by the above formula (2) is blocked with a terminal using a terminal group as in the case of the above PBO precursor. When a carboxylic acid component is used in excess of the molar amount of the component derived from the diamine, it is preferred to use a compound having an amine group or a hydroxyl group as a terminal group. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate. A nitrogen-containing cyclic compound such as 2-aminobenzotriazole, benzothiadiazole or tetrazole.

On the other hand, when the sum of the bisaminophenol component and the diamine component is used in excess of the molar amount of the dicarboxylic acid component, it is preferred to use an acid anhydride or a carboxylic acid as the compound having a terminal group. a compound such as ruthenium chloride or isocyanate group. Examples of the compound include benzamidine chloride, norbornene dicarboxylic anhydride, norbornenecarboxylic acid, 5-benzimidazolecarboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, and maleic anhydride. , phthalic anhydride, cyclohexanedicarboxylic anhydride, methylcyclohexanedicarboxylic anhydride, cyclohexene dicarboxylic anhydride, methacryloxyethyl methacrylate, phenyl isocyanate, methyl sulfonate醯 chloro, p-toluene sulfonium chloride, etc., wherein a preferred terminal group is selected from the group consisting of a nitrogen-containing cyclic compound such as 5-benzimidazolecarboxylic acid and a terminal group represented by the following formula (18); At least one terminal group in the group:

[化33]

In the formula, L ₁₀ represents -CH ₂ -, -O- or -S-, and L ₁₁ represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 6 carbon atoms.

Next, the structure represented by the above formula (4) is described as having X ₂ (NH ₂ ) ₂ (OH) _n8 (COOR ₇ ) _n9 and Y ₃ (COOH) in addition to the structure containing a crosslinking group. The structure of the soluble PI of the unit of ₄ , or Y ₄ (COOH) ₂ (OH) _n10 (COOR ₈ ) _n11 .

The soluble PI is an alkali-soluble polymer having a polyimine structure, and the polyimine structure is (X) X ₂ (NH ₂ ) ₂ (OH) in the structure represented by the above formula (4). _N8 (COOR ₇ ) _n9 and Y ₃ (COOH) ₄ , or Y ₄ (COOH) ₂ (OH) _n10 (COOR ₈ ) _n11 in n ₈ = 2, n ₉ =0, n ₁₀ =0~2 When n ₁₁ =1 or 2, the bisaminophenol used in the above PBO precursor is formed by polycondensation of a tricarboxylic acid and the above-mentioned ruthenium chloride compound, acid anhydride compound or tetracarboxylic dianhydride.

Examples of the diamine constituting X ₂ (NH ₂ ) ₂ (OH) _n8 (COOR ₇ ) _n9 include a bisaminophenol used in the above PBO precursor, and the above formula (12) and the above formula. (13) The "diamine having a PBO precursor structure in a molecule" as indicated.

Examples of the carboxylic acid constituting Y ₃ (COOH) ₄ and Y ₄ (COOH) ₂ (OH) _n10 (COOR ₈ ) _n11 may be exemplified in the case of n ₁₀ =0 and n ₁₁ =1 or 2. : trimellitic anhydride, trimellitic anhydride ruthenium chloride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, 4-chloroformylcyclohexanehydride, tetracarboxylic dianhydride. The tetracarboxylic dianhydride exemplified herein is preferably the same as the tetracarboxylic dianhydride used for the above PI precursor. Among them, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, bis(3,4-dicarboxyphenyl) is preferred. Ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy) bis(phthalic anhydride), wherein It is more preferably 5-(2,5-dioxotetrahydro-3-furanyl)-3- from the viewpoint of transparency of the i-line of the mercury lamp, solubility in an alkaline aqueous solution, and photosensitivity. Methyl-cyclohexene-1,2-dicarboxylic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride.

Therefore, from the viewpoint of the transparency of the i-line region and the solubility of the exposed portion in the alkaline developing solution, the soluble PI structure represented by the above formula (4) is preferably selected from the following points in the molecule. At least one polyimine structure of the structure represented by the general formula (20) and the structure represented by the following general formula (21):

[化34]

Wherein X ₇ represents a group selected from the group consisting of a single bond and the following formula (15):

[化35]

At least one of the group consisting of, and m ₄ is an integer from 1 to 1000};

[化36]

In the formula, X ₇ represents at least one structure selected from the group consisting of a single bond and the following formula (15), and m ₄ is an integer of from 1 to 1000}:

[化37]

Y ₄ when in _{(COOH) 2 (OH) n10} (COOR 8) in n ₁₀ = 1 or 2 and _n11 n ₁₁ = 2 case, the PI precursor used in the above mentioned in the above general formula (19) The represented molecule has two structures in which a group of amidoxime bonds and a phenolic hydroxyl group are located adjacent to each other.

In the structure represented by the above formula (4), X ₂ (NH ₂ ) ₂ (OH) _n8 (COOR ₇ ) _n9 may be used for controlling the alkali solubility, and may be used for the above PBO precursor. Amine or 2,4-diaminophenol. In this case, a sequential copolymerization condensate can also be formed by a sequential reaction. Further, when a raw material having three or more components is supplied, the raw material may be simultaneously introduced into the reaction system to form a random copolymer condensate.

The dehydration condensation reaction in the case of synthesizing a quinone imine structure having a phenolic hydroxyl group, for example, according to the method described in International Publication No. 01/034679, in the presence of an acid catalyst or a base catalyst, the above tetracarboxylic acid The dianhydride and the phenolic diamine are heated to 30 ° C to 220 ° C, preferably 170 ° C to 200 ° C, whereby a dehydration condensation reaction is carried out. As the acid catalyst, an inorganic acid such as sulfuric acid or an organic acid such as p-toluenesulfonic acid which is usually used for the production of polyimine can be used. It is also possible to use γ-valerolactone and pyridine. As the base catalyst, pyridine, triethylamine, dimethylaminopyridine, 1,8-diazabicyclo(5,4,0)undecene-7, 1,3,5,7 can also be used. - tetraazatricyclo (3,3,1,1,3,7)decane, triethylenediamine, and the like.

Further, a method in which a polycondensation catalyst or the like is not particularly added, and the temperature of the reaction liquid is maintained at a temperature higher than the temperature at which the oxime imidization reaction is carried out, and an azeotropic solvent such as toluene or the like is used to carry out the dehydration reaction. The produced water is removed to the outside of the reaction system, and the hydrazine imidation dehydration condensation reaction is completed.

In the above dehydration condensation reaction, as the reaction solvent, in addition to toluene which is a solvent for azeotroping water, a polar organic solvent for dissolving an alkali-soluble polymer soluble in an aqueous alkaline solution is preferably used. Examples of the polar solvent include γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, and cyclobutylhydrazine.

It is also preferred that the terminal end of the soluble PI is terminated by the same method as the PI precursor.

Polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (hereinafter also referred to as "GPC") of an alkali-soluble polymer having a structure represented by the above formula (2) or the above formula (4) Preferably, it is 3,000 to 70,000, more preferably 6,000 to 50,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the hardened concave-convex pattern, and is preferably 70,000 or less from the viewpoint of resolution. As a developing solvent for GPC, tetrahydrofuran (hereinafter also referred to as "THF") and N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP") are recommended. Further, the molecular weight can be determined from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko.

Among the above alkali-soluble polymers, from the viewpoint of sensitivity, an alkali-soluble polymer containing a PBO precursor structure is preferred, and a PBO precursor is particularly preferred.

Photoacid generator (B)

The photoacid generator (B) is a compound which generates an acid by irradiation with active light. Examples of such a compound include a halogen-containing compound, a phosphonium salt, and a compound having a naphthoquinonediazide structure (hereinafter also It is called "naphthoquinonediazide compound" and the like.

A photosensitive resin composition can be formed by using the photoacid generator (B). The photosensitive resin composition can also be formed into a positive or negative type by appropriate combination. Since the photosensitive resin composition contains an alkali-soluble polymer having a structure containing a crosslinking group, it exhibits an excellent cured shape and is excellent in chemical resistance, and in particular, a positive photosensitive resin composition is formed. In the case of time, it has good lithographic properties over time after exposure. Here, the good hardened shape means a high taper angle (50 degrees or more).

The halogen-containing compound may, for example, be a hydrocarbon compound containing a halogenated alkyl group, or preferably a trichloromethyl group. class.

As trichloromethyl-all three Specific examples of the class include: tris(2,4,6-trichloromethyl)-all three 2-phenyl-bis(4,6-trichloromethyl)-all three , 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-all three , 2-(2-chlorophenyl)-bis(4,6-trichloromethyl)-all three , 2-(4-methoxyphenyl)-bis(4,6-trichloromethyl)-all three , 2-(3-methoxyphenyl)-bis(4,6-trichloromethyl)-all three , 2-(2-methoxyphenyl)-bis(4,6-trichloromethyl)-all three , 2-(4-methylthienyl)-bis(4,6-trichloromethyl)-all three , 2-(3-methylthienyl)bis(4,6-trichloromethyl-all three , 2-(2-methylthienyl)-bis(4,6-trichloromethyl)-all three , 2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-all three , 2-(3-methoxynaphthyl)-bis(4,6-trichloromethyl)-all three , 2-(2-methoxynaphthyl)-bis(4,6-trichloromethyl)-all three , 2-(3,4,5-trimethoxy-β-styrene)-bis(4,6-trichloromethyl)-all three , 2-(4-methylthio-β-styrene)-bis(4,6-trichloromethyl)-all three , 2-(3-methylthio-β-styrene)-bis(4,6-trichloromethyl)-all three , 2-(2-methylthio-β-styrene)-bis(4,6-trichloromethyl)-all three Wait.

Examples of the onium salt include a phosphonium salt, a phosphonium salt, a phosphonium salt, an ammonium salt, a diazonium salt, and the like, and are preferably selected from the group consisting of a diarylsulfonium salt, a triarylsulfonium salt, and a trialkylsulfonium salt. The salt in the group.

Specific examples of the diarylsulfonium salt include diphenylphosphonium tetrafluoroborate, diphenylphosphonium tetrafluorophosphate, diphenylsulfonium tetrafluoroarsenate, and diphenylsulfonium trifluoromethanesulfonate. Acid salt, diphenylsulfonium trifluoroacetate, diphenylphosphonium-p-toluenesulfonate, 4-methoxyphenylphenylphosphonium tetrafluoroborate, 4-methoxyphenylphenylphosphonium hexafluorophosphate Phosphonate, 4-methoxyphenylphenylphosphonium hexafluoroarsenate, 4-methoxyphenylphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenylphenylphosphonium trifluoroacetate Salt, 4-methoxyphenylphenylphosphonium-p-toluenesulfonate, bis(4-t-butylphenyl)phosphonium tetrafluoroborate, bis(4-t-butylphenyl)phosphonium hexafluorophosphate Arsenate, bis(4-t-butylphenyl)phosphonium triflate, bis(4-t-butylphenyl)phosphonium trifluoroacetate, bis(4-tert-butylphenyl) ) 錪-p-toluenesulfonate and the like.

Specific examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium methanesulfonate. , triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphate Phosphonate, 4-methoxyphenyldiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium methanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoride Acetate, 4-methoxyphenyldiphenylphosphonium-p-toluenesulfonate, 4-phenylthienyldiphenyltetrafluoroborate, 4-phenylthienyldiphenylhexafluorophosphonate, 4-phenylthienyldiphenylhexafluoroarsenate, 4-phenylthienyldiphenyltrifluoromethanesulfonate, 4-phenylthienyldiphenyltrifluoroacetate, 4-phenylthiophene Diphenyl-p-toluenesulfonate and the like.

Within these compounds, as trichloromethyl-all three The class can be exemplified by 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-all three , 2-(4-chlorophenyl)-bis(4,6-trichloromethyl)-all three , 2-(4-methylthienyl)-bis(4,6-trichloromethyl)-all three , 2-(4-methoxy-β-styrene)-bis(4,6-trichloromethyl)-all three , 2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-all three Examples of the diarylsulfonium salt include diphenylsulfonium trifluoroacetate, diphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenylphenylphosphonium trifluoromethanesulfonate, and 4 a -methoxyphenylphenyl fluorene trifluoroacetate or the like, and examples of the triarylsulfonium salt include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, and 4-methoxyphenyl di Phenyl sulfonium methanesulfonate, 4-methoxyphenyl diphenyl fluorene trifluoroacetate, 4-phenylthienyl diphenyl trifluoromethanesulfonate, 4-phenylthienyl diphenyl three Fluoroacetate or the like is preferred.

In addition to the above, the compounds shown below can also be used.

(1) bismuth compound

Examples of the ruthenium compound include a β-ketooxime compound, a β-sulfonylhydrazine compound, and an α-diazo compound of the compound. Specific examples thereof include 4-tritylmethyl hydrazine. Benzobenzidine methyl hydrazine, bis(benzhydrylmethylsulfonyl) methane, and the like.

(2) sulfonic acid compound

Examples of the sulfonic acid compound include alkylsulfonates, halogenated alkylsulfonates, arylsulfonates, and imidosulfonates. Preferred examples of the sulfonic acid compound include benzoin toluene. An acid ester, pyrogallol tris(trifluoromethanesulfonate), o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate, and the like.

(3) Sulfonimide compounds

Specific examples of the sulfonium imine compound include N-(trifluoromethylsulfonyloxy)butaneimine and N-(trifluoromethylsulfonyloxy)phthalic acid. Amine, N-(trifluoromethylsulfonyloxy)diphenylmethylene iodide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine, N-(trifluoromethylsulfonyloxy)naphthylimine, and the like.

(4) oxime ester compounds

Either exemplified: 2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene]-2-(2-methylphenyl)acetonitrile (Ciba Specialty Chemicals, Inc., trade name "Irgacure PAG121"), [2-(propylsulfonyloxyimino)-2,3-dihydrothiophene-3-ylidene]-2- (2-methylphenyl)acetonitrile (product name "Irgacure PAG103" of Ciba Specialty Chemicals Co., Ltd.).

(5) Diazomethane compounds

Specific examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(phenylsulfonyl)diazomethane. Wait.

(6) Diazomethanone

Examples of the diazomethanone compound include a 1,3-diketone-2-diazo compound, a diazonium phthalide compound, and a diazonaphthoquinone compound. Specific examples thereof include 1,2-naphthalene of phenols. A quinone diazide-4-sulfonate compound.

In the case of forming a positive photosensitive resin composition, from the viewpoint of solvent solubility and storage stability, the above (6) azomethanone compound is preferred, and from the viewpoint of sensitivity, it is preferred. It is a compound having a naphthoquinonediazide structure (hereinafter also referred to as "naphthoquinonediazide compound").

Further, in the case of forming a negative photosensitive resin composition, the above (4) oxime ester compound is particularly preferable from the viewpoint of sensitivity.

The above naphthoquinonediazide compound is typically a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure, according to the specification of U.S. Patent No. 2,772,972, and U.S. Patent No. 2,797,213. A material known from the specification of U.S. Patent No. 3,669,658. The naphthoquinonediazide compound is typically 1,2-naphthoquinonediazide-4-sulfonate selected from a polyhydroxy compound having the specific structure described below, and 1,2-naphthoquinone of the polyhydroxy compound. At least one compound (hereinafter also referred to as "NQD compound") of a group consisting of diazide-5-sulfonate.

The NQD compound is obtained by the following method: using a chlorosulfonic acid or sulfinium chloride to form a naphthoquinonediazidesulfonic acid compound to form a sulfonium chloride, and the resulting naphthoquinone diazide sulfonium chloride is Polyhydroxy compound condensation reaction. For example, a specific amount of the polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride is A solvent such as an alkane, acetone or tetrahydrofuran is reacted in the presence of a basic catalyst such as triethylamine to carry out esterification, and the obtained product is washed with water and dried to obtain an NQD compound.

As the NQD compound, those enumerated below are preferably used.

An NQD compound of a polyhydroxy compound represented by the following formula (22)

[化38]

In the formula, X ₈ is selected from the following chemical formula:

[39]

At least one tetravalent group of the organic group represented, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ each independently represent a monovalent organic group, 1 is 0 or 1, m ₈ , m ₉ , m ₁₀ and m ₁₁ An integer representing 0 to 3, n ₁₈ , n ₁₉ , n _{20 ,} and n ₂₁ are integers of 0 to 2}.

Specific examples of the compound include compounds described in [Chem. 23] to [Chem. 28] of JP-A-2001-092138.

Among them, the NQD compound of the following polyhydroxy compound is preferred because of its high sensitivity and low precipitation in the positive photosensitive resin composition.

[化40]

[化41]

[化42]

[化43]

NQD compound of a polyhydroxy compound represented by the following formula (23)

[化44]

In the formula, M ₂ represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and A ₃ represents a chemical formula selected from the group consisting of:

[化45]

At least one divalent base of the indicated group}.

Specific examples of the compound include compounds described in JP-A-2003-131368 (Chem. 22) to (Chem. 28).

Among them, the NQD compound of the following polyhydroxy compound is preferred because the sensitivity is high and the precipitation property in the positive photosensitive resin composition is low.

[Chem. 46]

[化47]

In the formula, L ₁₂ represents -CH ₂ -, -O- or -S-, and L ₁₃ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and an alkenyl group}.

NQD compound of a polyhydroxy compound represented by the following formula (24)

[48]

In the formula, R ₁₉ , R ₂₀ and R ₂₁ each independently represent a monovalent organic group represented by the following formula:

[化49]

(wherein R ₂₂ each independently represents a hydrogen atom, or at least one monovalent organic group selected from the group consisting of an alkyl group and a cycloalkyl group, and m ₁₅ is an integer of 0 to 2), and m ₁₂ , m ₁₃ and m _{14 is} independently an integer of 0~2}.

Specific examples of the compound include an NQD compound of a polyhydroxy compound described in [Chem. 17] to [Chem. 22] of JP-A-2004-109849.

Among them, the NQD compound of the following polyhydroxy compound is preferred because the sensitivity is high and the precipitation property in the positive photosensitive resin composition is low.

[化50]

[化51]

NQD compound of a polyhydroxy compound represented by the following formula (25)

[化52]

In the formula, R ₂₃ represents a monovalent organic group represented by the following formula:

[化53]

(wherein R ₂₇ each independently represents a hydrogen atom or at least one monovalent organic group selected from the group consisting of an alkyl group and a cycloalkyl group, and m ₁₉ is an integer of 0 to 2), R ₂₄ , R ₂₅ and R ₂₆ represent a hydrogen atom or at least one monovalent organic group selected from the group consisting of an alkyl group and a cycloalkyl group, and m ₁₆ , m ₁₇ and m ₁₈ are integers of 0 to 2}.

Specific examples of the compound include NQD compounds of polyhydroxy compounds described in JP-A-2005-008626, and [Chem. 16].

