TWI491987B - A negative photosensitive resin composition, a hardened embossed pattern, and a semiconductor device - Google Patents

Description

Negative photosensitive resin composition, method for producing cured embossed pattern, and semiconductor device

The present invention relates to a photosensitive resin composition and a semiconductor device, a display device, and the like having a cured embossed pattern obtained by curing the photosensitive resin composition.

Conventionally, a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties has been used for an insulating material for an electronic component, a passivation film for a semiconductor device, a surface protective film, an interlayer insulating film, and the like. In the polyimine resin, the donor in the form of a photosensitive polyimide precursor can be easily formed by coating, exposing, developing, and curing the imidization of the precursor. Heat-resistant embossed pattern film. Such a photosensitive polyimide precursor has a significantly shorter step than the prior non-photosensitive polyimide resin.

On the other hand, in recent years, the mounting method of a semiconductor device to a printed wiring board is also changing from the viewpoint of improvement in the totality and calculation function, and the miniaturization of the wafer size. From the previous mounting methods using metal pins and lead-tin eutectic solders, BGA (Ball Grid Array), CSP (Chip Size Package), etc., which can be mounted at a higher density, are gradually used. A structure in which a polyimide film is directly contacted with a solder bump. When such a bump structure is formed, high heat resistance and chemical resistance are required for the film.

Further, due to the development of the miniaturization of the semiconductor device, the problem of wiring delay is surfaced. As a method of improving the wiring resistance of a semiconductor device, it is being used up to now. Gold or aluminum wiring changes to the wiring of copper or copper alloy with lower resistance. Further, a method of preventing wiring delay by improving insulation between wirings is also employed. In recent years, in many cases, a low dielectric constant material which is a material having high insulating properties constitutes a semiconductor device, and on the other hand, a low dielectric constant material is brittle and tends to be easily damaged, for example, via a reflow step. When it is mounted on a substrate together with a semiconductor wafer, there is a problem that the low dielectric constant material is partially damaged due to shrinkage caused by temperature change.

As a method for solving this problem, for example, Patent Document 1 discloses a photosensitive polyimide intermediate having a terminal group having a carbon number of 4 or more and a photosensitive group substituted with a hydrocarbon group having 1 to 3 carbon atoms.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-80776

However, the resolution or elongation of the photosensitive resin composition containing the polyimide precursor described in Patent Document 1 is improved, but the transparency of the photosensitive resin composition or the rigidity of the polyimide film (Yang) Modular modulus) There is room for improvement.

Therefore, an object of the present invention is to provide a photosensitive resin composition which is high in transparency and which provides a cured body having a high Young's modulus after heat curing, and which is cured by using the photosensitive resin composition. a method of embossing a pattern; and a semiconductor device or a display device having the hardened embossed pattern.

The inventors of the present invention have diligently studied and repeated experiments in view of the problems of the prior art described above, and as a result, have found that by incorporating a specific chemical structure into one of the side chains of the polyimide precursor, it is possible to form a polyimide-containing precursor. The photosensitive resin composition in the case where the photosensitive resin composition is improved in transparency and further improved in Young's modulus of the cured film after thermosetting The invention thus completes the invention. That is, the present invention is as follows.

[1] A negative photosensitive resin composition comprising: (A) having the following general formula (1):

In the formula, X ₁ is a tetravalent organic group having a carbon number of 6 to 40, Y ₁ is a divalent organic group having a carbon number of 6 to 40, n is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom. Or the following general formula (2) or (3):

(wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a carbon number of 1 to 3 organic ones, and m is an integer of 2 to 10)

-R ₆ (3)

(wherein R ₆ is an aliphatic group selected from a carbon number of 5 to 30 which may have a hetero atom or a valent group of an aromatic group having 6 to 30 carbon atoms)

The one-valent organic group is represented, and the ratio of the total of the one-valent organic group represented by the above formula (2) to the one-valent organic group represented by the above formula (3) with respect to all of R ₁ and R ₂ is 80 mol% or more, and the ratio of the monovalent organic group represented by the above formula (3) to all of R ₁ and R ₂ is 20 mol% to 80 mol%}

The polyimine precursor of the structure shown: 100 parts by mass; and (B) the photopolymerization initiator: 0.1 part by mass to 20 parts by mass.

[2] The negative photosensitive resin composition according to [1], wherein the R ₆ is an aliphatic group having a carbon number of 5 to 30.