Among them, the NQD compound of the following polyhydroxy compound is preferred because the sensitivity is high and the precipitation property in the positive photosensitive resin composition is low.

[54]

[化55]

As another structure, the following structure is preferable:

[化56]

As the naphthoquinonediazidesulfonyl group in the NQD compound, 5-naphthoquinonediazidesulfonyl group or 4-naphthoquinonediazidesulfonyl group is preferred.

The 4-naphthoquinonediazidesulfonyl ester compound has absorption in the i-line region of the mercury lamp and is suitable for i-line exposure. The absorption of the 5-naphthoquinonediazidesulfonyl ester compound extends to the g-line region of the mercury lamp and is suitable for g-line exposure. In the present invention, it is preferred to select any one of a 4-naphthoquinonediazidesulfonyl ester compound or a 5-naphthoquinonediazidesulfonyl ester compound depending on the wavelength used for exposure. Further, a naphthoquinonediazidesulfonyl ester compound having both 4-naphthoquinonediazidesulfonyl group and 5-naphthoquinonediazidesulfonyl group in the same molecule may also be used, and 4- The naphthoquinonediazidesulfonyl ester compound is used in combination with a 5-naphthoquinonediazidesulfonyl ester compound.

In the photosensitive resin composition of the present invention, the amount of the photoacid generator (B) is preferably from 1 to 50 parts by weight based on 100 parts by weight of the alkali-soluble polymer (A), and is soluble in a solvent. The viewpoint is preferably 2 to 40 parts by weight, and more preferably 5 to 25 parts by weight from the viewpoint of sensitivity. When the amount of the photoacid generator (B) is 1 part by weight or more, the patterning property of the resin is good. On the other hand, when the amount of the photoacid generator (B) is 50 parts by weight or less, the curing is performed. The tensile elongation of the film is good, and the development residue (residue) of the exposed portion is small.

Organic germanium compound (C)

In the photosensitive resin composition of the present invention, it is preferred to further compound the organic ruthenium compound (C) from the viewpoint of exhibiting better adhesion to the substrate.

The organic ruthenium compound (C) is a compound containing a monofunctional or higher alkoxyalkylene group and a decyl group, and is a bonding aid for improving adhesion to a ruthenium wafer. The carbon number of the organic hydrazine compound is preferably from 4 to 30, more preferably from 4 to 18, from the viewpoint of solubility in a solvent.

Specific examples of the compound include 3-mercaptopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Co., Ltd.: trade name Sila-Ace S810), 3-mercaptopropyl three Ethoxy decane (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Co., Ltd.: commodity SIM6474.0), 巯methyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), 巯methylmethyldimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0) , 3-mercaptopropyldiethoxymethoxydecane, 3-mercaptopropylethoxydimethoxydecane, 3-mercaptopropyltripropoxydecane, 3-mercaptopropyldiethoxypropane Oxydecane, 3-mercaptopropyloxydipropoxydecane, 3-mercaptopropyldimethoxypropoxydecane, 3-mercaptopropylmethoxydipropoxydecane, 2-indenyl Trimethoxy decane, 2-mercaptoethyl diethoxy methoxy decane, 2-mercaptoethyl ethoxy dimethoxy decane, 2- 巯Tripropoxydecane, 2-decylethyltripropoxydecane, 2-decylethylethoxydipropoxydecane, 2-decylethyldimethoxypropoxydecane, 2-fluorenylethyl Methoxydipropoxydecane, 4-decyl butyl trimethoxy decane, 4-decyl butyl triethoxy decane, 4-decyl butyl tripropoxy decane, N-(3-triethoxy)矽Alkylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxydecylpropyl)urea (limited by Azmax) Made by the company: trade name SIU9058.0), N-(3-diethoxymethoxydecylpropyl)urea, N-(3-ethoxydimethoxydecylpropyl)urea, N- (3-tripropoxydecylpropyl)urea, N-(3-diethoxypropoxydecylpropyl)urea, N-(3-ethoxydipropoxydecylpropyl) Urea, N-(3-dimethoxypropoxydecylpropyl)urea, N-(3-methoxydipropoxydecylpropyl)urea, N-(3-trimethoxydecylalkyl) Ethyl)urea, N-(3-ethoxydimethoxydecylethyl)urea, N-(3-tripropoxydecylethyl)urea, N-(3-tripropoxydecane base Urea, N-(3-ethoxydipropoxydecylethyl)urea, N-(3-dimethoxypropoxydecylethyl)urea, N-(3-methoxy Dipropoxydecylethyl)urea, N-(3-trimethoxydecylbutyl)urea, N-(3-triethoxydecylbutyl)urea, N-(3-tripropoxygen) Alkyl butyl)urea, 3-(m-aminophenoxy)propyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyltrimethoxydecane (Azmax) Manufactured by: Ltd.: trade name SLA0599.0), p-aminophenyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SLA0599.1), aminophenyltrimethoxydecane (manufactured by Azmax Co., Ltd.: commodity SLA0599.2), 2-(trimethoxydecylethyl)pyridine (manufactured by Azmax Co., Ltd.: trade name SIT8396.0), 2-(triethoxydecylethyl)pyridine, 2-(two Methoxydecylmethylethyl)pyridine, 2-(diethoxydecylmethylethyl)pyridine, (3-triethoxydecylpropyl)-tert-butylcarbamate , (3-glycidoxypropyl) triethoxy decane, tetramethoxy decane, tetraethoxy Decane, tetra-n-propoxy decane, tetra-isopropoxy decane, tetra-n-butoxy decane, tetra-isobutoxy decane, tetra-butoxy decane, tetrakis (methoxy ethoxy) Base decane), tetrakis(methoxy-n-propoxy decane), tetrakis(ethoxyethoxy decane), tetrakis(methoxyethoxyethoxy decane), bis(trimethoxydecyl) Ethane, bis(trimethoxydecyl)hexane, bis(triethoxydecyl)methane, bis(triethoxydecyl)ethane, bis(triethoxydecyl)ethylene, bis ( Triethoxynonyl)octane, bis(triethoxydecyl)octadiene, bis[3-(triethoxydecyl)propyl]disulfide, bis[3-(triethoxy) Base alkyl)propyl]tetrasulfide, di-t-butoxydiethoxydecane, di-isobutoxyaluminoxytriethoxydecane, bis(glutaric acid)titanium-O, O'-bis(oxyethyl)-aminopropyltriethoxydecane, phenyldecanetriol, methylphenyldecanediol, ethylphenyldecanediol, n-propylphenylnonane II Alcohol, isopropyl phenyl decane diol, n-butyl phenyl decane diol, isobutyl phenyl decane diol, tert-butyl phenyl矽 二醇 diol, diphenyl decane diol, dimethoxy diphenyl decane, diethoxy diphenyl decane, dimethoxy bis-p-tolyl decane, ethyl methyl phenyl decyl alcohol, positive Propylmethylphenylnonanol, isopropylmethylphenylnonanol, n-butylmethylphenylnonanol, isobutylmethylphenylnonanol, tert-butylmethylphenylnonanol, ethyl-n-propylbenzene Base alcohol, ethyl isopropyl phenyl decyl alcohol, n-butyl ethyl phenyl decyl alcohol, isobutyl ethyl phenyl decyl alcohol, tert-butyl ethyl phenyl decyl alcohol, methyl diphenyl Sterol, ethyl diphenyl decyl alcohol, n-propyl diphenyl decyl alcohol, isopropyl diphenyl decyl alcohol, n-butyl diphenyl decyl alcohol, isobutyl diphenyl decyl alcohol, third butyl Diphenyl sterol, triphenyl decyl alcohol, etc., but not limited thereto. These may be used alone or in combination.

The organic ruthenium compound (C) is preferably an organic ruthenium compound represented by the following formula (26) or the following formula (27) from the viewpoint of storage stability:

[化57]

In the formula, Z ₄ is an aromatic ring or a heterocyclic ring structure in which the number of carbon atoms is 1 to 14 and R ₂₈ is a hydrocarbon group having 1 to 20 carbon atoms, and R ₂₉ is a hydrogen atom or a carbon atom. Is a hydrocarbon group of 1 to 5, n ₂₂ is an integer of 1 to 3, n ₂₃ is an integer of 0 to 2, and n ₂₄ is an integer of 1 to 3, where n ₂₂ + n ₂₃ + n ₂₄ = 4}:

[化58]

The organic ruthenium compound (C) represented by the above formula (26) is more preferably a compound represented by the following formula (28) from the viewpoint of heat resistance:

[化59]

In the formula, R ₃₀ and R ₃₁ are a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and m ₂₀ = 5, and n ₂₅ and n ₂₆ are integers of 1 to 3, where n ₂₅ + n ₂₆ = 4}.

Specific examples of such compounds include phenyl decane triol, trimethoxy phenyl decane, trimethoxy (p-tolyl) decane, dimethoxy diphenyl decane, and diethoxy diphenyl decane. , diphenyl decanediol, dimethoxy bis-p-tolyl decane, triphenyl decyl alcohol, and the like.

The organic hydrazine compound (C) may be used singly or in combination of two or more. The compounding amount of the organic cerium compound (C) is preferably from 1 to 40 parts by weight, preferably from 2 to 30 parts by weight, more preferably from 4 to 20 parts by weight, per 100 parts by weight of the alkali-soluble polymer (A). When the compounding amount of the compound is 1 part by weight or more, the developing residue of the exposed portion does not exist, and the adhesion to the ruthenium substrate is good. On the other hand, when the compounding amount of the compound is 40 parts by weight or less, the cured film The tensile elongation is good, showing good adhesion and lithography properties.

Monocarboxylic acid compound (D)

In the photosensitive resin composition of the present invention, it is preferred to further compound the monocarboxylic acid compound (D) from the viewpoint of exhibiting higher sensitivity lithography performance.

The monocarboxylic acid compound (D) refers to a compound having only one carboxylic acid in its molecule, and is a compound having 6 to 30 carbon atoms. Further, a compound having a branched structure, a ring structure or an unsaturated double bond and having 6 to 30 carbon atoms is preferred. Specific examples thereof include 2-decenoic acid, isodecanoic acid, 2-decenoic acid, 10-undecenoic acid, 3-cyclohexene-1-carboxylic acid, meta-anisic acid, m-toluic acid, and m-toluic acid. , o-anisic acid, o-toluic acid, o-toluic acid, p-anisic acid, p-toluic acid, p-toluic acid, 3-phenyllactate, 4-hydroxyphenyllactate, 4-hydroxymandelic acid, 3,4 - Dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2-(1-naphthyl)propionic acid, mandelic acid, phenyllactate, acetaminopicmandelic acid , α-methoxyphenylacetic acid, and the like.

Since the monocarboxylic acid compound exhibits an effect by remaining in the film during prebaking, it is preferably a carboxylic acid compound having a carbon number of 8 or more from the viewpoint of remaining in the prebaked film. From the viewpoint of the solubility in the viewpoint of the solubility, the carbon number is preferably 30 or less, and more preferably the carbon number is 20 or less, and particularly preferably 15 or less from the viewpoint of precipitation after the lapse of time. Further, as a method of effectively leaving a carboxylic acid in the film, a functional group selected from a hydroxyl group, an ether group, and an ester group is preferably present at the α position of the carboxyl group, and particularly, an ether group or an ester group is bonded to the substrate. It is preferable from the viewpoint of the adhesion, and in view of the sensitivity, it is particularly preferable to form a crosslinking group such as a methylol group or an alkoxymethyl group at the α position of the carboxyl group when the cured resin film is formed. The carboxylic acid compound remaining after prebaking is a nonvolatile resin composition.

These monocarboxylic acid compounds (D) may be used alone or in combination of two or more. Regarding the effect in the case of adding the monocarboxylic acid compound (D), the PBO precursor exhibits a higher sensitivity lithography performance than the PI precursor and the soluble PI due to the difference in the interaction with the polymer.

The amount of the monocarboxylic acid compound (D) to be added is preferably from 1 to 40 parts by weight, preferably from 5 to 10 parts by weight, per 100 parts by weight of the alkali-soluble polymer (A). When the amount of the monocarboxylic acid compound (D) is 1 part by weight or more, the development residue in the exposed portion is reduced, and the film formed using the photosensitive resin composition has good adhesion to the ruthenium substrate. When the amount is 40 parts by weight or less, the film reduction at the time of curing is small, and the tensile elongation of the film after curing is good.

Phenol compound (E)

In the photosensitive resin composition of the present invention, it is preferred to further formulate the phenol compound (E) from the viewpoint of exhibiting higher sensitivity lithography performance.

The phenol compound (E) includes a compound having at least one phenolic group and a polymer obtained by polymerizing the compound.

The compound having at least one phenolic group is a compound having 6 to 40 carbon atoms, and specific examples thereof include a ballast agent or a pair of the predetermined carbon atoms used in the photosensitive diazonium compound. Non-linear phenols such as phenols, bisphenols, resorcinols, MtrisPC, MtetraPC, etc. (manufactured by Honshu Chemical Industry Co., Ltd.: trade name), TrisP-HAP, TrisP-PHBA, TrisP-PA, etc. a compound (manufactured by Honshu Chemical Industry Co., Ltd.: trade name), a compound in which 2 to 5 hydrogen atoms of a phenyl group of diphenylmethane are substituted by a hydroxyl group, and a phenyl group in which 2,2-diphenylpropane is substituted by a hydroxyl group ~5 hydrogen compounds and the like. In addition, the ballast agent refers to a phenol compound used as a raw material in the above-mentioned photosensitive diazonium compound which is a phenol compound in which a part of a phenolic hydrogen atom is esterified with naphthoquinonediazide.

Among the compounds having at least one phenolic group, from the viewpoint of promoting alkali dissolution, a phenol compound having two or more phenol groups is preferred, and from the viewpoint of suppressing generation of residue, the most preferable is isophthalic acid. Phenols. Examples of the resorcinol include resorcin, 2-methylresorcin, 4-methylresorcin, 5-methylresorcin, and 2,5-dimethyl Hydroquinone, 4-ethyl resorcinol, 4-hexyl resorcinol, and the like.

Examples of the polymer obtained by polymerizing the compound include a phenol resin and a derivative thereof, polyhydroxystyrene, and a derivative thereof.

Specific examples of the phenol resin and its derivative include a novolac type resin. As the novolak type resin, those widely used in the field of resists can be used. The novolac type resin can be obtained, for example, by reacting a phenol with an aldehyde or a ketone in the presence of an acidic catalyst.

Examples of the phenols include, in addition to the above-exemplified compounds, phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, and 3. 4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6 -trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-methylresorcinol, 4-methylresorcinol, 5- Methyl resorcinol, 4-tert-butyl catechol, 2-methoxyphenol, 3-methoxyphenol, 2-propyl phenol, 3-propyl phenol, 4-propyl phenol, 2-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, thymol, isothanol, and the like. These may be used alone or in combination of two or more.

Examples of the aldehydes include formaldehyde, formalin, paraformaldehyde, and trisole. Alkane, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzene Formaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, terephthalaldehyde, and the like. Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, and benzophenone. These may be used alone or in combination of two or more.

Among the above, it is particularly preferable from the viewpoint of sensitivity controllability by using m-cresol and p-cresol to form a novolak-type resin which is condensed with formaldehyde, formalin or paraformaldehyde. The weight ratio of m-cresol to p-cresol is usually 20:80 to 80:20, preferably 50:50 to 70:30.

The molecular weight is usually from 1,000 to 20,000, preferably from 1,000 to 15,000, more preferably from 1,000 to 10,000, based on the weight average molecular weight. The weight average molecular weight of the above resin can be controlled to a desired range by adjusting the synthesis conditions. Moreover, the sensitivity of the molecular weight distribution is increased, so that the resin obtained by the synthesis can be solid-liquid extracted by using an organic solvent having a suitable solubility, or the resin can be dissolved in a good solvent and added to the poor solvent. The solid-liquid or liquid-liquid extraction is carried out by adding or adding a poor solvent to control the molecular weight distribution. Specific examples of the phenol resin include EP4000B (asahi organic material industry: trade name), EP4020G (asahi organic material industry: trade name), EP4050G (asahi organic material industry: trade name), and EP4080G (asahi organic material industry: Product name).

Specific examples of the polyhydroxystyrene or a derivative thereof include poly-o-hydroxystyrene, poly-m-hydroxystyrene, poly-p-hydroxystyrene, poly-α-methyl-o-hydroxystyrene, and the like. Poly-α-methyl-m-hydroxystyrene, poly-α-methyl-p-hydroxystyrene or a part of acetylated compounds, decyl compounds and the like. The polyhydroxystyrene or a derivative thereof has a weight average molecular weight of from 3,000 to 100,000, particularly preferably from 4,000 to 20,000.

In the case of formulating the phenol compound (E), the compounding amount is preferably from 1 to 100 parts by weight, based on 100 parts by weight of the alkali-soluble polymer (A), and preferably from 1 to 70 parts by weight in terms of hardening shape. Share. When the amount added is 70 parts by weight or less, the heat resistance of the film after heat curing is good. These may be used alone or in combination of two or more.

Compound (F) which undergoes crosslinking reaction by heat

In the photosensitive resin composition of the present invention, in view of exhibiting better lithographic performance, it is preferred to further compound the compound (F) which undergoes a crosslinking reaction by heat.

The compound (F) which undergoes a crosslinking reaction by heat is a compound which undergoes crosslinking reaction with the alkali-soluble polymer (A) by heat. Here, as the temperature at which the crosslinking reaction occurs, it is preferably 150 to 350 °C. The crosslinking reaction occurs when heat treatment is performed after patterning by development.

Examples of the specific compound include an epoxy compound, an oxetane compound, a melamine compound, and an alkenyl compound, and a compound having a structure represented by the following formula (5), and having the following formula (6) The compound having the structure shown and the compound having the structure represented by the following formula (7) are not limited thereto.

The alkenyl compound herein means a compound containing an unsaturated double bond group such as a (meth) acrylate group, an allyl group or a vinyl group.

Specific examples of the epoxy compound include a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, a glycidylamine type epoxy resin, a polysulfide type epoxy resin, and the like. , but not limited to these.

The oxetane compound is a compound having a 4-membered cyclic ether structure, and can undergo a cationic ring-opening polymerization reaction or an addition reaction with a carboxylic acid, a mercaptan or a phenol. Specific examples of the oxetane compound include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene and bis[1-ethyl ( 3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 4,4'-bis (3 -ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxo Heterocyclic butyl methyl)ether, bis(3-ethyl-3-oxetanylmethyl)diphenolate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol Tetrakis(3-ethyl-3-oxetanylmethyl)ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]sesquioxane] Derivatives, oxetane decanoate, phenol novolac type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 ( East Asian synthesis: trade name), OXT221 (East Asian synthesis: trade name), etc., but is not limited to these.

From the viewpoint of heat resistance, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 4,4'-bis (3- Ethyl-3-oxetanylmethoxy)biphenyl, OXT121 (East Asian synthesis: trade name).

Specific examples of the melamine compound include trimethylol melamine, hexamethylol melamine, trimethoxymethyl melamine, and hexamethoxymethyl melamine. From the viewpoint of storage stability, trimethoxy is preferable. Methyl melamine, hexamethoxymethyl melamine.

Specific examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, olefin Phenol, allylphenyl hydrazine, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate Ester, diallyl isocyanurate, triallylamine, triallyl cyanurate, triallyl cyanurate, triallylamine, 1,3,5-benzene Triallyl tricarboxylate, triallyl trimellitate (TRIAM 705, manufactured by Wako Pure Chemical Industries, Ltd.), triallyl pyromellitate (manufactured by Wako Pure Chemical Industries, Ltd., TRIAM805), oxydiphthalate Triallylcarboxylate, triallyl phosphate, triallyl phosphite, triallyl citrate, but not limited thereto. From the viewpoint of sensitivity, triallyl trimellitate (TRIAM 705, manufactured by Wako Pure Chemical Industries, Ltd.), triallyl pyromellitic acid (manufactured by Wako Pure Chemical Industries, Ltd., TRIAM 805) is preferred.

The (meth) acrylate compound means a compound selected from the group consisting of acrylate, methacrylate, acrylamide, and methacrylamide.

Specific examples of the preferred ones include M-20G, M-40G, M-90G, M-230G, CB-1, SA, S, and AMP-10G of the NK-ester series manufactured by Shin-Nakamura Chemical Industry Co., Ltd. AMP-20G, AMP-60G, AM-90G, A-SA, LA, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, BPE-100, BPE-200, BPE-500, BPE-1300, A-200, A-400, A-600, A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4, 701A, TMPT, A-TMPT, A-TMM-3, A-TMM-3L, A-TMMT and 1-(acryloxy)-3-(methacryloxy)-2-propanol, 1,3-double (acryloxy)-2-propanol or the like, but is not limited thereto. The (meth) acrylate compound preferably has 9 or more carbon atoms, and is preferably 30 or less from the viewpoint of solubility in a solvent.

Further, from the viewpoint of alkali solubility, the (meth) acrylate compound preferably contains a polar group such as a hydroxyl group, a carboxyl group, a carbonyl group, a decylamino group or a thiol group, and is preferably a viewpoint of adhesion. The polar group is a hydroxyl group. Specific examples of the compound include NK-701, 1-(acryloxy)-3-(methacryloxy)-2-propanol, and 1,3-bis(acryloxy)-2. -propanol and the like. The (meth) acrylate means acrylate or methacrylate.

As a compound having a structure represented by the following formula (5):

[60]

Wherein R ₉ is a hydrogen atom or a monovalent group selected from the group consisting of methyl, ethyl, n-propyl, and isopropyl, R ₁₀ is a hydrogen atom, or is selected from a hydroxyl group, carbon At least one monovalent organic group of a group consisting of an alkyl group having 1 to 6 atoms, an alkoxy group, an ester group having 2 to 10 carbon atoms, and an amine group having 2 to 10 carbon atoms n ₁₂ is an integer from 1 to 5, and n ₁₃ is an integer from 0 to 4. Here, n ₁₂ + n ₁₃ = 5, m ₆ is an integer from 1 to 4, and Z ₂ is CH at m ₆ =1. ₂ OR ₉ or R ₁₀ , when m ₆ = 2~4, is a single bond or a 2 to 4 valence organic group, where, in the case of a plurality of CH ₂ OR ₉ and R ₁₀ , R ₉ and R ₁₀ may be the same or different from each other}, and a methylol compound or an alkoxymethyl compound may be mentioned. Here, the organic group having a valence of 2 to 4 of Z ₂ may, for example, be an ether group, a thioether group, a sulfonyl group, a hydrocarbon group having 1 to 11 carbon atoms or a fluorine-containing hydrocarbon group. Examples of the fluorine-containing hydrocarbon group include hexafluoropropane and the like.

The specific example of the compound represented by the formula (5) is more preferably a compound selected from the group consisting of the following general formula (29) and the following general formula (30) from the viewpoint of sensitivity:

[化61]

[化62]

As a compound having a structure represented by the following formula (6):

[化63]

In the formula, R ₁₁ and R ₁₂ are each independently a hydrogen atom, or a hydrocarbon group selected from a carbon number of 1 to 10, and R ₁₃ CO- (wherein R ₁₃ is a hydrocarbon group having 1 to 10 carbon atoms) Examples of the group in the group to be formed include an N-methylol compound or an N-alkoxymethyl compound.

The compound represented by the formula (6) is preferably a compound selected from the group consisting of the following formula (31) from the viewpoint of sensitivity:

[化64]

As the compound having a structure represented by the following formula (7):

[化65]

In the formula, D ₁ is a functional group selected from the group consisting of an alkyl group or an alkenyl group having 1 to 6 carbon atoms and an organic group capable of crosslinking, and M ₁ is selected from -CH ₂ -, a group in the group consisting of -O-, and -S-, Z ₃ is a divalent organic group, and n ₁₄ is an integer of 0 to 4. When there are a plurality of D ₁ , a plurality of D ₁ may be the same The bisallyl diimide compound or the double norbornene quinone imine compound may, for example, be mentioned. Here, the organic group capable of crosslinking in D ₁ may, for example, be an epoxy group or an oxetanyl group, and the organic group having a valence of Z _{3 may} be a hydrocarbon group having 1 to 12 carbon atoms.

The compound represented by the formula (7) is more preferably a compound selected from the group consisting of the following formula (32) from the viewpoint of sensitivity:

[化66]

The compound (F) which undergoes the crosslinking reaction by heat may be used singly or in combination of two or more.

The amount of the compound (F) to be crosslinked by heat is preferably from 1 to 50 parts by weight, more preferably from 2 to 30 parts by weight, based on 100 parts by weight of the alkali-soluble polymer (A). It is 4 to 20 parts by weight. When the compounding amount of the compound is 1 part by weight or more, the hardened shape at the time of curing becomes good, and when the compounding amount of the compound is 50 parts by weight or less, the tensile elongation of the film after curing is good and the performance is good. Good adhesion and lithography performance.

An acid-producing compound (G) by heat

In the photosensitive resin composition of the present invention, it is preferred to heat-treat the concavo-convex pattern obtained after development (hereinafter referred to as "hardening"), and to exhibit better adhesion to the substrate. In order to further formulate a compound (G) which generates an acid by heat.

The compound (G) which generates an acid by heat is a compound which promotes the reaction of the compound (F) which undergoes the crosslinking reaction by heat, and the temperature at which the acid is generated is preferably 150 to 350 °C.

Specific examples of the compound include ethyl acetate, methyl acetate, tert-butyl acetate, tert-butyl acetate, tributyl acrylate, allyl chloroacetate, n-butyl chloroacetate, and chloroacetic acid. Third butyl ester, ethyl chloroacetate, methyl chloroacetate, benzyl fluoroacetate, isopropyl chloroacetate, 2-methoxyethyl chloroacetate, methyl dichloroacetate, methyl trichloroacetate, trichloro Ethyl acetate, 2-ethoxyethyl trichloroacetate, tert-butyl cyanoacetate, tert-butyl methacrylate, ethyl trifluoroacetate, methyl trifluoroacetate, phenyl trifluoroacetate, three Vinyl fluoroacetate, isopropyl trifluoroacetate, allyl trifluoroacetate, ethyl benzoate, methyl benzoate, tert-butyl benzoate, methyl 2-chlorobenzoate, ethyl 2-chlorobenzoate Ester, ethyl 4-chlorobenzoate, ethyl 2,5-dichlorobenzoate, methyl 2,4-dichlorobenzoate, ethyl p-fluorobenzoate, methyl p-fluorobenzoate, pentachlorophenyl Carboxylic acid esters such as tert-butyl formate, methyl pentafluoropropionate, ethyl pentafluoropropionate, and tributyl butyl crotonate; cyclic carboxylic acid esters such as phenolphthalein and rethroquinone, methanesulfonate Ethyl ester, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, 2-isopropoxyethyl methanesulfonate, phenyl p-toluenesulfonate, ethyl p-toluenesulfonate, p-toluenesulfonic acid Methyl ester, 2-phenylethyl p-toluenesulfonate, n-propyl p-toluenesulfonate, n-butyl p-toluenesulfonate, tert-butyl p-toluenesulfonate, n-hexyl p-toluenesulfonate, p-toluenesulfonic acid Heptyl ester, n-octyl p-toluenesulfonate, 2-methoxyethyl p-toluenesulfonate, propargyl p-toluenesulfonate, 3-butynyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, three Sulfonic acid esters such as n-butyl fluoromethanesulfonate, ethyl perfluorobutanesulfonate, methyl perfluorobutanesulfonate, and ethyl perfluorooctanesulfonate, 1,4-butene lactone, 2,4- Cyclic sulfonates such as butarolactone, 1,3-propane lactone, phenol red, bromocresol green, bromocresol purple, 2-sulfobenzoic anhydride, p-toluenesulfonic anhydride, ortho-benzene Formic anhydride and the like.

Preferred among the acid derivative compounds include ethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, and 2-isopropoxyethyl methanesulfonate. , p-toluenesulfonate phenyl ester, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, 2-methoxyethyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate , sulfonate esters such as ethyl perfluorobutanesulfonate, methyl perfluorobutanesulfonate, ethyl perfluorooctanesulfonate, 1,4-butane lactone, 2,4-butane lactone, 2- Sulfobenzoic anhydride, p-toluenesulfonic anhydride.

Further, from the viewpoint of adhesion to the substrate, examples of a more preferable compound include ethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, and ethyl p-toluenesulfonate. Methyl p-toluenesulfonate, 2-methoxyethyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, 1,4-butene lactone, 2,4-butyl Sulfonate, 2-sulfobenzoic anhydride, p-toluenesulfonic anhydride, and the like. Further, these compounds may be used singly or in combination of two or more.

The compounding amount of the compound (G) which generates an acid by heat is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the alkali-soluble polymer (A). It is 2 to 10 parts by weight. When the amount is 0.1 part by weight or more, the effect of maintaining the pattern after heat curing is obtained. On the other hand, when the amount is 30 parts by weight or less, the lithographic performance is not adversely affected, and the stability of the composition is stabilized. good.

a compound capable of crosslinking by the action of an acid (H)

In the case of forming a negative photosensitive resin composition, it is necessary to formulate a compound (H) which can be crosslinked by the action of an acid.

The compound (H) which can be crosslinked by the action of an acid is preferably a melamine resin and a monomer thereof selected from a N-position substituted with a methylol group or an alkoxymethyl group, and a urea resin and a monomer thereof. Examples of such an example include an alkoxymethylated melamine resin, an alkoxymethylated benzene melamine resin, an alkoxymethylated glycoluril resin, an alkoxymethylated urea resin, and the like. . Within such alkoxymethylated melamine resin, alkoxymethylated benzene melamine resin, alkoxymethylated glycoluril resin, alkoxymethylated urea resin, and the like It is obtained by converting a known methylolated melamine resin, a methylolated benzene melamine resin, a methylolated urea resin, and a methylol group thereof into an alkoxymethyl group.

Examples of the type of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Commercially available Cymel 300 can be preferably used. 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Mitsui Cytec), Nikalac MX-270 -280, -290, Nikalac MS-11, Nikalac MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.), and the like. These compounds may be used singly or in combination.

The monomer of the above resin is also used as a crosslinking agent, and examples thereof include hexamethoxymethylmelamine and dimethoxymethylurea. When the compound which can be crosslinked with the polymer by the action of an acid is added, when the coating film is heat-hardened, the heat-resistant alkali-soluble polymer (A) can be cross-linked or it can form a cross. It is connected to the ground, so heat resistance can be enhanced.

The compounding amount (H) of the compound which can be crosslinked by the action of an acid is preferably from 1 to 50 parts by weight based on 100 parts by weight of the alkali-soluble polymer (A). When the amount is more than 1 part by weight, the crosslinking is sufficiently performed, and the patterning property is improved. When the amount is 50 parts by weight or less, the mechanical properties after curing can be maintained.

a compound that becomes a sensitizer (I)

In the case of forming a negative photosensitive resin composition, it is preferred to add a compound (I) which is a sensitizer to improve photosensitivity.

Specific examples of the compound (I) to be a sensitizer include: mithicone, 4,4'-bis(diethylamino)benzophenone, and 2,5-bis (4'-di Ethylaminobenzylidene)cyclopentanone, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-dimethylaminobenzylidene 4-methylcyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino) Chalconketone, 4,4'-bis(diethylamino)chalcone, 2-(4'-dimethylaminophenylallyl) indanone, 2-(4'- Dimethylaminobenzylidene)indanone, 2-(p--4'-dimethylaminobiphenyl)benzothiazole, 1,3-bis(4-dimethylaminobenzylidene Acetone, 1,3-bis(4-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-ethenyl-7 - dimethylamino coumarin, 3-ethoxycarbonyl-7-dimethylamino coumarin, 3-benzyloxycarbonyl-7-dimethylamino coumarin, 3-methoxy Carbocarbonyl-7-diethylamino coumarin, 3-ethoxycarbonyl-7-diethylamino coumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenyl Alcoholamine, N,N-bis(2-hydroxyethyl)aniline, 4-morpholinylbenzophenone, isoamyl 4-dimethylaminobenzoate, 4-diethylaminobenzoic acid Amyl ester, benzotriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3, 4-tetrazole, 1-(t-butyl)-5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzene and Oxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphthoquinone (1,2-p)thiazole, 2-(p-dimethyl Amino benzhydryl) styrene and the like. Preferably, the addition is selected from the group consisting of benzotriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-fluorenyl -1,2,3,4-tetrazole, and 1-(t-butyl)-5-mercapto-1,2,3,4-tetrazole, having a substituent at the 3-position and/or the 7-position Coumarins, flavonoids, dibenzylidene acetonide, dibenzylidene hexane, chalcone, xanthones, 9-oxosulfur One or more sensitizers of the group consisting of steroids, porphyrins, phthalocyanines, acridines, and quinones having a substituent at the 9-position. The compound (I) which is a sensitizer described above may be used alone or in combination of two or more.

The compounding amount of the compound (I) to be a sensitizer is preferably from 1 to 20 parts by weight, more preferably from 1 to 10 parts by weight, per 100 parts by weight of the alkali-soluble polymer (A).

In addition, the monocarboxylic acid compound (D) and the phenol compound (E) described in the positive photosensitive resin composition may be added to the negative photosensitive resin combination species as needed, and a crosslinking reaction occurs by heat. Compound (F), and compound (G) which generates an acid by heat.

Organic solvent (J)

In the present invention, it is preferred to dissolve the above various components in an organic solvent (J) to form a varnish, and to use it as a solution of the photosensitive resin composition. As such an organic solvent (J), it can be used singly or in combination: N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as "GBL"), cyclopentanone, cyclohexanone, isophorone , N,N-dimethylacetamide (hereinafter also referred to as "DMAc"), dimethyl imidazolidinone, tetramethyl urea, dimethyl hydrazine, diethylene glycol dimethyl ether (hereinafter also referred to as "DMDG"), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, lactate B Ester, butyl lactate, methyl 1,3-butanediol, 1,3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate Wait. Among these solvents, a non-amine-based solvent is preferred from the viewpoint of less influence on a photoresist or the like. Specific preferred examples thereof include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and tetrahydrofurfuryl alcohol. These organic solvents may be used singly or in combination of two or more.

When the organic solvent (J) is blended, the blending amount is preferably 100 to 2000 parts by weight based on 100 parts by weight of the alkali-soluble polymer (A), and the viscosity can be controlled by changing the amount of the organic solvent added, more preferably 100 to 1000 parts by weight, particularly preferably 100 to 1000 parts by weight. By adjusting the amount of addition of the organic solvent to form a viscosity suitable for the coating apparatus and the coating thickness, the production of the hardened concave-convex pattern can be facilitated.

Other additives (K)

In the photosensitive resin composition, a hydroxyl group-containing compound, a dye, a fragrance, and a surfactant for improving the in-plane uniformity of the coating film may be added as needed, or may be added. A bonding aid for improving the adhesion to the ruthenium substrate or the copper substrate, a polymerization inhibitor for improving the stability of the viscosity or photosensitivity of the composition solution during storage, and the like.

When the above additives are more specifically described, the hydroxyl group-containing compound preferably has 4 to 14 carbon atoms, and specific examples thereof include cyclopropylmethanol, 2-cyclohexen-1-ol, cyclohexane methanol, and 4- Methyl-1-cyclohexanemethanol, 3,4-dimethylcyclohexanol, 4-ethylcyclohexanol, 4-tert-butylcyclohexanol, cyclohexaneethanol, 3-cyclohexyl-1 -propanol, 1-cyclohexyl-1-pentanol, 3,3,5-trimethylcyclohexanol, norbornane-2-methanol, cyclooctanol, 2,3,4-trimethyl-3 -pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, trans-2-hepten-1-ol, cis-4-hepten-1-ol, cis 3-octene-1-ol, 4-ethyl-1-octyn-3-ol, 2,7-octadienol, 3,6-dimethyl-1-heptyn-3-ol, 3-ethyl-2-methyl-3-pentanol, 2-ethyl-1-hexanol, 2,3-dimethyl-2-hexanol, 2,5-dimethyl-2-hexanol , trans, cis-2,6-nonadien-1-ol, 1-decen-3-ol, cis-2-butene-1,4-diol, 2,2-diethyl-1, 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,5-hexadiene-3,4-diol, 2,5-dimethyl-3-hexyne -2,5-diol, 2,4,7,9,tetramethyl-5-decyne-4,7-diol, 2,2,4,4-tetramethyl-1,3-cyclobutane Alkanediol, 1,2-cyclohexane Glycol, trans-p-menthane-3,8-diol, 2,4-dimethoxybenzyl alcohol, butanol, and the like.

Among these, 2,3,4-trimethyl-3-pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, and trans-2-heptane are preferred. En-1-ol, cis-4-hepten-1-ol, cis-3-octene-1-ol, trans, cis-2,6-decadien-1-ol, cis-2-butene a hydroxyl group-containing compound having an unsaturated bond or a branched structure such as a 1,4-diol or a 1,5-hexadiene-3,4-diol, and the monool is excellent in terms of adhesion to a substrate. Among the diols, particularly preferred are 2,3,4-trimethyl-3-pentanol, 3-ethyl-2-methyl-3-pentanol, glycerol-α,α'-diallyl ether.

These hydroxyl group-containing compounds may be used singly or in combination of two or more.

The compounding amount in the case of formulating the above hydroxyl group-containing compound is preferably 0.01 to 70 parts by weight, more preferably 0.1 to 50 parts by weight, even more preferably 1 to 40, based on 100 parts by weight of the alkali-soluble polymer (A). The weight is preferably 5~25. When the compounding amount of the hydroxyl group-containing compound is 0.01 parts by weight or more, the development residue of the exposed portion is reduced, and when the compounding amount of the hydroxyl group-containing compound is 70 parts by weight or less, the tensile elongation of the film after curing is good.