[3] The negative photosensitive resin composition according to [1] or [2], wherein in the above formula (1), the monovalent organic group represented by the above formula (2) and the above formula (3) The ratio of the total number of the one-valent organic groups to the total of R ₁ and R ₂ is 90 mol% or more, and the one-valent organic group represented by the above formula (3) is relative to R ₁ and R ₂ The ratio of all is 25 mol% to 75 mol%.

[4] The negative photosensitive resin composition according to any one of [1] to [3], which further comprises (C) heat exchange with respect to the (A) polyimine precursor: 100 parts by mass Jointing agent: 0.1 parts by mass to 30 parts by mass.

[5] A method of manufacturing a hardened relief pattern, comprising the steps of: (1) A step of applying a negative photosensitive resin composition according to any one of [1] to [4] onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer; (3) a step of developing the exposed photosensitive resin layer to form a relief pattern; (4) a step of heat-treating the embossed pattern to form a hardened embossed pattern.

[6] A hardened relief pattern produced by the method as described in [5].

[7] A semiconductor device comprising a semiconductor element and a cured film provided on an upper portion of the semiconductor element, wherein the cured film is a cured embossed pattern as described in [6].

[8] A display device comprising a display element and a cured film provided on an upper portion of the display element, wherein the cured film is a cured embossed pattern as described in [6].

According to the present invention, it is possible to provide a photosensitive resin composition which has high transparency as a resin composition and which provides a cured body having a high Young's modulus after heat curing; A method of producing a cured embossed pattern by a photoresin composition; and a semiconductor device or a display device having the cured embossed pattern.

Hereinafter, the form for carrying out the invention (hereinafter simply referred to as "embodiment") will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

In the embodiment, the photosensitive resin composition contains (A) a polyimide precursor, (B) a starter, a (C) thermal crosslinking agent, and other components as required. The ingredients are described below in order.

Furthermore, in the present specification, when a plurality of structures are represented by a symbol in the general formula, they may be the same or different from each other.

(A) Polyimine precursor

In the embodiment, the (A) polyimine precursor is a resin component contained in the negative photosensitive resin composition, and is a polyamine having a structure represented by the following formula (1).

In the formula, X ₁ is a tetravalent organic group having a carbon number of 6 to 40, Y ₁ is a divalent organic group having a carbon number of 6 to 40, n is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom. Or the following general formula (2) or (3):

(wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a carbon number of 1 to 3 organic ones, and m is an integer of 2 to 10)

-R ₆ (3)

(wherein R ₆ is an aliphatic group selected from a carbon number of 5 to 30 which may have a hetero atom or a valent group of an aromatic group having 6 to 30 carbon atoms)

The one-valent organic group is represented, and the total of the one-valent organic group represented by the above formula (2) and the one-valent organic group represented by the above formula (3) is 80 mol with respect to all of R ₁ and R ₂ More than or equal to the ear, and the ratio of the one-valent organic group represented by the above formula (3) to all of R ₁ and R ₂ is 20 mol% to 80 mol%}

In the above formula (1), X ₁ is not limited as long as it is a tetravalent organic group having 6 to 40 carbon atoms, but from the viewpoint of heat resistance and photosensitivity, it is preferably -COOR ₁ group and - An aromatic group or an alicyclic aliphatic group in which the COOR ₂ group and the -CONH- group are ortho to each other. Further, the tetravalent organic group represented by X ₁ is preferably an organic group having an aromatic ring and having 6 to 40 carbon atoms.

Further, X ₁ is preferably a tetravalent organic group represented by the following formula (5).

[Chemical 5]

Further, the structure of X ₁ may be one type or a combination of two or more types.

In the above formula (1), Y ₁ is not limited as long as it is a divalent organic group having 6 to 40 carbon atoms, but it is preferably 1 to 4 in terms of heat resistance and photosensitivity. A cyclic organic group substituted with an aromatic ring or an aliphatic ring, or an aliphatic group or a fluorenylalkyl group having no cyclic structure. More preferably, Y ₁ is a structure represented by the following formula (6) or (7).

[Chemical 6]

[Chemistry 7]

(wherein A represents independently a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ) or a butyl group (-C ₄ H ₉ ).

Further, the structure of Y ₁ may be one type or a combination of two or more types.

R ₁ and R ₂ in the above formula (1) are each independently a hydrogen atom or a monovalent organic group represented by the above formula (2) or (3).