Examples of the dye include methyl violet, crystal violet, and malachite green. The amount of the dye in the case of blending the dye is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the alkali-soluble polymer (A). When the amount is 10 parts by weight or less, the heat resistance of the film after heat curing is good.

The perfume may, for example, be a terpene compound, and from the viewpoint of solubility in a solvent, a monoterpene compound or a sesquiterpene compound is preferable.

Specific examples thereof include: linalool, isofhytol, dihydro eugenol, linalyl acetate, oxidized linalool, geranyl linalol, lavandolol, tetrahydro lavanol, acetic acid Alcohol, nerol, nerol acetate, geranyl alcohol, citral, geranyl acetate, geranyl acetone, geranic acid, citral dimethyl acetal, Citronellol, citronellal, hydroxycitronellal, dimethyl octanal, citronellic acid, citronellyl acetate, tagetone, artemisia ketone, long leaf mint (pulegol) ), iso-long leaf mint, menthol, menthol acetate, isomenthol, neomenthol, menthanol, menthane triol, menthane tetraol, fragrant celery Phenol (carvomenthol), Oxyacetic acid, perillyl-alcohol, perillyl aldehyde, carveol, pepperitol, terpene-4-ol, rosinol, terpinenol, dihydrogen rosin Alcohol, sobrerol, thymol, borneol, borneol acetate, isobornyl, isobornyl acetate, cineole, pinol, pinocarveol, peach gold Myrtenol, myrtenol, verfenol, pinocampheol, camphorsulfonic acid, nerolidol, terpinene, ionone, terpenes, Camphene, camphoral aldehyde, camphoronic acid, isoxalic acid, camphoric acid, rosin acid, glycyrrhizic acid, and the like. These terpene compounds may be used singly or in combination of two or more.

The blending amount in the case of blending the fragrance is preferably 0.1 to 70 parts by weight, more preferably 1 to 50 parts by weight, per 100 parts by weight of the alkali-soluble polymer (A). When the amount added is 70 parts by weight or less, the heat resistance of the film after heat curing is good.

Examples of the surfactant include nonionic surfactants including polyalcohols such as polypropylene glycol and polyoxyethylene lauryl ether, and derivatives thereof. Further, a fluorine-based surfactant such as Fluorad (manufactured by Sumitomo 3M Co., Ltd.), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.), and Lumiflon (manufactured by Asahi Glass Co., Ltd.) can be cited. Further, an organic oxoxane surfactant such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name), DBE (manufactured by Chisso Co., Ltd.), and Glanol (manufactured by Kyoyosha Chemical Co., Ltd.) can be cited. By adding the surfactant, shrinkage of the coating film at the edge of the wafer during coating can be made less likely to occur.

The blending amount in the case of blending the surfactant is preferably from 0 to 10 parts by weight, more preferably from 0.01 to 1 part by weight, per 100 parts by weight of the alkali-soluble polymer (A). When the amount is 10 parts by weight or less, the heat resistance of the film after heat curing is good.

Examples of the adhesion aid for improving the adhesion to the ruthenium substrate or the copper substrate include alkyl imidazoline, polyvinyl methyl ether, epoxy polymer, triazole, and tetrazole. A heterocyclic structural compound such as azole, thiazole, or imidazole.

Specific examples of the heterocyclic structural compound include 2-mercaptobenzoene. Oxazole, 2-mercaptobenzothiazole, 1,3-dimethyl-5-pyrazolone, 3,5-dimethylpyrazole, 5,5-dimethylhydantoin, 3-methyl -5-pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 2-methylimidazole, 1,10-morpholine, thiophene ,coffee Order Thio, mercaptobenzothiazole, mercaptobenzo Oxazole, methylthiobenzothiazole, dibenzothiazole disulfide, methylthiobenzimidazole, benzimidazole, phenylmercaptothiazoline, nonylphenyltetrazole, and fluorenylmethyltetrazole. Further, examples of the benzotriazoles include the following compounds:

[67]

In the formula, Z ₅ is a hydrogen atom, or at least one selected from the group consisting of a hydrocarbon group having 1 to 5 carbon atoms and a carboxyl group, and Z ₆ is a hydrogen atom or is selected from a hydroxyl group and a carbon atom. At least one of a group consisting of a hydrocarbon group of 1 to 5 and an aminoalkyl group.

The heterocyclic-containing compound is more preferably selected from the group consisting of 5-mercapto-1-phenyltetrazole, 1,2,3-benzotriazole, benzothiazole, from the viewpoint of sensitivity on a copper substrate. Benzo Oxazole, benzimidazole, and 2-mercaptobenzophenone a compound in a group consisting of azoles.

These heterocyclic-containing compounds may be used singly or in combination of two or more.

The compounding amount in the case of formulating the compound containing a hetero ring is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the alkali-soluble polymer (A). When the compounding amount of the compound containing a hetero ring is 0.1 part by weight or more, the adhesion of the film after thermosetting to the copper substrate is good, and when the compounding amount of the compound containing a hetero ring is 30 parts by weight or less, the combination is The stability of the object is good.

As the polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butyl catechol, and thiophene can be used. , N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-t-butyl-p-methyl Phenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl- N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine aluminum, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N-(1- Naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-di-t-butyl)phenylmethane, and the like.

The amount of the polymerization inhibitor is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 1 part by weight, per 100 parts by weight of the alkali-soluble polymer (A). When the amount added is within 5 parts by weight, the heat-resistant film after heat curing is good.

<Hardened concave-convex pattern and method of manufacturing semiconductor device>

Next, a method of producing the cured concave-convex pattern of the present invention will be specifically described below.

Using the photosensitive resin group organism of the present invention, a cured concavo-convex pattern can be produced by the following method.

The manufacturing method of the hardened concave-convex pattern includes the following steps:

(1) a step of forming a photosensitive resin layer obtained by applying a solution of the photosensitive resin composition or the photosensitive resin composition on a substrate;

(2) an exposure step;

(3) a developing step;

(4) A step of heat-treating the obtained concave-convex pattern.

(1) a step of forming a photosensitive resin layer containing a photosensitive resin composition on a substrate (first step)

The photosensitive resin composition or a solution thereof is applied to, for example, a tantalum wafer, a ceramic substrate, an aluminum substrate, or the like by spin coating using a spin coater or a coater such as a die coater or a roll coater. Substrate. The organic solvent (hereinafter also referred to as "soft bake" or "pre-baked") is removed by applying an oven or a hot plate to a heat of 50 to 140 ° C, preferably 100 to 140 ° C.

(2) a step of performing exposure by irradiating with an actinic ray or directly irradiating light, an electron beam or an ion beam (second step)

Then, the photosensitive resin layer is exposed to an actinic ray through a mask using a contact aligner or a stepper, or directly irradiated with light, an electron beam or an ion beam to perform exposure. As the active light, a g-line, an h-line, an i-line, or a KrF laser can also be used.

In the case of a negative photosensitive composition, it is heated again at 80 to 140 ° C for 30 seconds to 600 seconds after exposure. This is called post-exposure baking (hereinafter also referred to as PEB). By this step, the acid generated by the exposure is used as a catalyst, and the compound (G) which can be crosslinked by the action of an acid is generated by the action of the compound (G) which generates an acid by the heat of the exposed portion. Thermal crosslinking reaction, insoluble in alkaline aqueous solution.

(3) a step of developing or removing the exposed portion by a developing solution in the case of a positive photosensitive composition, and developing or removing the unexposed portion in the case of a negative photosensitive composition to develop (in the case of a negative photosensitive composition) Third step)

Then, the exposed portion is dissolved and removed in the case of the positive photosensitive composition by the developer, and the unexposed portion is dissolved and removed in the case of the negative photosensitive composition, followed by elution with the eluent. Thereby obtaining the desired concave and convex pattern. As the developing method, a method such as spraying, stirring, dipping, or ultrasonic can be used. Distilled water, deionized water, or the like can be used as the eluent.

In the developer for developing the film formed of the photosensitive resin composition, the alkali-soluble polymer (A) is dissolved and removed, and it is necessary to form an alkaline aqueous solution in which a basic compound is dissolved. The basic compound dissolved in the developer may be either an inorganic basic compound or an organic basic compound.

Examples of the inorganic basic compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium niobate, sodium citrate, and potassium citrate. Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia, and the like.

Further, examples of the organic basic compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, and trimethylamine. , monoethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine , ethanolamine, and triethanolamine.

Further, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol or ethylene glycol, a surfactant, a storage stabilizer, a dissolution inhibitor of the resin, or the like may be added to the alkaline aqueous solution as needed.

(4) a step of heat-treating the obtained concavo-convex pattern (fourth step). Finally, the obtained concavo-convex pattern is hardened to form a polyphenylene-containing material. A heat-resistant hardened concave-convex pattern of a resin having an azole structure. As the heating device, an oven furnace, a heating plate, a vertical furnace, a conveyor belt furnace, a pressure oven, or the like can be used. As the heating method, heating by hot air, infrared rays, electromagnetic induction or the like is recommended. The temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C. The heating time is preferably from 15 minutes to 8 hours, more preferably from 1 hour to 4 hours. The ambient gas is preferably an inert gas such as nitrogen or argon.

The semiconductor device produced by using the photosensitive resin composition of the present invention can be produced as a surface protective film by being combined with a known method for producing a semiconductor device to have a cured uneven pattern containing a photosensitive resin composition. An interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, and a protective film of a device having a bump structure.

Examples of the use of the semiconductor device include a passivation film formed by forming a cured film of the photosensitive resin composition on a semiconductor element, and a buffer film formed by forming a cured film of the photosensitive resin composition on a passivation film. An insulating film such as an interlayer insulating film obtained by forming a cured film of the positive photosensitive resin composition on a circuit formed on a semiconductor element, an α-ray blocking film, a planarizing film, and a protrusion (resin column). Next door, etc.

Further, the photosensitive resin composition of the present invention is also used for applications such as interlayer insulation of a multilayer circuit, a protective layer of a flexible copper foil sheet, a solder resist film, a liquid crystal alignment film of a display device, and the like, and a light-emitting element.

Examples of the use of the display device include a protective film formed of a cured film of the photosensitive resin composition on a display element, a TFT thin film transistor, a color filter, or the like. An insulating film, a planarizing film, a protrusion for use in a MVA (Multi-domain Vertical Alignment) type liquid crystal display device, a partition wall for an organic EL element cathode, or the like. The method of use is based on the use of a semiconductor device, and the patterned photosensitive resin composition layer is formed on the substrate on which the display element or the color filter is formed by the above method. In the use of the display device, particularly in the use of an insulating film or a planarizing film, high transparency is required, and a resin layer excellent in transparency can be obtained by the post-hardening exposure step of the photosensitive resin composition layer. Therefore, the photosensitive resin composition of the present invention is particularly practical in such applications.

[Examples]

Hereinafter, the present invention will be described based on reference examples, examples, and comparative examples.

<Manufacture of bis(carboxy)tricyclo[5,2,1,0 ^2,6 ]decane> [Reference Example 1]

Tricyclo[5,2,1,0 ^2,6 ]decane dimethanol was placed in a glass separable three-necked flask equipped with an anchor stirrer made of Teflon (registered trademark). (manufactured by Tokyo Chemical Industry Co., Ltd.) 71.9 g (0.366 mol) dissolved in 1 L of acetonitrile, dissolving 256.7 g (1.808 mol) of disodium hydrogen phosphate and 217.1 g (1.809 mol) of sodium dihydrogen phosphate in ion-exchanged water 1.4 It is made up of L. 2,2,6,6-tetramethylpiperidine-1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter also referred to as "TEMPO") was added thereto to 2.8 g (0.0179 mol), and the mixture was stirred. Dissolved.

143.2 g (1.267 mol) of 80% sodium chlorite was diluted with 850 mL of ion-exchanged water, and added dropwise to the reaction solution. Then, 3.7 mL of a 5% sodium hypochlorite aqueous solution was diluted with 7 mL of ion-exchanged water, and the mixture was added dropwise to the reaction liquid. The reaction solution was kept at 35 to 38 ° C by a constant temperature layer and stirred for 20 hours to cause a reaction.

After the reaction, the reaction solution was cooled to 12 ° C, and an aqueous solution of 75 g of sodium sulfite dissolved in 300 mL of ion-exchanged water was added dropwise to the reaction solution, and after excess sodium chlorite was deactivated, 500 mL of acetic acid was used. Ethyl ester is used for cleaning. Thereafter, 115 mL of 10% hydrochloric acid was added dropwise to adjust the pH of the reaction mixture to 3 to 4, and the precipitate was recovered by decantation. The precipitate was dissolved in 200 mL of tetrahydrofuran. Further, the aqueous layer was extracted twice with 500 mL of ethyl acetate, and then washed with brine, and the precipitate was dissolved in tetrahydrofuran. The tetrahydrofuran solution was mixed and dried using anhydrous sodium sulfate. This solution was concentrated and dried by an evaporator, whereby 58.4 g of bis(carboxy)tricyclo[5,2,1,0 ^2,6 ]decane (yield: 71.1%) of white crystals was obtained.

<Manufacture of bis(chlorocarbonyl)tricyclo[5,2,1,0 ^2,6 ]decane> [Reference Example 2]

The bis(carboxy)tricyclo[5,2,1,0 ^2,6 ]decane 62.5 g (278 mmol), sulfoxide 95 mL (1.33 mol), and pyridine 0.4 mL (5.0) obtained from Reference Example 1. Ment) was placed in a reaction vessel and stirred at 25 to 50 ° C for 18 hours to cause a reaction. After completion of the reaction, toluene was added, and excess sulfinium chloride was azeotroped with toluene under reduced pressure to concentrate to obtain an oily bis(chlorocarbonyl)tricyclo[5,2,1,0 ^2,6 ] decane 73.3 g (yield 100%).

<Synthesis of photoacid generator (B) naphthoquinonediazide compound> [Reference Example 3]

2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 109.9 g (0.3 mol), tetrahydrofuran (THF, tetrahydrofuran) 330 g, pyridine were placed in a separable flask of 1 L. 47.5 g (0.6 mol) was added thereto directly at room temperature in the form of powder to which 5-norbornene-2,3-dicarboxylic anhydride 98.5 g (0.6 mol). The reaction was carried out by stirring at room temperature for 3 days, and the reaction was confirmed by HPLC (high performance liquid chromatography). As a result, the starting material was not detected at all, and the product was detected as a single peak at a purity of 99%. . The reaction solution was directly added dropwise to 1 L of ion-exchanged water under stirring, and the precipitate was separated by filtration. Thereafter, 500 ml of THF was added thereto and stirred to dissolve, and the homogeneous solution was passed through with a cation exchange resin: Amberlyst 15 (manufactured by Organo) 100 g of glass column to remove residual pyridine. Then, the solution was added dropwise to 3 L of ion-exchanged water under high-speed stirring, whereby the product was precipitated, separated by filtration, and then vacuum dried.

The quinone imidization of the product was confirmed by the characteristic absorption of the imidium imine group of 1394 cm ^-1 and 1774 cm ^-1 in the IR (Infrared) spectrum, without the presence of 1540 cm ^-1 and The characteristic absorption of the guanamine group near 1650 cm ^-1 ; and the proton peak of guanamine and carboxylic acid are not present in the NMR (nuclear magnetic resonance) spectrum.

Then, the product 65.9 g (0.1 mol), 1,2-naphthoquinonediazide-4-sulfonyl chloride 53.7 g (0.2 mol) was added to 560 g of acetone, and dissolved by stirring at 20 °C. A mixture of 21.2 g (0.21 mol) of triethylamine diluted with acetone 106.2 g was added dropwise thereto at a fixed rate for 30 minutes. At this time, the temperature of the reaction liquid is controlled to be in the range of 20 to 30 ° C using an ice water bath or the like.

After completion of the dropwise addition, the mixture was further stirred at 20 ° C for 30 minutes, and then 5.6 g of a 36% by weight aqueous hydrochloric acid solution was added in one portion, and then the reaction liquid was cooled by an ice water bath, and the precipitated solid component was separated by suction filtration. The filtrate obtained at this time was added to 5 L of a 0.5% by weight aqueous hydrochloric acid solution under stirring for 1 hour, and the target was precipitated, and subjected to suction filtration separation to be recovered. The obtained cake-like recovered product was again dispersed in 5 L of ion-exchanged water, stirred, washed, separated by filtration, and the water washing operation was repeated three times. The finally obtained cake was vacuum dried at 40 ° C for 24 hours to obtain a photosensitive diazonium compound (Q-1).

[Reference Example 4]

4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene) double as a polyhydroxy compound in a separable flask with a capacity of 1 L 30 g (0.0707 mol) of a compound of phenol (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Tris-PA), to which 1,2-naphthoquinonediazide which is equivalent to 83.3 mol% of the OH group is added thereto 4-sulfonyl chloride 47.49 g (0.177 mol) was stirred and dissolved in 300 g of acetone, and the flask was adjusted to 30 ° C using a thermostatic bath. Then, 17.9 g of triethylamine was dissolved in 18 g of acetone, and the mixture was placed in a dropping funnel, and then added dropwise to the flask over 30 minutes. Stirring was continued for another 30 minutes after the completion of the dropwise addition, and then hydrochloric acid was added dropwise thereto, followed by stirring for 30 minutes to complete the reaction. Thereafter, triethylamine hydrochloride was removed by filtration. The filtrate obtained here was added dropwise to a 3 L beaker which was stirred and stirred with 1640 g of pure water and 30 g of hydrochloric acid while stirring to obtain a precipitate. The precipitate was washed with water and filtered, and then dried under reduced pressure at 40 ° C for 48 hours to obtain a photoacid generator (B) (Q-2).