The n in the above formula (1) is not particularly limited as long as it is an integer of from 2 to 150. From the viewpoint of the photosensitive property and mechanical properties of the photosensitive resin composition, it is preferably an integer of from 3 to 100, more preferably It is an integer from 5 to 70.

In the above formula (1), the one-valent organic group represented by the above formula (2) and one of the formula (3) are represented from the viewpoint of the photosensitive property and mechanical properties of the photosensitive resin composition. The ratio of the total of the valence organic groups to the total of R ₁ and R ₂ is 80 mol% or more, and the ratio of the monovalent organic group represented by the above formula (3) to all of R ₁ and R ₂ is 20 Mole%~80% by mole. Further, in the general formula (1), the total of the monovalent organic group represented by the above formula (2) and the one-valent organic group represented by the above formula (3) is more preferably relative to R ₁ and R ₂ . The ratio of all is 90 mol% or more, and the ratio of the monovalent organic group represented by the above formula (3) to all of R ₁ and R ₂ is from 25 mol% to 75 mol%.

R ₃ in the above formula (2) is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. However, from the viewpoint of the photosensitive property of the photosensitive resin composition, a hydrogen atom is preferred. Or methyl.

R ₄ and R ₅ in the above formula (2) are not limited as long as they are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but from the viewpoint of the photosensitive characteristics of the photosensitive resin composition, It is preferably a hydrogen atom.

In the above formula (2), m is an integer of 2 or more and 10 or less, and is preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitivity.

R ₆ in the above formula (3) is not limited as long as it is one selected from the group consisting of an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom or an aromatic group having 6 to 30 carbon atoms. It is preferably an aliphatic group having 5 to 30 carbon atoms, more preferably an aliphatic group having a carbon number of 5 to 30 carbon atoms. Further, the aliphatic group having 5 to 30 carbon atoms may be a saturated hydrocarbon group, and part or all of one of the hydrogen atoms of the saturated hydrocarbon group may be substituted with a monovalent saturated organic group containing a hetero atom or a monovalent aromatic group. Preferably, R ₆ in the above formula (3) is selected from the group consisting of neopentyl, octyl, benzyl, and a group derived from polyethylene glycol monomethyl ether.

Further, examples of the hetero atom in the present invention include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom.

The (A) polyimine precursor can be converted to polyimine by subjecting to a cyclization treatment by heating (for example, 200 ° C or higher).

[(A) Preparation method of polyimine precursor]

The polyimine precursor represented by the above formula (1) in the present embodiment is obtained, for example, by reacting a tetracarboxylic dianhydride containing the above-mentioned carbon number 6 to 40 tetravalent organic group X ₁ with (a) an alcohol in which a monovalent organic group represented by the above formula (2) is bonded to a hydroxyl group, and (b) a monovalent organic group represented by the above formula (3) bonded to a hydroxyl group The alcohol is reacted to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester), which is then condensed with a diamine containing the above-mentioned divalent organic group Y _{1 having a} carbon number of 6 to 40.

(Preparation of acid/ester)

In the present embodiment, examples of the tetracarboxylic dianhydride containing a tetravalent organic group X _{1 having} 6 to 40 carbon atoms include pyromellitic dianhydride and diphenyl ether-3, 3', 4, and 4. '-Tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl Base-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4- Phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and the like. Further, these may be used alone or in combination of two or more.

In the present embodiment, examples of the (a) alcohol having the structure represented by the above formula (2) include 2-propenyloxyethanol, 1-propenyloxy-3-propanol, and hydroxy group. Methyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxy acrylate Propyl propyl ester, 2-methyl propylene methoxy ethoxyethanol, 1-methyl propylene decyloxy-3-propanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy methacrylate 3-butoxypropyl ester, 2-hydroxy-3-butoxypropyl methacrylate, and the like.

(b) The aliphatic group having 5 to 30 carbon atoms or the aromatic alcohol having 6 to 30 carbon atoms represented by the above formula (3), for example, 1-pentanol, 2-pentanol, 3-pentane Alcohol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, three Ethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, and the like.

Negative photosensitive resin composition of the component (a) and the total content of the component (b) with respect to the above-described formula (1) in all of the content of R ₁ and R _2, preferably 80 mole% The content of the component (b) is preferably from 20 mol% to 80 mol% based on the total content of R ₁ and R ₂ . When the content of the component (b) is 80% by mole or less, the desired photosensitive property can be obtained, which is preferable. On the other hand, when the content of the component (b) is 20% by mole or more, it becomes easy to be expressed. Transparency is preferred.

By stirring, dissolving and mixing the above tetracarboxylic dianhydride and the above alcohol in a reaction solvent at a reaction temperature of 20 to 50 ° C for 4 to 10 hours in the presence of an alkaline catalyst such as pyridine, acid 2 can be carried out. The half esterification of the anhydride provides the desired acid/ester body.

The reaction solvent is preferably a polyimine precursor which dissolves the acid/ester body and a polycondensation product of the acid/ester body and a diamine, and examples thereof include N-methyl-2- Pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylhydrazine, tetramethylurea, γ-butyrolactone, ketones, esters, internal Esters, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, B Diol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, g Alkane, benzene, toluene, xylene, and the like. These may be used singly or in combination of two or more.

(Preparation of polyimine precursors)

In the above acid/ester body (typically a solution in the above reaction solvent), a known dehydrating condensing agent such as dicyclohexylcarbodiimide or 1-ethoxycarbonyl group is introduced under ice bath cooling. 2-Ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-d-butylenediminocarbonate After the ester or the like is mixed and the acid/ester is made into a polyanhydride, the diamine containing the divalent organic group Y ₁ having a carbon number of 6 to 40 is additionally dissolved or dispersed in a solvent. Further, polycondensation is carried out, whereby a polyimide precursor which can be used in the embodiment can be obtained.

6 to 40. As the divalent organic group comprising carbon number of Y ₁ of the diamines include, for example: p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'- Aminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-two Aminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4' -diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diamino Benzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-di Aminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminobenzene) Oxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 4,4-bis(4-amine Phenyloxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3- Aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-amine Phenyl) fluorene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-amino) Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylmethylalkyl) Benzene, o-tolidine oxime, 9,9-bis(4-aminophenyl)anthracene, and one of the hydrogen atoms on the benzene ring are partially methyl, ethyl, hydroxymethyl or hydroxyethyl a halogen or the like, such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3 '-Dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy -4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, a mixture thereof, and the like, but is not limited thereto.

In the embodiment, in order to improve the adhesion between the photosensitive resin layer formed on the substrate and the various substrates by applying the negative photosensitive resin composition to the substrate, the (A) polyimine precursor is prepared. In the case of copolymerization, a diamine group such as 1,3-bis(3-aminopropyl)tetramethyldioxane or 1,3-bis(3-aminopropyl)tetraphenyldioxane may be copolymerized. Oxanes.

After the completion of the polycondensation reaction, the water-absorbing by-products of the dehydration condensing agent coexisting in the reaction liquid are separated by filtration, and the water, the aliphatic lower alcohol, or a mixture thereof, etc. The poor solvent is introduced into the reaction liquid to analyze the polymer, and the re-dissolution, reprecipitation, and precipitation operations are repeated, whereby the polymer is purified and vacuum-dried to separate the polyimine which can be used in the embodiment. Precursor. In order to increase the degree of purification, the solution of the polymer may be removed by pulverizing the anion and/or cation exchange resin with a suitable organic solvent to remove the ionic impurities.

The molecular weight of the (A) polyimine precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, as measured by a polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography. Good is 20,000~40,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and therefore, it is preferable. On the other hand, when the weight average molecular weight is 150,000 or less, the dispersibility to the developer and the resolution of the embossed pattern are good, which is preferable. As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. Further, the molecular weight was determined based on a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to be selected from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

(B) Photopolymerization initiator

The (B) photopolymerization initiator in the present embodiment will be described. As the (B) photopolymerization initiator, a compound previously used as a photopolymerization initiator for UV (Ultraviolet) curing can be arbitrarily selected. For example, as the (B) photopolymerization initiator, benzophenone, methyl orthobenzoate, 4-benzylidene-4'-methyldiphenyl ketone, and the like are preferably exemplified. Benzophenone derivatives such as benzyl ketone and anthrone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone 9-oxosulfur 2-methyl 9-oxosulfur 2-isopropyl 9-oxosulfur Diethyl 9-oxosulfur 9-oxosulfur Derivatives; benzoin derivatives such as benzophenone, benzoin dimethyl ketal, benzoin-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl -1,2-butanedione-2-(O-methoxycarbonyl)anthracene, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)anthracene, 1-phenyl -1,2-propanedione-2-(O-ethoxycarbonyl)anthracene, 1-phenyl-1,2-propanedione-2-(O-benzylidene) fluorene, 1,3- Anthracene such as diphenylpropanetrione-2-(O-ethoxycarbonyl)anthracene, 1-phenyl-3-ethoxypropanetrione-2-(O-benzylidene) hydrazine; N- N-arylglycines such as phenylglycine; peroxides such as benzamidine chloride; aromatic biimidazoles, etc., but are not limited thereto. Further, these may be used alone or in combination of two or more. Among the above (B) photopolymerization initiators, in particular, in terms of photosensitivity, it is more preferably an anthracene.