<Preparation of organic hydrazine compound (C)> [Reference Example 5]

In a 500 mL three-necked flask equipped with a blender, a dropping funnel and a thermometer, put 13-100 g (0.6 mol) of di-tert-butyl dicarbonate and GBL 780 g, and slowly add 3-aminopropyltriethoxy at room temperature. Base decane 132.8 g (0.6 mol). The reaction solution was heated to about 40 ° C with the dropwise addition. Further, as the reaction progressed, it was confirmed that carbon dioxide was generated. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then the reaction liquid was confirmed by high performance liquid chromatography (HPLC). As a result, the starting material was not detected at all, and the product C-1 was in the form of a single peak. It was detected with a purity of 98%. Thus, an organic cerium compound (C) C-1 solution was obtained. The obtained reaction solution was adjusted in such a manner that C-1 reached 20% by weight with respect to GBL. The structure of C-1 is shown below:

[化68]

[Reference Example 6]

To a 500 mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 88.9 g (0.6 mol) of phthalic anhydride and 540 g of NMP were added and stirred, and the flask was adjusted to 30 ° C in a thermostatic bath. After 132.8 g (0.6 mol) of γ-aminopropyltriethoxydecane was placed in a dropping funnel, it was added dropwise to the flask over 30 minutes, and stirred at room temperature for 12 hours to obtain an organic hydrazine compound ( C) C-2 solution. The obtained reaction solution was adjusted in such a manner that C-2 reached 20% by weight with respect to GBL. The structure of C-2 is shown below:

[化69]

[Reference Example 7]

To a 500 mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 132.8 g (0.6 mol) of γ-aminopropyltriethoxydecane and GBL 780 g were added and stirred, and the flask was adjusted to 30 ° C by a thermostatic bath. After 71.4 g (0.6 mol) of phenyl isocyanate was placed in a dropping funnel, it was added dropwise to the flask over 30 minutes, and the liquid temperature was raised to 50 °C. An organic hydrazine compound (C) C-3 solution was obtained. The obtained reaction solution was adjusted in such a manner that C-3 reached 20% by weight with respect to GBL. The structure of C-3 is shown below:

[化70]

<Synthesis of Alkali Soluble Polymer (A)> [Example 1]

The mixture was stirred in a three-necked flask having a capacity of 500 mL in an anchor type stirrer made of Teflon (registered trademark), and mixed with stirring at 0 ° C to have the following structure:

[71]

TMOM-BP (Honzhou Chemical: trade name) 7.24 g (0.02 mol), pyridine 3.16 g (0.04 mol), and GBL 43.5 g solution, added dropwise in GBL143, 4 g dissolved 4,4' - Diphenyl ether dimethyl hydrazine chloride 53.1 g (0.18 mol). The time required for the dropwise addition was 20 minutes, and the temperature of the reaction liquid was at most 18 °C.

After the dropwise addition, the reaction solution which was stirred for 1 hour was added dropwise to the following reaction solution using a dropping funnel, and the reaction solution was a capacity of 2 in an anchor type stirrer additionally equipped with Teflon (registered trademark). In a separable flask of L, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (hereinafter also referred to as "6FAP") 65.9 g was stirred and stirred at room temperature (25 ° C). (0.18 mol), pyridine 18.9 g (0.24 mol), GBL 395 g, and DMAc 131.8 g were dissolved, and the reaction vessel was immersed in a vessel in which dry ice was added to methanol, and cooled to -15 ° C. The reaction system was maintained at -15 to 0 ° C and required to be added dropwise to the reaction vessel for 45 minutes. After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at 0 to 10 ° C and stirred for 1 hour. Further, pyridine 9.49 g of 0.12 mol) was added.

After ethanol was added to the above reaction solution to precipitate a polymer, the polymer was recovered and dissolved in GBL 697 g. Then, ion exchange was carried out with 52.1 g of a cation exchange resin (Amberlyst A21, manufactured by Organo Co., Ltd.) and an anion exchange resin (Amberlyst 15 manufactured by Organo Co., Ltd.). The solution is added dropwise to 12 L of ion-exchanged water under high-speed agitation, the polymer is dispersed and precipitated, and recovered, and vacuum-dried after appropriate water washing and dehydration to obtain a structure having a PBO precursor structure and a cross-linking group. Powder of alkali-soluble polymer (A) (P-1).

The weight average molecular weight (Mw) of the alkali-soluble polymer thus synthesized by GPC (High Performance Liquid Chromatography) is a single steep curve in terms of polystyrene of 18,100, and is a single composition. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

The results of ¹³ C-NMR of the obtained alkali-soluble polymer (A) P-1 are shown in Fig. 2 . The peak derived from methoxymethyl was observed near 58 ppm and 69-70 ppm. Further, a peak derived from an ester group was observed in the vicinity of 167 ppm.

[Embodiment 2]

TMOM-BP (Hondon Chemical: trade name) 14.5 g was mixed and stirred at 0 °C in a three-necked flask equipped with a Teflon (registered trademark) anchor stirrer with a capacity of 500 mL. The solution of (0.04 mol), pyridine 6.33 g (0.08 mol) and GBL 86.9 g was added dropwise to GBL142 g to dissolve the bis(chlorocarbonyl)tricyclo[5,2,1 produced in Reference Example 2. , 0 ^2,6 ] decane 47.5 g (0.18 mol). The time required for the dropwise addition was 30 minutes, and the temperature of the reaction liquid was at most 16 °C.

After the dropwise addition, the reaction solution which was stirred for 1 hour was added dropwise to the following reaction solution using a dropping funnel, and the reaction solution was a capacity of 2 in an anchor type stirrer additionally equipped with Teflon (registered trademark). In a separable flask of L, bis(3-amino-4-hydroxyphenyl)propane (hereinafter referred to as "BAP") (41.3 g) was mixed and stirred at room temperature (25 ° C). 0.16 mol), pyridine 16.6 g (0.21 mol), GBL 248 g, and DMAc 82.8 g were dissolved, and the reaction vessel was immersed in a vessel in which dry ice was added to methanol, and cooled to -15 ° C. The reaction system was maintained at -15 to 0 ° C and required to be added dropwise to the reaction vessel for 45 minutes. After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at 0 to 10 ° C and stirred for 1 hour. Further, 9.49 g (0.12 mol) of pyridine was added.

After adding ethanol to the reaction liquid to precipitate a polymer, the polymer was recovered and dissolved in GBL646 g. Then, ion exchange was carried out with 52.1 g of a cation exchange resin (Amberlyst A21, manufactured by Organo Co., Ltd.) and an anion exchange resin (Amberlyst 15 manufactured by Organo Co., Ltd.). The solution is added dropwise to 12 L of ion-exchanged water under high-speed agitation, the polymer is dispersed and precipitated, and recovered, and vacuum-dried after appropriate water washing and dehydration to obtain a structure having a PBO precursor structure and a cross-linking group. Powder of alkali-soluble polymer (A) (P-2).

The weight average molecular weight (Mw) of GPC by the alkali-soluble polymer thus synthesized is a single steep curve of 16,000 in terms of polystyrene, and is a single composition. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

The results of ¹³ C-NMR of the obtained alkali-soluble polymer (A) P-2 are shown in Fig. 3 . The peak derived from methoxymethyl was observed near 58 ppm and 69-70 ppm. Further, peaks derived from ester groups were observed in the vicinity of 172 to 174 ppm and 176 to 178 ppm.

[Example 3]

Using a dropping funnel, the TMOM-BP (Honori Chemical: trade name) 7.24 g was mixed and mixed at 0 ° C in a three-necked flask equipped with a Teflon (registered trademark) anchor type stirrer. The solution of 0.02 mol), pyridine 3.16 g (0.04 mol) and GBL 43.5 g was added dropwise to GBL142 g to dissolve the bis(chlorocarbonyl)tricyclic ring produced in Reference Example 2 [5,2, 1,0 ^2,6 ]decane 47.5 g (0.18 mol). The time required for the dropwise addition was 30 minutes, and the temperature of the reaction liquid was at most 16 °C.

After the dropwise addition, the reaction solution which was stirred for 1 hour was added dropwise to the following reaction solution using a dropping funnel, and the reaction solution was a capacity of 2 in an anchor type stirrer additionally equipped with Teflon (registered trademark). In a separable flask of L, 6FAP65.9 g (0.18 mol), pyridine 18.9 g (0.24 mol), GBL395 g and DMAcl 31.8 g were mixed and dissolved at room temperature (25 ° C) to dissolve the reaction. The container was immersed in a container in which dry ice was added to methanol, and cooled to -15 ° C. The reaction system was maintained at -15 to 0 ° C and required to be added dropwise to the reaction vessel for 45 minutes. After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at 0 to 10 ° C and stirred for 1 hour. Further, 9.49 g (0.12 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, and 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 19.7 g (0.12 mol) and pyridine 9.49 g (0.12 mol), and immersed in 50. In a hot water bath of ° C, the reaction solution was allowed to stand at 50 ° C for 18 hours.

After ethanol was added to the above reaction solution to precipitate a polymer, the polymer was recovered and dissolved in GBL 697 g. Then, ion exchange was carried out with 52.1 g of a cation exchange resin (Amberlyst A21, manufactured by Organo Co., Ltd.) and an anion exchange resin (Amberlyst 15 manufactured by Organo Co., Ltd.). The solution is added dropwise to 12 L of ion-exchanged water under high-speed agitation, the polymer is dispersed and precipitated, and recovered, and vacuum-dried after appropriate water washing and dehydration to obtain a structure having a PBO precursor structure and a cross-linking group. Powder of alkali-soluble polymer (A) (P-3).

The weight average molecular weight (Mw) of GPC by the alkali-soluble polymer thus synthesized is a single steep curve of 25,500 in terms of polystyrene, and is a single composition. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

The results of ¹³ C-NMR of the obtained alkali-soluble polymer (A) P-3 are shown in Fig. 4 . The peak derived from methoxymethyl was observed near 58 ppm and 69-70 ppm. Further, peaks derived from ester groups were observed in the vicinity of 172 to 174 ppm and 176 to 178 ppm.

[Example 4]

TMOM-BP (Honori Chemical: trade name) 21.7 g was mixed and stirred at 0 ° C in a three-necked flask equipped with a Teflon (registered trademark) anchor type stirrer using a Teflon (registered trademark). A solution of (0.06 mol), pyridine 9.48 g (0.12 mol) and GBL 130 g was added dropwise to GBL142 g to dissolve the bis(chlorocarbonyl)tricyclo[5,2,1 produced in Reference Example 2. , 0 ^2,6 ] decane 47.5 g (0.18 mol). The time required for the dropwise addition was 40 minutes, and the reaction liquid temperature was at most 16 °C.

After the dropwise addition, the reaction solution which was stirred for 1 hour was added dropwise to the following reaction solution using a dropping funnel, and the reaction solution was a capacity of 2 in an anchor type stirrer additionally equipped with Teflon (registered trademark). In a separable flask of L, 6FAP 51.2 g (0.14 mol), pyridine 15.0 g (0.19 mol), GBL307 g and DMAc 102 g were mixed and dissolved at room temperature (25 ° C), and the reaction vessel was immersed. It was cooled to -15 ° C in a container in which dry ice was added to methanol. The reaction system was maintained at -15 to 0 ° C and required to be added dropwise to the reaction vessel for 45 minutes. After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at 0 to 10 ° C and stirred for 1 hour. Further, 7.12 g (0.09 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, and 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 19.7 g (0.12 mol) and pyridine 9.49 g (0.12 mol), and immersed in 50. In a hot water bath of ° C, the reaction solution was allowed to stand at 50 ° C for 18 hours.

After adding ethanol to the reaction liquid to precipitate a polymer, the polymer was recovered and dissolved in GBL626 g. Then, ion exchange was carried out with 52.1 g of a cation exchange resin (Amberlyst A21, manufactured by Organo Co., Ltd.) and an anion exchange resin (Amberlyst 15 manufactured by Organo Co., Ltd.). The solution is added dropwise to 12 L of ion-exchanged water under high-speed agitation, the polymer is dispersed and precipitated, and recovered, and vacuum-dried after appropriate water washing and dehydration to obtain a structure having a PBO precursor structure and a cross-linking group. Powder of alkali-soluble polymer (A) (P-4).

The weight average molecular weight (Mw) of GPC by the alkali-soluble polymer thus synthesized is a single steep curve in terms of polystyrene of 13,200, and is a single composition. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

The results of ¹³ C-NMR of the obtained alkali-soluble polymer (A) P-4 are shown in Fig. 5 . The peak derived from methoxymethyl was observed near 58 ppm and 69-70 ppm. Further, peaks derived from ester groups were observed in the vicinity of 172 to 174 ppm and 176 to 178 ppm.

[Example 5]

The mixture was stirred at 0 ° C in a three-necked flask having a capacity of 500 mL equipped with an anchor type stirrer made of Teflon (registered trademark) using a dropping funnel to have the following structure:

[化72]

TMOM-BPA (Honzhou Chemical: trade name) 32.4 g (0.08 mol), pyridine 12.7 g (0.16 mol) and GBL194 g in a solution, added dropwise in GBL142 g dissolved in the reference example 2 It is a bis(chlorocarbonyl)tricyclo[5,2,1,0 ^2,6 ]decane 47.5 g (0.18 mol). The time required for the dropwise addition was 50 minutes, and the temperature of the reaction liquid was at most 16 °C.

After the dropwise addition, the reaction solution which was stirred for 1 hour was added dropwise to the following reaction solution using a dropping funnel, and the reaction solution was a capacity of 2 in an anchor type stirrer additionally equipped with Teflon (registered trademark). In a separable flask of L, 6FAP 43.9 g (0.12 mol), pyridine 12.7 g (0.16 mol), GBL263 g and DMAc 87.8 g were mixed and dissolved at room temperature (25 ° C) to dissolve the reaction. The container was immersed in a container in which dry ice was added to methanol, and cooled to -15 ° C. The reaction system was maintained at -15 to 0 ° C and required to be added dropwise to the reaction vessel for 45 minutes. After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at 0 to 10 ° C and stirred for 1 hour. Further, pyridine 6.32 g (0.08 mol) was added. Thereafter, the reaction solution was returned to room temperature, and 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 19.7 g (0.12 mol) and pyridine 9.49 g (0.12 mol), and immersed in 50. In a hot water bath of ° C, the reaction solution was allowed to stand at 50 ° C for 18 hours.

After adding ethanol to the reaction liquid to precipitate a polymer, the polymer was recovered and dissolved in GBL626 g. Then, ion exchange was carried out with 52.1 g of a cation exchange resin (Amberlyst A21, manufactured by Organo Co., Ltd.) and an anion exchange resin (Amberlyst 15 manufactured by Organo Co., Ltd.). The solution is added dropwise to 12 L of ion-exchanged water under high-speed agitation, the polymer is dispersed and precipitated, and recovered, and vacuum-dried after appropriate water washing and dehydration to obtain a structure having a PBO precursor structure and a cross-linking group. Powder of alkali-soluble polymer (A) (P-5).

The weight average molecular weight (Mw) of GPC by the alkali-soluble polymer thus synthesized is a single steep curve of 10,200 in terms of polystyrene, and is a single composition. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

The results of ¹³ C-NMR of the obtained alkali-soluble polymer (A) P-5 are shown in Fig. 6 . The peak derived from methoxymethyl was observed near 58 ppm and 69-70 ppm. Further, peaks derived from ester groups were observed in the vicinity of 172 to 174 ppm and 176 to 178 ppm.

[Embodiment 6]

Using a dropping funnel, the TMOM-BP (Honori Chemical: trade name) 14.5 g was mixed and mixed at 0 ° C in a three-necked flask equipped with a Teflon (registered trademark) anchor type stirrer. 0.04 mol), pyridine 6.33 g (0.08 mol) and GBL87 g were added to the solution, and another 16.8 g (0.08 mol) of trimellitic anhydride ruthenium chloride was dissolved in GBL151 g. The time required for the dropwise addition was 30 minutes, and the temperature of the reaction liquid was at most 18 °C.

After the dropwise addition, the reaction solution stirred for 1 hour was put into the capacity of a cooling tube equipped with a Teflon (registered trademark) anchor type agitator and a Dean-Stark trap. In a 2 L separable flask, add 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (Tokyo 31.7 g (0.12 mol), BAP 56.8 g (0.22 mol), GBL 340 g, DMAc 113 g, and 48.6 g of toluene were heated and stirred at a bath temperature of 50 ° C for 8 hours while passing nitrogen gas. Thereafter, the mixture was heated to a bath temperature of 180 ° C, and heated and stirred for 2 hours to remove a toluene component of toluene and water during the reaction. After the imidization reaction was completed, it was returned to room temperature.

The reaction droplets obtained above were added to 12 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, vacuum-dried after appropriate water washing and dehydration to obtain a soluble PI structure and a cross-linking group. Structure of the alkali soluble polymer (A) (P-6). The weight average molecular weight (Mw) of GPC by the alkali-soluble polymer thus synthesized is a single steep curve in terms of polystyrene of 19,000. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

[Embodiment 7]

Using a dropping funnel, the TMOM-BP (Honori Chemical: trade name) 25.4 g was mixed and mixed at 0 ° C in a three-necked flask equipped with a Teflon (registered trademark) anchor type stirrer. 0.07 mol), pyridine 11.0 g (0.14 mol) and GBL152 g were added to the solution, and another 29.5 g (0.14 mol) of trimellitic anhydride ruthenium chloride was dissolved in GBL118 g. The time required for the dropwise addition was 50 minutes, and the temperature of the reaction liquid was at most 18 °C.

After the dropwise addition, the reaction solution stirred for 1 hour was placed in a separable flask having a capacity of 2 L equipped with an anchor type stirrer made of Teflon (registered trademark), and then double (3, 4-) was added. Carboxyphenyl)ether dianhydride 18.6 g (0.06 mol), NMP 93 g, followed by the addition of 48.0 g (0.19 mol) of 4,4'-diaminodiphenyl ether in NMP176 g, at room temperature ( The mixture was stirred at 25 ° C for 1 hour, and further reacted at a bath temperature of 50 ° C for 4 hours.

Then, 2.16 g (0.04 mol) of isobutanol was added, and 7.5 g (0.04 mol) of dicyclohexylcarbodiimide was dissolved in GBL 37.5 g by adding 40 minutes while stirring under ice-cooling. The solution was formed and stirred at room temperature for 2 hours.

Thereafter, 30 mL of ethanol was added, and the mixture was stirred for 1 hour. Further, DMAc 250 mL and THF (400 mL) were added, and ethanol was added to the reaction liquid obtained by removing the precipitate by suction filtration, and the resulting precipitate was separated by filtration and then vacuum dried. An alkali-soluble polymer (A) (P-7) having a polyimine precursor structure and a structure containing a crosslinking group is obtained. The weight average molecular weight (Mw) of GPC by the alkali-soluble polymer thus synthesized is a single steep curve in terms of polystyrene of 11,000. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

[Comparative Example 1]

6FAP 73.2 g (0.20 mol), pyridine 21.1 g were mixed and stirred at room temperature (25 ° C) in a 2 L separable flask equipped with an anchor stirrer made of Teflon (registered trademark). (0.27 mol), GBL439 g, and DMAc146 g, and dissolved. Using a dropping funnel, 6.6 g (0.04 mol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in GBL88 g. The time required for the dropwise addition was 25 minutes, and the temperature of the reaction liquid was at most 28 °C.

After completion of the dropwise addition, the reaction liquid was heated to 50 ° C by a hot water bath, and stirred for 18 hours, and then IR spectrum measurement of the reaction liquid was carried out to confirm the properties of the quinone imine group exhibiting 1385 cm ^-1 and 1772 cm ^-1 . absorb.