(B) The amount of the photopolymerization initiator to be added is 0.1 parts by mass to 20 parts by mass based on 100 parts by mass of the (A) polyimine precursor, and is preferably 2 parts by mass in terms of photosensitivity characteristics. 15 parts by mass. The photosensitive resin composition is excellent in photosensitivity by adjusting the (B) photopolymerization initiator in an amount of 0.1 part by mass or more based on 100 parts by mass of the (A) polyimine precursor, and on the other hand, by massing 20 parts by mass. Hereinafter, the photosensitive resin composition is excellent in thick film hardenability.

(C) Thermal crosslinking agent

In the embodiment, the negative photosensitive resin composition preferably further contains (C) a thermal crosslinking agent. The thermal crosslinking agent may be used to crosslink the (A) polyimine precursor when the embossed pattern formed using the negative photosensitive resin composition is heat-hardened, or the thermal crosslinking agent itself may form a network. Crosslinker. (C) The thermal crosslinking agent is more preferable because it can further enhance the heat resistance and chemical resistance of the cured film formed of the negative photosensitive resin composition. As the (C) thermal crosslinking agent, an amine-based resin and a derivative thereof can be preferably used, and among them, a urea resin, an intramethylene urea resin, a hydroxyethylene urea resin, a melamine resin, a benzoguanamine can be preferably used. Resins, and such derivatives. Further, an alkoxymethylated urea compound and an alkoxymethylated melamine compound are exemplified by MX-290 (manufactured by Nippon Carbide Co., Ltd.), UFR-65 (manufactured by Nihon Cytec Co., Ltd.), and MW-390 (Nippon Carbide). The company manufactures) as an example.

The amount of the (C) thermal crosslinking agent is not particularly limited as long as it is 0.1 parts by mass to 30 parts by mass based on 100 parts by mass of the (A) polyimine precursor. Among them, it is preferably from 0.5 part by mass to 20 parts by mass, more preferably from 2 parts by mass to 10 parts by mass. When the compounding amount is 0.1 parts by mass or more, it exhibits good heat resistance and chemical resistance, and on the other hand, When it is 30 mass parts or less, since it is excellent in storage stability, it is preferable.

Other ingredients

In the embodiment, the negative photosensitive resin composition may further contain components other than the components (A) to (C). Examples of the other component include a solvent, a resin component other than the above (A) polyimine precursor, a sensitizer, a monomer having a photopolymerizable unsaturated bond, a secondary auxiliary agent, a thermal polymerization inhibitor, and the like. An azole compound, a hindered phenol compound, an organotitanium compound, or the like.

As the solvent, it is preferred to use a polar organic solvent in terms of solubility of the (A) polyimine precursor. Specific examples thereof include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide. , dimethyl hydrazine, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-ethinyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl- 2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, and the like, these may be used singly or in combination of two or more.

The solvent may have a coating film thickness and a viscosity which are required for the negative photosensitive resin composition, and may be, for example, in the range of 30 parts by mass to 1,500 parts by mass based on 100 parts by mass of the (A) polyimide precursor. It is preferably used in the range of 100 parts by mass to 1000 parts by mass.

Further, from the viewpoint of improving the storage stability of the negative photosensitive resin composition, a solvent containing an alcohol is preferable. The alcohol which can be preferably used is typically an alcohol having an alcoholic hydroxyl group in the molecule and having no olefinic double bond, and specific examples thereof include methanol, ethanol, n-propanol, isopropanol, and An alkanol such as butanol, isobutanol or tert-butanol; a lactate such as ethyl lactate; propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, Propylene glycol monoalkyl ethers such as propylene glycol-1-n-propyl ether, propylene glycol-2-n-propyl ether; monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether; 2-hydroxyisobutyric acid Esters; glycols such as ethylene glycol and propylene glycol. Among these, preferred are lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate, and ethanol, and more preferably ethyl lactate, propylene glycol-1-methyl ether, and propylene glycol-1. -ether, and propylene glycol-1-n-propyl ether.