Then, it was cooled to 8 ° C by a water bath, and 53.1 g (0.18 mol) of 4,4'-diphenylether dimethyl hydrazine chloride dissolved in GBL212 g was added dropwise thereto using a dropping funnel. The time required for the dropwise addition was 60 minutes, and the temperature of the reaction liquid was at most 12 °C.

After ethanol was added to the above reaction solution to precipitate a polymer, the polymer was recovered and dissolved in GBL671 g. Then, ion exchange was carried out with 52.1 g of a cation exchange resin (Amberlyst A21, manufactured by Organo Co., Ltd.) and an anion exchange resin (Amberlyst 15 manufactured by Organo Co., Ltd.). The solution was added dropwise to 12 L of water under high-speed stirring to disperse the polymer, and it was recovered, and vacuum-dried after appropriate washing and dehydration to obtain a PBO precursor as an alkali-soluble polymer (A). (P-8). The weight average molecular weight (Mw) of GPC using the alkali-soluble polymer thus synthesized was a single steep curve of 14,000 in terms of polystyrene, and it was confirmed that a single composition was obtained. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

For comparison, the results of ¹³ C-NMR of the obtained alkali-soluble polymer (A) P-8 are shown in Fig. 7 . The peaks near 58 ppm and 69-70 ppm derived from the methoxymethyl group and the peaks near the 167 ppm derived from the ester group were not observed in Example 1.

[Comparative Example 2]

BSP 51.7 g (0.20 mol), pyridine 21.1 g (0.27 mol), GBL 310 g, and a separable flask with a capacity of 2 L installed in an anchor stirrer made of Teflon (registered trademark) DMAc103 g. After the BAP was dissolved, the reaction vessel was immersed in a vessel to which dry ice was added in methanol to be cooled. 47.5 g (0.18 mol) of bis(chlorocarbonyl)tricyclo[5,2,1,0 ² , ⁶ ]decane produced in Reference Example 2 was dissolved in GBL142 g and kept at -10 to -19 ° C and It takes 30 minutes to drip into the reaction vessel. After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at 0 to 10 ° C and stirred for 2 hours. Further, 9.49 g (0.12 mol) of pyridine was added to the reaction vessel.

After ethanol was added to the above reaction solution to precipitate a polymer, the polymer was recovered and dissolved in GBL671 g. Then, ion exchange was carried out with 52.1 g of a cation exchange resin (Amberlyst A21, manufactured by Organo Co., Ltd.) and an anion exchange resin (Amberlyst 15 manufactured by Organo Co., Ltd.). The solution was added dropwise to 12 L of ion-exchanged water under high-speed agitation, the polymer was dispersed and precipitated, and recovered, and vacuum-dried after appropriate washing and dehydration to obtain a PBO precursor as an alkali-soluble polymer (A) ( P-9). The weight average molecular weight (Mw) of GPC using the alkali-soluble polymer thus synthesized was a single steep curve of 36,800 in terms of polystyrene, and it was confirmed that a single composition was obtained. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 ml/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

[Comparative Example 3]

Dissolved 6FAP 73.3 g (0.20 mol), pyridine 21.1 g (0.27 mol), GBL 440 g, and a separable flask with a capacity of 2 L of an anchor stirrer manufactured by Teflon (registered trademark). DMAc147 g. After the 6FAP was dissolved, the reaction vessel was immersed in a vessel in which dry ice was added to methanol, and cooled. 47.5 g (0.18 mol) of bis(chlorocarbonyl)tricyclo[5,2,1,0 ^2,6 ]decane produced in Reference Example 2 was dissolved in GBL 142 g and kept at -10 to -19 ° C. It takes 30 minutes to drip into the reaction vessel. After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at 0 to 10 ° C and stirred for 2 hours. Further, 9.49 g (0.12 mol) of pyridine was added to the reaction vessel.

After ethanol was added to the above reaction solution to precipitate a polymer, the polymer was recovered and dissolved in GBL 696 g. Then, ion exchange was carried out with 52.1 g of a cation exchange resin (Amberlyst A21, manufactured by Organo Co., Ltd.) and an anion exchange resin (Amberlyst 15 manufactured by Organo Co., Ltd.). The solution was added dropwise to 12 L of ion-exchanged water under high-speed agitation, the polymer was dispersed and precipitated, and recovered, and vacuum-dried after appropriate washing and dehydration to obtain a PBO precursor as an alkali-soluble polymer (A) ( P-10). The weight average molecular weight (Mw) of GPC using the alkali-soluble polymer thus synthesized was a single steep curve of 36,800 in terms of polystyrene, and it was confirmed that a single composition was obtained. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 ml/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

[Comparative Example 4]

A cooling tube with a Dean-Stark separator was installed in a separable flask having a capacity of 2 L equipped with an anchor type agitator made of Teflon (registered trademark). 5-(2,5-Dioxytetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 26.4 g (0.1) Mol), bis(3,4-dicarboxyphenyl)ether dianhydride 31.0 g (0.1 mol), BAP 56.8 g (0.22 mol), GBL 569 g, toluene 48.6 g, stirred at room temperature for 4 hours, added 5-norbornene-2,3-dicarboxylic anhydride 4.6 g (28 mmol) was stirred under nitrogen at a bath temperature of 50 ° C for 8 hours. Thereafter, the temperature was raised to a bath temperature of 180 ° C, and the mixture was heated and stirred for 2 hours. The distillate component of toluene and water was removed during the reaction. After the imidization reaction was completed, it was returned to room temperature.

The reaction droplets obtained above were added to 12 L of water under high-speed stirring to disperse the polymer, which was recovered, and subjected to appropriate water washing and dehydration, followed by vacuum drying to obtain soluble PI as an alkali-soluble polymer (A) ( P-11). The weight average molecular weight (Mw) of GPC by the alkali-soluble polymer thus synthesized is a single steep curve of 23,000 in terms of polystyrene. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

[Comparative Example 5]

Adding bis(3,4-dicarboxyphenyl)ether dianhydride 62.0 g (0.20 mol) to NMP311 in a 2 L separable flask equipped with an anchor stirrer made of Teflon (registered trademark) g, followed by adding 48.0 g (0.19 mol) of 4,4'-diaminodiphenyl ether dissolved in NMP 145 g, stirred at room temperature (25 ° C) for 1 hour, and further at a bath temperature of 50 ° C The reaction was carried out for 4 hours.

Then, 18 g (0.30 mol) of isobutanol was added, and 61.9 g (0.30 mol) of dicyclohexylcarbodiimide was dissolved in GBL413 g by adding 50 minutes while stirring under ice-cooling. The solution was stirred at room temperature for 2 hours.

Thereafter, 30 mL of ethanol was added, and the mixture was stirred for 1 hour, and further, DMAc 250 mL and THF (400 mL) were added, and ethanol was added to the reaction liquid obtained by removing the precipitate by suction filtration, and the resulting polymer was separated by filtration and then vacuum dried. A PI precursor was obtained as the polyphthalate (P-12) of the alkali-soluble polymer (A). The weight average molecular weight (Mw) of GPC by the alkali-soluble polymer thus synthesized is a single steep curve in terms of polystyrene of 33,000. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

[Comparative Example 6]

In a separable flask with a capacity of 1 L equipped with an anchor stirrer of Teflon (registered trademark), 18.1 g (0.10 mol) of 5-aminoisophthalic acid was dissolved in NMP 200 g and pyridine 15.8. In a mixed solvent of g (0.20 mol), 18.9 g (0.11 mol) of 4-ethynyl-1,2-phthalic anhydride dissolved in GBL 36 g was added dropwise to the obtained solution, and stirred at room temperature 2 hour. The ice bath was cooled to 0 ° C, and 35.7 g (0.30 mol) of sulfite chlorine dissolved in GBL 105 g was added dropwise thereto at 30 ° C for 30 minutes, followed by stirring for 1 hour. After stirring, the mixture was returned to room temperature, and a vacuum pump was used to distill off unreacted sulfinium chloride and by-product sulfurous acid gas. This solution was used as the reaction liquid 1.

Then, in a 0.5 L Erlenmeyer flask, GBL 90 g was dissolved in 2,4'-diphenylether dimethylhydrazine chloride 29.5 g (0.1 mol). This solution was used as the reaction liquid 2.

6FAP80.6 g (0.22 mol), pyridine 31.6 g, mixed in a 2 L separable flask equipped with a Teflon (registered trademark) anchor stirrer at room temperature (25 ° C) (0.40 mol), GBL439 g, and DMAc146 g, and dissolved. Then, it was cooled to 0 ° C by a water bath while the above reaction liquid 1 and reaction liquid 2 were added dropwise. After the completion of the dropwise addition, the mixture was returned to room temperature and stirred for 2 hours.

After ethanol was added to the above reaction solution to precipitate a polymer, the polymer was recovered and dissolved in GBL671 g. Then, ion exchange was carried out with 52.1 g of a cation exchange resin (Amberlyst A21, manufactured by Organo Co., Ltd.) and an anion exchange resin (Amberlyst 15 manufactured by Organo Co., Ltd.). The solution was added dropwise to 12 L of water under high-speed stirring to disperse and precipitate the polymer, and it was vacuum-dried after appropriate washing and dehydration to obtain a PBO precursor having a crosslinked structure in a branched chain. As the alkali-soluble polymer (A) (P-13). The weight average molecular weight (Mw) of GPC by the alkali-soluble polymer thus synthesized was a single steep curve of 11,000 in terms of polystyrene, and it was confirmed that a single composition was obtained. The analysis conditions of GPC are described below.

Pipe column: manufactured by Showa Denko, brand name, Shodex 805M/806M series

Dissolution: N-methylpyrrolidone, 40 ° C

Flow rate: 1.0 mL/min

Detector: manufactured by Japan Spectroscopic Corporation, trade name, RI-930

<Evaluation of alkali soluble polymer> (1) Determination of residual film rate during hardening

The alkali-soluble polymer (A) (P-1 to P-13) obtained in the above Examples 1 to 7 and Pyridines 1 to 6 was dissolved in GBL to prepare a resin solid content of 35 mass%. A solution of the alkali soluble polymer (A). P-7 and P-12 having poor solubility in GBL are dissolved in NMP to prepare an alkali-soluble polymer solution having a resin solid content of 35 mass%, and each alkali-soluble polymer solution is a filter of 0.2 μm. Prepared by filtration.

The above-mentioned alkali-soluble polymer solution was applied onto a 6-inch wafer by a spin coater (manufactured by Tokyo Electron Co., Ltd., Clean Track Mark 8), and dried at 125 ° C for 180 seconds, and then used. A temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B) was heated at 320 ° C for 1 hour under a nitrogen atmosphere.

The residual film ratio (%) at the time of hardening was determined by (thickness of the film after hardening) / (film thickness of the uneven pattern after development) × 100. The results are shown in Table 1 below.

(2) Determination of glass transition temperature (Tg) of cured film

The alkali-soluble polymer (A) (P-1 to P-13) obtained in the above Examples 1 to 7 and Pyridines 1 to 6 was dissolved in GBL to prepare a resin solid content of 35 mass%. A solution of an alkali soluble polymer. P-7 and P-12 having poor solubility in GBL are dissolved in NMP to prepare an alkali-soluble polymer solution having a resin solid content of 35 mass%, and each alkali-soluble polymer solution is a filter of 0.2 μm. Prepared by filtration.

The above-mentioned alkali-soluble polymer solution was applied onto a 6-inch wafer by a spin coater (manufactured by Tokyo Vision Co., Ltd., Clean Track Mark 8), and dried at 125 ° C for 180 seconds, and then a temperature-increasing oven was used. Manufactured by Koyo Thermo Systems, Inc., VF200B), heated at 320 ° C for 1 hour under a nitrogen atmosphere to obtain a cured film having a film thickness of 10.0 μm.

The cured film was cut into a width of 3 mm, and the film was peeled off in a dilute hydrofluoric acid aqueous solution for one night, and the film was peeled off and dried. The resultant was subjected to TMA (Thermomechanical Analysis) apparatus (manufactured by Shimadzu Corporation, TMA). -50) The glass transition temperature was measured by a nitrogen flow rate of 50 ml/min and a temperature increase rate of 10 ° C/min. The results are shown in Table 1 below.

(3) Determination of elastic modulus and ductility of cured films

The alkali-soluble polymer (A) solution prepared in the measurement of the glass transition temperature (Tg) of the above (2) cured film was applied to 6 by a spin coater (manufactured by Tokyo Vision Co., Ltd., Clean Track Mark 8). On a enamel wafer, after drying at 125 ° C for 180 seconds, a temperature-increasing oven (manufactured by Koyo Thermo Systems, VF200B) was used, and heated at 320 ° C for 1 hour under a nitrogen atmosphere to obtain a film thickness of 10.0 μm. Heat resistant cured film.

The cured film was cut to a width of 3 mm, and the film was peeled off in a dilute hydrofluoric acid aqueous solution for one night, and the film was peeled off, and the resultant was cut to a length of 50 mm, using TENSILON (Orientec). UTM-II-20), the elastic modulus and ductility of the cured film were measured under the conditions of a test speed of 40 mm/min and an initial load of 0.5 fs. The results are shown in Table 1 below.

[Table 1]

Regarding the case where the alkali-soluble polymer is compared with the presence or absence of the structure containing a crosslinking group, the alkali-soluble polymer (A) (P-1 to P-7) obtained in the above Examples 1 to 7 is compared with The alkali-soluble polymer (P-8 to P-13) obtained in Examples 1 to 6 is excellent in any of residual film rate (%), Tg (°C), or ductility (%) at the time of hardening. .

In this case, it is understood that Example 1 is similar to Comparative Example 1 or Comparative Example 6 having substantially the same structure except for the structure containing no crosslinking group, and Example 2 is similar to Comparative Example 2 in comparison. In the third embodiment, compared with the comparative example 3, the sixth embodiment is compared with the comparative example 4, and the seventh embodiment is compared with the comparative example 5, and the above-described effects are exhibited.

<Preparation of Positive Photosensitive Resin Composition> [Examples 8 to 14 and Comparative Examples 7 to 12]

The positive photosensitive resin compositions of Examples 8 to 14 and Comparative Examples 7 to 12 were obtained from the alkali-soluble polymers (A) (P) obtained in the above Examples 1 to 7 and Comparative Examples 1 to 6. -1 to P-13) 100 parts by weight of the naphthoquinonediazide compound (Q-1 and Q) obtained as the photoacid generator (B) obtained in the above Reference Examples 3 and 4 in the amounts shown in Table 2 below. -2) Dissolved in GBL to prepare an alkali-soluble polymer solution having a resin solid content of 35 mass%. P-7 and P-12 having poor solubility in GBL are dissolved in NMP to prepare an alkali-soluble polymer resin solution having a resin solid content of 35 mass%, and each alkali-soluble polymer solution is filtered by 0.2 μm. Prepared by filtration.

[Table 2]

<Evaluation of photosensitive resin composition>

(1) Evaluation of patterning characteristics

‧Pre-baked film production and film thickness measurement

The positive photosensitive resin compositions of the above Examples 8 to 14 and Comparative Examples 7 to 12 were spin-coated on a 6-inch wafer by a spin coater (manufactured by Tokyo Vision Co., Ltd., Clean Track Mark 8). The film for evaluation was pre-baked on a hot plate at 125 ° C for 180 seconds. The initial film thickness of each composition was 7 μm, P-6, P-1~P-5 and P-8~P-10, after hardening at 320 ° C for 1 hour. The P-7 and P-11 to P-13 are adjusted in such a manner as to reach 5 μm. The film thickness was measured by a film thickness measuring device (Lambda ACE manufactured by Dainippon Screen Mfg.).

‧exposure

With respect to the coating film, exposure was performed by gradually changing the exposure amount by a stepper (NSR2005i8A manufactured by Nikon Co., Ltd.) having an exposure wavelength of i line (365 nm) by a mask having a test pattern.

‧development

For the above-mentioned exposed coating film, an alkaline developing solution (AZ300MIF developing solution manufactured by AZ Electronic Materials Co., Ltd., 2.38 mass% aqueous solution of tetramethylammonium hydroxide) was used, and the film thickness reached the initial film thickness after development at 23 ° C. The developing time was adjusted by 85%, and development was carried out, and the water was rinsed with pure water to form a positive-concave pattern.

[sensitivity (mJ/cm ² )]

In the coating film produced by the above conditions, the minimum exposure amount in which the 3.5 μm square concave-convex pattern of the exposed portion was completely dissolved and removed was evaluated as the sensitivity. The results are shown in Table 3 below.

[After time sensitivity (mJ/cm ² )]

The coating film produced by the above conditions was developed 24 hours after the exposure, and developed using the development conditions required for the sensitivity evaluation described above, and the minimum exposure amount of the 3.5 μm square concave-convex pattern of the exposed portion of the coating film was completely dissolved and removed. The evaluation was performed as the sensitivity after the passage. The results are shown in Table 3 below.

(2) Evaluation of the shape of the pattern after hardening (evaluation by cone angle)

The evaluation of the taper angle was carried out by using a temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B), and heating the sample having the positive-type concave-convex pattern obtained in the above (1) evaluation of the patterning property at 320 ° C under a nitrogen atmosphere. A cured film was obtained in an hour, and a section of a 50 μm line of the cured film was observed using an S-2400-shaped Hitachi scanning electron microscope manufactured by Hitachi, Ltd. In this cross section, as shown in Fig. 1, the angle formed by the pattern side surface of the line and the substrate was determined as the taper angle (θ). When the taper angle exceeds 50°, it can be determined that the cured film is preferably a surface protective film of a semiconductor device or an interlayer insulating film. The results are shown in Table 3 below.

(3) Chemical resistance test ("Residual film rate" measurement and "pattern observation")

The sample having the positive-type uneven pattern obtained in the above (1) evaluation of the patterning property was heated at 350 ° C for 1 hour and 30 minutes in a nitrogen atmosphere using a temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B).

The obtained cured film was immersed in a bath filled with a resist stripping solution TOK105 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) heated to 80 ° C for 5 minutes, and after washing with pure water, the film thickness was measured, and the residual film ratio was measured. . Then observe the state of the pattern. The results are shown in Table 3 below.

[table 3]

In the case of comparison with an alkali-soluble polymer (A) having a similar skeleton, a solution prepared by using the alkali-soluble polymer (A) (P-1 to P-7) obtained in the above Examples 1 to 7 ( Examples 8 to 14) were compared with the solutions prepared by using the alkali-soluble polymers (P-8 to P-13) obtained in Comparative Examples 1 to 6 (Comparative Examples 7 to 12) in terms of sensitivity, hardened shape, or resistance. Excellent in any of the chemical properties. Further, in the solution of the alkali-soluble polymer (P-13) having a cross-linking group in the branched chain (Comparative Example 12), the sensitivity after the lapse of time was observed, but the alkali obtained in the above Examples 1 to 7 was used. In the solutions prepared in the soluble polymer (A) (P-1 to P-7) (Examples 8 to 14), the decrease in sensitivity after the passage was not observed.

In this case, Example 8 is similar to Comparative Example 7 and Comparative Example 12 having substantially the same structure except for the structure containing no crosslinking group, and Example 9 is similar to Comparative Example 8 in comparison. In Examples 10 to 12, compared with Comparative Example 9, Example 13 was compared with Comparative Example 10, and Example 14 was compared with Comparative Example 11, and the above effects were exhibited.

[Examples 8 to 29, Comparative Examples 7 to 18]

The positive photosensitive resin compositions of Examples 8 to 29 and Comparative Examples 7 to 18 were obtained from the alkali-soluble polymers (A) (P) obtained in the above Examples 1 to 7 and Comparative Examples 1 to 6. -1 to P-13) 100 parts by weight of the naphthoquinonediazide compound (Q-1 and Q) obtained as the photoacid generator (B) obtained in the above Reference Examples 3 and 4 in the amounts shown in Table 4 below. -2) dissolved in GBL to further obtain the organic ruthenium compound (C) (C-1 to C-3) obtained in the above Reference Examples 5 to 7 and the following organic compound of (C-4 to C-9) (C) Dissolved in GBL to prepare an alkali-soluble polymer solution having a resin solid content of 35 mass%. P-7 and P-12 having poor solubility in GBL were dissolved in NMP to prepare an alkali-soluble polymer solution having a resin solid content of 35 mass%, and each alkali-soluble polymer solution was a filter of 0.2 μm. Prepared by filtration.

(C-4) N-phenyl-γ-aminopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, KBM573)

(C-5) γ-Methyl propylene methoxy propyl triethoxy decane (manufactured by Shin-Etsu Silicones Co., Ltd., trade name KBE503)

(C-6) Vinyl triethoxy decane (manufactured by Shin-Etsu Oil Co., Ltd., trade name KBE1003)

(C-7) triphenyl decyl alcohol

(C-8) diphenyl decanediol

(C-9) diethoxydiphenyl decane

[Table 4]

<Evaluation of photosensitive resin composition> (1) Evaluation of patterning characteristics ‧Pre-baked film production and film thickness measurement

The positive photosensitive resin composition of the above examples and comparative examples was spin-coated on a 6-inch wafer on a hot plate by a spin coater (Clean Track Mark 8 manufactured by Tokyo Vision Co., Ltd.). The film for evaluation was obtained by prebaking at 125 ° C for 180 seconds. The initial film thickness of each composition was 7 μm, P-6, P-1~P-5 and P-8~P-10, after hardening at 320 ° C for 1 hour. Adjust P-7 and P-11~P-13 to 5 μm. The film thickness was measured by a film thickness measuring device (Lambda ACE manufactured by Dainippon Screen Manufacturing Co., Ltd.).

. exposure

With respect to this coating film, exposure was performed by stepwise changing the exposure amount by a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i line (365 nm) through a mask with a test pattern.

. development

For the above-mentioned exposed coating film, an alkaline developing solution (AZ300MIF developing solution manufactured by AZ Electronic Materials Co., Ltd., 2.38 mass% aqueous solution of tetramethylammonium hydroxide) was used, and the film thickness reached the initial film after development at 23 ° C. The development time was adjusted by 85% of the thickness to develop, and the water was rinsed with pure water to form a positive-concave pattern.

[sensitivity (mJ/cm ² )]

In the coating film produced by the above conditions, the minimum exposure amount in which the 3.5 μm square concave-convex pattern of the exposed portion was completely dissolved and removed was evaluated as the sensitivity. The results are shown in Table 5 below.

[Adhesiveness]

Observe the pattern corresponding to the exposure amount twice as much as the above exposure amount, and observe the pattern of five lines and slits of 1:1 length 1 cm, and the line and gap of the smallest dimension which is completely followed by 5 The pattern is defined as the minimum follow-up pattern, which compares the adhesion of the pattern during development. The results are shown in Table 5 below.

The pattern size is 1 to 50 μm, and in this case, the development of the smaller size line and the gap holder is better.

(2) Evaluation of adhesion after hardening

The sample having the positive-type concave-convex pattern obtained in the above (1) evaluation of the patterning property was heated at 320 ° C for 1 hour in a nitrogen atmosphere using a temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B) to obtain a cured film. The obtained cured film was treated by a pressure cooker (131 ° C, 2.0 atm) for 100 hours, and then a mesh test (JIS K5400) was used to form a 100 square 1 mm square with a cutting blade, from above. The Cellophane (registered trademark) tape was attached and peeled off, and the number of squares remaining on the substrate without adhering to the Cellophane (registered trademark) tape was counted, thereby evaluating the adhesion after hardening. Table 5 below shows the number of squares remaining on the tantalum wafer after the tape peeling test. The more the number, the better the next.

(3) 4 week viscosity change rate at room temperature

The positive-type photosensitive resin composition adjusted by the above conditions was placed at room temperature for 3 days as a sample after preparation, and then placed at room temperature for 4 weeks as a sample after 4 weeks. The viscosity at 23 ° C was measured using a viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) equipped with a temperature controller.

The viscosity change rate at room temperature for 4 weeks was determined by [(viscosity of sample after 4 weeks) - (viscosity of adjusted sample)] / (viscosity of adjusted sample) × 100. The results are shown in Table 5 below.

[table 5]

By adding the component (C), the adhesion during development and the adhesion after curing are improved, and among the effects, the organic bismuth compound (C) (C-1 to C-3) obtained in the above Reference Examples 5 to 7 is obtained. And C-4 is especially excellent.

Further, in the comparative example in which the same component (C) was added, the increase in the viscosity change rate after 4 weeks at room temperature was large in the comparative example using the previous resin, and the results obtained in the above Examples 1 to 7 were used. The increase in the viscosity change rate after 4 weeks at room temperature in the solution prepared by the alkali-soluble polymer (A) (P-1 to P-7) was slight.

[Examples 15, 16, 22, and 26 to 50]

The positive photosensitive resin compositions of Examples 15, 16, 22, and 26 to 50 are the alkali-soluble polymers (A) (P-1 to P-7) obtained in the above Examples 1 to 7. 100 parts by weight, the naphthoquinonediazide compounds (Q-1 and Q-2) as the photoacid generator (B) obtained in the above Reference Examples 3 and 4 in the amounts shown in Table 6 below were dissolved in GBL. Further, 30 parts by weight of the organic cerium compound (C) C-1 obtained in the above Reference Example 5, or the organic cerium compound (C) C-2 30 weight obtained in the above Reference Example 6, in an amount shown in the following Table 6 The fraction and the following monocarboxylic acid compound (D) (D-1 to D-12) were dissolved in GBL to prepare an alkali-soluble polymer solution having a resin solid content of 35 mass%. P-7 having poor solubility in GBL was dissolved in NMP to prepare an alkali-soluble polymer resin solution having a resin solid content of 35 mass%, and each alkali-soluble polymer solution was filtered using a 0.2 μm filter. Prepared by filtration.

(D-1) m-toluic acid

(D-2) m-toluoacetic acid

(D-3) anisic acid

(D-4) o-toluic acid

(D-5) 3-cyclohexene-1-carboxylic acid

(D-6) Mandelic acid

(D-7) α-methoxyphenylacetic acid

(D-8) O-acetamidomandelic acid

(D-9) isophthalic acid

(D-10) 10-undecenoic acid

(D-11) 4-(3-butoxy)benzoic acid

(D-12) 4-biphenylacetic acid

[Table 6]

As a component C, C-1 is 30 parts by weight.

(In Examples 29 and 50, C-2 was 30 parts by weight and C-1 was 30 parts by weight)

<Evaluation of photosensitive resin composition> (1) Evaluation of patterning characteristics ‧Pre-baked film production and film thickness measurement

The positive photosensitive resin composition of the above example was spin-coated on a 6-inch wafer by a spin coater (manufactured by Tokyo Vision Co., Ltd., Clean Track Mark 8), and heated at 125 ° C on a hot plate. The film for evaluation was obtained by prebaking for 180 seconds. The initial film thickness of each composition was 7 μm from P-1 to P-5, and 5 μm from P-6 to P-7 at a resin film thickness after hardening at 320 ° C for 1 hour. The way to adjust. The film thickness was measured by a film thickness measuring device (Lambda ACE manufactured by Dainippon Screen Manufacturing Co., Ltd.).

‧exposure

With respect to this coating film, exposure was performed by stepwise changing the exposure amount by a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i line (365 nm) through a mask with a test pattern.

‧development

For the above-mentioned exposed coating film, an alkaline developing solution (AZ300MIF developing solution manufactured by AZ Electronic Materials Co., Ltd., 2.38 mass% aqueous solution of tetramethylammonium hydroxide) was used, and the film thickness reached the initial film after development at 23 ° C. The development time was adjusted by 85% of the thickness to develop, and the water was rinsed with pure water to form a positive-concave pattern.

[sensitivity (mJ/cm ² )]

In the coating film produced by the above conditions, the minimum exposure amount in which the 3.5 μm square concave-convex pattern of the exposed portion was completely dissolved and removed was evaluated as the sensitivity. The results are shown in Table 7 below.

[Development time (seconds)]

The time when the coating film produced by the above conditions was developed was taken as the development time (second). The results are shown in Table 7 below.

(2) Determination of residual film rate during hardening

The sample having the positive-type uneven pattern obtained in the above (1) evaluation of the patterning property was heated at 320 ° C for 1 hour in a nitrogen atmosphere using a temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B).

The residual film ratio at the time of hardening was determined by (thickness of the film after hardening) / (film thickness of the uneven pattern after development) × 100. The results are shown in Table 7 below.

[Table 7]

In the case of comparison with the same alkali-soluble polymer (A), it is understood that the development time is increased by the addition of the component (D), and the sensitivity is further improved.

[Examples 32, 39, 45 to 47, and 49 to 72]

The positive photosensitive resin compositions of Examples 32, 39, 45 to 47, and 49 to 72 were based on the alkali-soluble polymer (A) (P-1 to P- obtained in the above Examples 1 to 7). 7) 100 parts by weight, and the naphthoquinonediazide compounds (Q-1 and Q-2) as the photoacid generator (B) obtained in the above Reference Examples 3 and 4 in the amounts shown in the following Table 8 were dissolved in In GBL, 30 parts by weight of the organic ruthenium compound (C) C-1 obtained in the above Reference Example 5, or the organic ruthenium compound (C) C-2 obtained in the above Reference Example 6, in an amount shown in the following Table 8 30 parts by weight, 6 parts by weight of the monocarboxylic acid compound (D) (D-7 above), and the following phenol compound (E) (E-1 to E-8) were dissolved in GBL to prepare a resin solid content of 35 A concentration of the alkali soluble polymer solution. P-7 having poor solubility in GBL was dissolved in NMP to prepare an alkali-soluble polymer solution having a resin solid content of 35% by mass, and each alkali-soluble polymer solution was filtered using a 0.2 μm filter. And prepared.

(E-1) pair Phenol

(E-2) 4-hexyl resorcinol

(E-3) 2,2'-dihydroxydiphenylmethane

(E-4) 2,2'-bis(4-hydroxy-3-methylphenyl)propane

(E-5) The following formula:

[化73]

TrisP-PHBA (manufactured by Honshu Chemical Industry Co., Ltd.: trade name)

(E-6) the following formula:

[化74]

TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.: trade name)

(E-7) EP4000B (Asahi Organic Industry: Trade Name)

(E-8) EP4080G (Asahi Organic Industry: Trade Name)

[Table 8]

As a component C, C-1 is 30 parts by weight.

(In Examples 50, 71, and 72, C-2 was 30 parts by weight and C-1 was 30 parts by weight)

As component D, D-7 is 6 parts by weight.

<Evaluation of photosensitive resin composition> (1) Evaluation of patterning characteristics ‧Pre-baked film production and film thickness measurement

The positive photosensitive resin composition of the above example was spin-coated on a 6-inch wafer by a spin coater (manufactured by Tokyo Vision Co., Ltd., Clean Track Mark 8), and heated at 125 ° C on a hot plate. The film for evaluation was obtained by prebaking for 180 seconds. The initial film thickness of each composition is 7 μm from P-1 to P-5, 5 μm from P-6, and 5 μm from P-7 at a resin film thickness of 1 hour after hardening at 320 ° C. The way to adjust. The film thickness was measured by a film thickness measuring device (Lambda ACE manufactured by Dainippon Screen Manufacturing Co., Ltd.).

‧exposure

With respect to this coating film, exposure was performed by stepwise changing the exposure amount by a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i line (365 nm) through a mask with a test pattern.

‧development

For the above-mentioned exposed coating film, an alkaline developing solution (AZ300MIF developing solution manufactured by AZ Electronic Materials Co., Ltd., 2.38 mass% aqueous solution of tetramethylammonium hydroxide) was used, and the film thickness reached the initial film after development at 23 ° C. The development time was adjusted by 85% of the thickness to develop, and the water was rinsed with pure water to form a positive-concave pattern.

[sensitivity (mJ/cm ² )]

In the coating film produced by the above conditions, the minimum exposure amount in which the 3.5 μm square concave-convex pattern of the exposed portion was completely dissolved and removed was evaluated as the sensitivity. The results are shown in Table 9 below.

[Development time (seconds)]

The time when the coating film produced by the above conditions was developed was taken as the development time (second). The results are shown in Table 9 below.

(2) Determination of residual film rate during hardening

The sample having the positive-type uneven pattern obtained in the above (1) evaluation of the patterning property was heated at 320 ° C for 1 hour in a nitrogen atmosphere using a temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B).

The residual film ratio at the time of hardening was determined by (thickness of the film after hardening) / (film thickness of the uneven pattern after development) × 100. The results are shown in Table 9 below.

[Table 9]

In the case of comparison with the same alkali-soluble polymer (A), it is understood that the sensitivity is further improved by the addition of the component (E).

[Examples 32, 39, 45 to 47, 49, 50, and 73 to 100]

The positive photosensitive resin compositions of Examples 32, 39, 45 to 47, 49, 50, and 73 to 100 were based on the alkali-soluble polymer (A) (P-1) obtained in the above Examples 1 to 7. ~P-7) 100 parts by weight of the naphthoquinonediazide compound (Q-1 and Q-2) obtained as the photoacid generator (B) obtained in the above Reference Examples 3 and 4 in the amounts shown in Table 10 below. The organic ruthenium compound (C) C-1 obtained in the above Reference Example 5 in an amount shown in the following Table 10, 30 parts by weight or the organic ruthenium compound (C) obtained in the above Reference Example 6 was dissolved in GBL. C-2 30 parts by weight, 6 parts by weight of the monocarboxylic acid compound (D) (D-7 above), and the following compound (F) (F-1 to F-16) which is crosslinked by heat is dissolved In the GBL, an alkali-soluble polymer solution having a resin solid content of 35 mass% was produced. P-7 having poor solubility in GBL was dissolved in NMP to prepare an alkali-soluble polymer solution having a resin solid content of 35% by mass, and each alkali-soluble polymer solution was filtered using a 0.2 μm filter. And prepared.

(F-1) BANI-M (Maruzen Petrochemical: trade name)

(F-2) BANI-X (Maruzen Petrochemical: trade name)

(F-3) TMOM-BP (Honori Chemical Industry: Trade Name)

(F-4) TMOM-BPA (Honori Chemical Industry: Trade Name)

(F-5) 4,4'-bis(methoxymethyl)biphenyl

(F-6) The following formula:

[化75]

TML-BPAF-MF (Honori Chemical Industry: Trade Name)

(F-7) 1,3,4,6-tetrakis(methoxymethyl)glycoluril

(F-8) hexamethoxymethyl melamine

(F-9) TRIAM705 (Wako Pure Medicine: Trade Name)

(F-10) TRIAM805 (Wako Pure Medicine: Trade Name)

(F-11) 1,3-bis(methacryloxy)-2-propanol

(F-12) Trimethylolpropane Trimethacrylate

(F-13) Trimethylolpropane triacrylate

(F-14) OXT121 (East Asian synthesis: trade name)

(F-15) 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl

(F-16) 9,10-epoxy-1,5-cyclododecaene

[Table 10]

As a component C, C-1 is 30 parts by weight.

(In Examples 50 and 100, C-2 was 30 parts by weight and C-1 was 30 parts by weight)

As component D, D-7 is 6 parts by weight.

<Evaluation of photosensitive resin composition> (1) Evaluation of patterning characteristics ‧Pre-baked film production and film thickness measurement

The positive photosensitive resin composition of the above example was spin-coated on a 6-inch wafer by a spin coater (manufactured by Tokyo Vision Co., Ltd., Clean Track Mark 8), and heated at 125 ° C on a hot plate. The film for evaluation was obtained by prebaking for 180 seconds. The initial film thickness of each composition is 7 μm from P-1 to P-5, 5 μm from P-6, and 5 μm from P-7 at a resin film thickness of 1 hour after hardening at 320 ° C. The way to adjust. The film thickness was measured by a film thickness measuring device (Lambda ACE manufactured by Dainippon Screen Manufacturing Co., Ltd.).

‧exposure

With respect to this coating film, exposure was performed by stepwise changing the exposure amount by a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i line (365 nm) through a mask with a test pattern.

‧development

For the above-mentioned exposed coating film, an alkaline developing solution (AZ300MIF developing solution manufactured by AZ Electronic Materials Co., Ltd., 2.38 mass% aqueous solution of tetramethylammonium hydroxide) was used, and the film thickness reached the initial film after development at 23 ° C. The development time was adjusted by 85% of the thickness to develop, and the water was rinsed with pure water to form a positive-concave pattern.

[sensitivity (mJ/cm ² )]

In the coating film produced by the above conditions, the minimum exposure amount in which the 3.5 μm square concave-convex pattern of the exposed portion was completely dissolved and removed was evaluated as the sensitivity. The results are shown in Table 11 below.

(2) Determination of residual film rate during hardening

The sample having the positive-type uneven pattern obtained in the above (1) evaluation of the patterning property was heated at 320 ° C for 1 hour in a nitrogen atmosphere using a temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B).

The residual film ratio at the time of hardening was determined by (thickness of the film after hardening) / (film thickness of the uneven pattern after development) × 100. The results are shown in Table 11 below.

(3) Determination of Tg

The cured film obtained by measuring the residual film ratio at the time of curing (2) was cut into a width of 3 mm, and the film was peeled off in a dilute hydrofluoric acid aqueous solution for one night, and dried, and the TMA device was used for the obtained product. Manufactured by Shimadzu Corporation, TMA-50), the glass transition temperature was measured by a nitrogen flow rate of 50 ml/min and a temperature increase rate of 10 ° C/min. The results are shown in Table 11 below.

[Table 11]

In the case of comparison with the same alkali-soluble polymer (A), it is understood that the residual film ratio, Tg and sensitivity at the time of hardening are further increased by adding a compound which is a component of the component (F) to cause a crosslinking reaction by heat. improve.

[Example 77, and 101 to 115]

The positive photosensitive resin compositions of Examples 77 and 101 to 115 are based on the alkali-soluble polymers (A) (P-1 to P-5, and P-7) obtained in the above Examples 1 to 7. 100 parts by weight, the naphthoquinonediazide compounds (Q-1 and Q-2) obtained as the photoacid generator (B) obtained in the above Reference Examples 3 and 4 in the amounts shown in Table 12 below were dissolved in GBL. Further, 30 parts by weight of the organic cerium compound (C) C-1 obtained in the above Reference Example 5 in the amount shown in Table 12 below, or the organic cerium compound (C) C-2 30 obtained in the above Reference Example 6 6 parts by weight of the monocarboxylic acid compound (D) (D-7), 10 parts by weight of the compound (F) (F-4) which undergoes crosslinking reaction by heat, and the following by heat The acid-producing compound (G) (G-1 to G-4) was dissolved in GBL to prepare an alkali-soluble polymer solution having a resin solid content of 35% by mass. P-7 having poor solubility in GBL was dissolved in NMP to prepare an alkali-soluble polymer resin solution having a resin solid content of 35 mass%, and each alkali-soluble polymer solution was filtered using a 0.2 μm filter. Prepared by filtration.

(G-1) 2-methoxyethyl methanesulfonate

(G-2) methyl p-toluenesulfonate

(G-3) 2-methoxyethyl p-toluenesulfonate

(G-4) 2,4-butene lactone

[Table 12]

As a component C, C-1 is 30 parts by weight.

(In Examples 114 and 115, C-2 was 30 parts by weight and C-1 was 30 parts by weight)

As component D, D-7 is 6 parts by weight.

As the F component, F-4 is made up to 10 parts by weight.

<Evaluation of photosensitive resin composition> (1) Evaluation of patterning characteristics ‧Pre-baked film production and film thickness measurement

The positive photosensitive resin composition of the above example was spin-coated on a 6-inch wafer by a spin coater (manufactured by Tokyo Vision Co., Ltd., Clean Track Mark 8), and heated at 125 ° C on a hot plate. The film for evaluation was obtained by prebaking for 180 seconds. The initial film thickness of each composition was adjusted so that the resin film thickness after hardening at 320 ° C for 1 hour was 7 μm from P-1 to P-5 and 5 μm from P-7. The film thickness was measured by a film thickness measuring device (Lambda ACE manufactured by Dainippon Screen Manufacturing Co., Ltd.).

‧exposure

With respect to this coating film, exposure was performed by stepwise changing the exposure amount by a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i line (365 nm) through a mask with a test pattern.

‧development

For the above-mentioned exposed coating film, an alkaline developing solution (AZ300MIF developing solution manufactured by AZ Electronic Materials Co., Ltd., 2.38 mass% aqueous solution of tetramethylammonium hydroxide) was used, and the film thickness reached the initial film after development at 23 ° C. The development time was adjusted by 85% of the thickness to develop, and the water was rinsed with pure water to form a positive-concave pattern.

(2) Determination of residual film rate during hardening

The sample having the positive-type uneven pattern obtained in the above (1) evaluation of the patterning property was heated at 320 ° C for 1 hour in a nitrogen atmosphere using a temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B).

The residual film ratio at the time of hardening was determined by (thickness of the film after hardening) / (film thickness of the uneven pattern after development) × 100. The results are shown in Table 13 below.

(3) Evaluation of adhesion after hardening

The sample in which the positive-type concave-convex pattern obtained in the above (1) patterning property evaluation was formed was heated at 270 ° C for 1 hour in a nitrogen atmosphere using a temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B) to obtain a cured film. The obtained cured film was treated by a pressure cooker (131 ° C, 2.0 atm) for 100 hours, and then a mesh test (JIS K5400) was used to form a 100 square 1 mm square with a cutting blade, from above. The Cellophane (registered trademark) tape was attached and peeled off, and the number of squares remaining on the substrate without adhering to the Cellophane (registered trademark) tape was counted, thereby evaluating the adhesion after hardening. Table 13 below shows the number of squares remaining on the tantalum wafer after the tape peeling test. The more the number, the better the next.

[Table 13]

In the case of comparison with the same alkali-soluble polymer (A), it is understood that the adhesion after curing under the above conditions is further improved by the addition of the component (G).

<Preparation of Negative Photosensitive Resin Composition> [Examples 116 to 136, Comparative Examples 19 to 22]

The negative photosensitive resin compositions of Examples 116 to 136 and Comparative Examples 19 to 26 were obtained from the alkali-soluble polymers (A) obtained in the above Examples 1 to 7 and Comparative Examples 1 to 6 (P- 1 to P-13) 100 parts by weight, only the photoacid generator (B) 2-[2-(4-methylphenylsulfonyloxyimino) was added in the amounts shown in Table 14 below. -2,3-dihydrothiophene-3-ylidene-2-(2-methylphenyl)acetonitrile (Irgacure PAG121, manufactured by Ciba Japan Co., Ltd.) 5 parts by weight of the organic hydrazine compound obtained in the above Reference Example 5 ( C) 30 parts by weight of C-1 or 30 parts by weight of the organic hydrazine compound (C) C-2 obtained in Reference Example 6 dissolved in GBL, or further, the following amounts shown in Table 14 below The compound (H) (H-1 to H-3) which can be crosslinked by the action of an acid, and the following (I) sensitizer (I-1) are dissolved in GBL to form a resin solid component. A solution of an alkali-soluble polymer resin having a concentration of 35 mass%. P-7 and P-12 having poor solubility in GBL are dissolved in NMP to prepare an alkali-soluble polymer solution having a resin solid content of 35% by mass, and each alkali-soluble polymer solution is filtered by 0.2 μm. Prepared by filtration.

(H-1) TMOM-BP (Honori Chemical Industry: Trade Name)

(H-2) TML-BPAF-MF (Honori Chemical Industry: Trade Name)

(H-3) 1,3,4,6-tetrakis(methoxymethyl)glycoluril

(I-1) N-phenylethanolamine

[Table 14]

As component B, 2-[2-(4-methylphenylsulfonyloxyimino)-2,3-dihydrothiophene-3-ylidene]-2-(2-methylphenyl) ) acetonitrile (Irgacure PAG121, manufactured by Ciba Japan Co., Ltd.) is 5 parts by weight

<Evaluation of photosensitive resin composition> (1) Evaluation of patterning characteristics ‧Pre-baked film production and film thickness measurement

The negative photosensitive resin compositions of the above examples and comparative examples were spin-coated on a 6-inch wafer on a hot plate by a spin coater (manufactured by Tokyo Wealth Co., Ltd., Clean Track Mark 8). The film for evaluation was preliminarily baked at 110 ° C for 180 seconds to obtain a film having a thickness of about 15 μm. The film thickness was measured by a film thickness measuring device (Lambda ACE manufactured by Dainippon Screen Manufacturing Co., Ltd.).

‧exposure

With respect to this coating film, exposure was performed by stepwise changing the exposure amount by a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i line (365 nm) through a mask with a test pattern.

‧Baked after exposure

The exposed wafer was subjected to post-exposure baking on a hot plate at 120 ° C for 3 minutes.

‧development

The above-mentioned exposure-baked coating film was developed using an alkaline developing solution (AZ300MIF developing solution manufactured by AZ Electronic Materials Co., Ltd., 2.38 mass% aqueous solution of tetramethylammonium hydroxide), and rinsed with pure water to form Negative concave and convex pattern.

[sensitivity (mJ/cm ² )]

When the film thickness measured by the above conditions was observed under a microscope, and the film thickness was measured using a film thickness measuring device (Lambda ACE manufactured by Dainippon Screen Manufacturing Co., Ltd.), about 90% of the film thickness was maintained in the exposed region. Part of the exposure amount was evaluated as sensitivity. The results are shown in Table 15 below.

[resolution (μm)]

The coating film produced by the above conditions was observed under a microscope, and the size of the through hole in which the square concave-convex pattern of the unexposed portion was completely dissolved was taken as the resolution. The results are shown in Table 15 below.

(2) Evaluation of the shape of the pattern after hardening (evaluation by cone angle)

The evaluation of the taper angle was carried out by heating a sample having the negative concavo-convex pattern obtained in the above (1) evaluation of the patterning property at 320 ° C in a nitrogen atmosphere using a temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B). A cured film was obtained in an hour, and a section of a 50 μm line of the cured film was observed using an S-2400-shaped Hitachi scanning electron microscope manufactured by Hitachi, Ltd. In this cross section, as shown in Fig. 1, the angle formed by the pattern side surface of the line and the substrate was determined as a taper angle. When the taper angle exceeds 50°, it can be determined that the cured film is preferably a surface protective film of a semiconductor device or an interlayer insulating film. The results are shown in Table 15 below.

(3) Chemical resistance test ("Residual film rate" measurement and "pattern observation")

The sample in which the negative concavo-convex pattern obtained in the above (1) evaluation of the patterning property was formed was heated at 350 ° C for 1 hour and 30 minutes in a nitrogen atmosphere using a temperature-raising oven (manufactured by Koyo Thermo Systems, Inc., VF200B).

The obtained cured film was immersed in a bath filled with a resist stripping solution TOK105 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) heated to 80 ° C for 5 minutes, and after washing with pure water, the film thickness was measured, and the residual film ratio was measured. . Then observe the state of the pattern. The results are shown in Table 15 below.

[Table 15]

When the polymers having the same basic skeleton are compared with each other, the solution prepared by using the alkali-soluble polymer (A) (P-1 to P-7) obtained in the above Examples 1 to 7 is compared with the use. The solution prepared by the alkali-soluble polymer (A) (P-8 to P-13) obtained in Examples 1 to 6 was superior in sensitivity.

[Industrial availability]

The photosensitive resin composition of the present invention can be preferably used as a surface protective film for a semiconductor device and a light-emitting device, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, and a device having a bump structure. A film, an interlayer insulating film of a multilayer circuit, a protective layer of a flexible copper foil plate, a solder resist film, and a liquid crystal alignment film.

a. . . Substrate surface

b. . . Pattern side of the surface protective film

θ. . . Cone angle

Fig. 1 is a cross-sectional view showing a 50 μm line of a post-hardening concavo-convex pattern observed using an S-2400-shaped Hitachi scanning electron microscope manufactured by Hitachi, Ltd.

Figure 2 shows the results of ¹³ C-NMR of the alkali-soluble polymer (A) P-1.

Figure 3 shows the results of ¹³ C-NMR of the alkali-soluble polymer (A) P-2.

Figure 4 shows the results of ¹³ C-NMR of the alkali-soluble polymer (A) P-3.

Fig. 5 shows the results of ¹³ C-NMR of the alkali-soluble polymer (A) P-4.

Fig. 6 shows the results of ¹³ C-NMR of the alkali-soluble polymer (A) P-5.

Fig. 7 shows the results of ¹³ C-NMR of the alkali-soluble polymer (A) P-8.

Claims (17)

An alkali-soluble polymer having a structure synthesized from at least one carboxylic acid compound selected from the group consisting of polyvalent carboxylic acids and derivatives thereof and a polyamine compound; and derived from a crosslinking group capable of a structure containing a crosslinking group of a compound which reacts with the above polycarboxylic acid or a derivative thereof; wherein the structure containing the crosslinking group is a structure represented by the following formula (1): In the formula, R ₁ and R ₂ are each independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from a hydroxyl group, an alkoxy group, and an alkenyl group. a group of at least one group of the group consisting of an epoxy group and an oxetane group, and W ₁ is an organic group having a (n ₁ +2) valence of 1 to 30, and m ₁ is 1~ An integer of 500, and n ₁ is an integer from 1 to 12. An alkali-soluble polymer having at least one selected from the group consisting of a structure represented by the following general formula (2) and a structure represented by the following general formula (4): [Chemical 2] In the formula, X ₁ , Y ₁ and Y ₂ are each independently a 2 to 4 valent organic group having at least 2 carbon atoms, and Z ₁ has a structure represented by the following formula (3): (wherein R ₁ and R ₂ are each independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from a hydroxyl group, an alkoxy group, and an alkenyl group; a group of at least one group of the group consisting of an epoxy group and an oxetane group, W ₂ is an organic group having a (n ₁ + 2) valence of 1 to 30, and B is selected from the group consisting of - a group in the group consisting of NH-, -O-, and -S-, and n ₁ is an integer of 1 to 12), and R ₄ to R ₆ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. m ₂ is an integer from 1 to 1000, and m ₃ is an integer from 1 to 500, where m ₂ /(m ₂ +m ₃ )=0.05 to 0.99, and n ₂ to n ₇ are each independently an integer of 0 to 2 _{, n 2 + n 3 + n} 4 + n 5 + n 6 + n 7> 0, where, X ₁ and Y m comprising the ₁₂ units, and the arrangement comprising Z ₁ and the m Y _{2 3} units of The order is not limited to;; [Chemical 4] In the formula, Y ₃ is a tetravalent organic group having at least 2 carbon atoms, and X ₂ and Y ₄ are each independently a 2 to 4 valent organic group having at least 2 carbon atoms, and Z ₁ has the following formula (3) The structure represented: (wherein R ₁ and R ₂ are each independently at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms, and R ₃ is selected from a hydroxyl group, an alkoxy group, and an alkenyl group; a group of at least one group of the group consisting of an epoxy group and an oxetane group, W ₂ is an organic group having a (n ₁ + 2) valence of 1 to 30, and B is selected from the group consisting of - a group in the group consisting of NH-, -O-, and -S-, and n ₁ is an integer of 1 to 12), and R ₇ and R ₈ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. m ₄ is an integer from 1 to 1000, and m ₅ is an integer from 1 to 500. Here, m ₄ /(m ₄ +m ₅ )=0.05 to 0.99, n ₈ to n ₁₁ are integers of 0 to 2, n _{8 + n 9 + n 10 + n} 11> 0, where, X _2, and comprising Y m ₃ of the _four units, and the order in which Z ₁ and Y m ₄ of the _five units are not limited to include}. A method for producing an alkali-soluble polymer, which comprises the following steps in sequence: A polycarboxylic acid or a derivative thereof is reacted with a compound containing a crosslinking group to synthesize a compound having a structure containing a crosslinking group having a carboxylic acid or a derivative thereof at both ends; and having the above two terminals as a carboxylic acid or a derivative thereof The compound having a structure of a crosslinking group is polycondensed with a polyamine compound. A photosensitive resin composition comprising 1 to 50 parts by weight of the photoacid generator (B) per 100 parts by weight of the alkali-soluble polymer (A) according to claim 1 or 2. The photosensitive resin composition of claim 4, further comprising 1 to 40 parts by weight of the organic cerium compound (C) based on 100 parts by weight of the alkali-soluble polymer (A). The photosensitive resin composition of claim 4, wherein the photoacid generator (B) is a naphthoquinonediazide compound, and further comprises a monocarboxylic acid compound (D) based on 100 parts by weight of the alkali-soluble polymer (A). ) 1 to 40 parts by weight. The photosensitive resin composition of claim 4, further comprising 1 to 100 parts by weight of the phenol compound (E) based on 100 parts by weight of the alkali-soluble polymer (A). The photosensitive resin composition of claim 4, wherein the compound (F) which undergoes a crosslinking reaction by heat is further contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the alkali-soluble polymer (A). The photosensitive resin composition of claim 4, wherein the compound (F) which is crosslinked by heat is selected from the group consisting of an epoxy compound, an oxetane compound, a melamine compound, an alkenyl compound, and the following At least one of the structure represented by the formula (5), the structure represented by the following formula (6), and the group represented by the following formula (7): In the formula, R ₉ is a hydrogen atom or a monovalent group selected from the group consisting of methyl, ethyl, n-propyl and isopropyl, and R ₁₀ is selected from a hydrogen atom, a hydroxyl group, and a carbon atom. a monovalent organic group of at least one of the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group, an ester group having 2 to 10 carbon atoms, and an amine group having 2 to 10 carbon atoms, n ₁₂ is an integer from 1 to 5, and n ₁₃ is an integer from 0 to 4, where n ₁₂ + n ₁₃ = 5, m ₆ is an integer from 1 to 4, and Z ₂ is CH ₂ OR when m ₆ =1. ₉ or R ₁₀ , in the case of m ₆ = 2 to 4, a single bond or a 2 to 4 valent organic group, where R ₉ and R ₁₀ may be the same when a plurality of CH ₂ OR ₉ and R ₁₀ are present. Can also be different}; Wherein R ₁₁ and R ₁₂ are each independently a hydrogen atom or a hydrocarbon group selected from the group consisting of 1 to 10 carbon atoms and R ₁₃ CO- (wherein R ₁₃ is a hydrocarbon group having 1 to 10 carbon atoms) The base of the group}; [Chemical 8] In the formula, D ₁ is a functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an organic group capable of crosslinking, and M ₁ is selected from -CH ₂ -, a group in the group consisting of -O-, and -S-, Z ₃ is a divalent organic group, and n ₁₄ is an integer of 0 to 4. When there are a plurality of D ₁ , a plurality of D ₁ may be the same Can also be different}. The photosensitive resin composition of claim 4, wherein the compound (G) which generates an acid by heat is further contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the alkali-soluble polymer (A). A photosensitive resin composition comprising 0.5 to 30 parts by weight of a photoacid generator (B) relative to 100 parts by weight of the alkali-soluble polymer (A) according to claim 1 or 2, and capable of acting by an acid The crosslinked compound (H) is 1 to 50 parts by weight. The photosensitive resin composition of claim 11, wherein the compound (H) which can be crosslinked by the action of an acid is a compound having a methylol group or an alkoxymethyl group in the molecule. The photosensitive resin composition of claim 11 or 12, further comprising 1 to 20 parts by weight of the compound (I) which is a sensitizer with respect to 100 parts by weight of the alkali-soluble polymer (A). A solution of the photosensitive resin composition of claim 4, which further comprises an organic solvent (J). A method of producing a hardened concave-convex pattern, comprising the steps of: (1) forming a photosensitive resin composition according to any one of claims 4 to 13 or a photosensitive resin composition solution according to claim 14 on a substrate And the step of obtaining the photosensitive resin layer; (2) the exposing step; (3) the developing step; and (4) the step of heat-treating the obtained concavo-convex pattern. A semiconductor device comprising: a semiconductor substrate; a semiconductor element provided on the semiconductor substrate; and an insulating film provided on an upper portion of the semiconductor element; and the insulating film is obtained by the manufacturing method of claim 15. Hardened concave and convex pattern. A light-emitting device comprising: a display element substrate; an insulating film covering a surface of the substrate; and a display element provided on an upper portion of the display element substrate; and the insulating film is manufactured by the request item 15 The hardened concave-convex pattern obtained by the method.