When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably from 5% by mass to 50% by mass based on the mass of the total solvent, more preferably It is 10% by mass to 30% by mass. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the negative photosensitive resin composition is good, and when it is 50% by mass or less, (A) The solubility of the polyimide precursor is good, and therefore it is preferred.

In the embodiment, the negative photosensitive resin composition may further contain a resin component other than the (A) polyimine precursor. The resin component which can be contained in the negative photosensitive resin composition is, for example, polyimine, poly Azole, poly An azole precursor, a phenol resin, a polyamide, an epoxy resin, a decane resin, an acrylic resin, or the like. The amount of the resin component to be added is preferably in the range of 0.01 part by mass to 20 parts by mass based on 100 parts by mass of the (A) polyimine precursor.

In the embodiment, in order to improve the photosensitivity, the sensitizer may be optionally blended in the negative photosensitive resin composition. Examples of the sensitizer include: mireconone, 4,4'-bis(diethylamino)benzophenone, and 2,5-bis(4'-diethylaminobenzylidene) ring. Pentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnaminylindanone, p-dimethylamino Benzylidene indanone, 2-(p-dimethylaminophenyl-extension benzene)-benzothiazole, 2-(p-dimethylaminophenyl-vinyl)benzothiazole, 2-(p-dimethylene) Aminophenylvinyl)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-ethylindol-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylamine Bean, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Coumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4- Phenyl benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzoene Thiazole, 2-(p-dimethylaminostyryl) benzo Azole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylamino) Benzopyridinyl) styrene and the like. These may be used singly or in combination of plural (for example, 2 to 5).

The blending amount of the sensitizer is preferably from 0.1 part by mass to 25 parts by mass based on 100 parts by mass of the (A) polyimine precursor.

In the embodiment, in order to improve the resolution of the embossed pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily formulated in the negative photosensitive resin composition. The (meth)acrylic compound which is subjected to radical polymerization by a photopolymerization initiator is preferably not limited to the following, and examples thereof include diethylene glycol dimethacrylate. Ester, tetraethylene glycol dimethacrylate is a single or diacrylate of methacrylate or polyethylene glycol and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, Mono, di or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylates and dimethacrylates of 1,4-butanediol, 1,6- Diacrylate and dimethacrylate of hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono or diacrylate of bisphenol A, methacrylate, benzenetrimethacrylate Acrylic Ester and methacrylic acid Ester, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol di or triacrylate and methacrylate, pentaerythritol , tris, or tetraacrylates and methacrylates, and compounds such as ethylene oxide or propylene oxide adducts of such compounds.

The amount of the monomer having a photopolymerizable unsaturated bond is preferably from 1 part by mass to 50 parts by mass based on 100 parts by mass of the (A) polyimine precursor.

In the embodiment, in order to improve the adhesion between the film formed using the negative photosensitive resin composition and the substrate, the adhesion aid can be arbitrarily formulated in the negative photosensitive resin composition. in. Examples of the auxiliary auxiliary agent include γ-aminopropyl dimethoxydecane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxydecane, and γ-glycidol. Oxypropyl propyl dimethoxy decane, γ-mercaptopropyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl dimethoxy methyl decane, 3-methyl propylene oxime Propyltrimethoxydecane, dimethoxymethyl-3-piperidinylpropylnonane, diethoxy-3-glycidoxypropylmethyldecane, N-(3-diethoxy Methyl decyl propyl) butyl quinone imine, N-[3-(triethoxydecyl)propyl] phthalic acid, benzophenone-3,3'-double (N -[3-triethoxydecylalkyl]propyl decylamine)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxydecyl]propyl decylamine a decane coupling agent such as -2,5-dicarboxylic acid, 3-(triethoxydecyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxy decane, and tris(ethyl acetamidine) An aluminum-based adhesion aid such as aluminum acetate, tris(acetonitrile)aluminum, (acetonitrile ethyl acetate) or aluminum diisopropoxide.

Among these secondary auxiliaries, a decane coupling agent is more preferably used in terms of adhesion. The amount of the auxiliary agent is preferably in the range of 0.5 part by mass to 25 parts by mass based on 100 parts by mass of the (A) polyimine precursor.

In the embodiment, the thermal polymerization inhibitor can be arbitrarily formulated, in particular, in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition during storage in a state in which the solvent is contained. As the thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, and thiophene can be used. , N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-t-butyl-p-methylphenol, 5 -nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfonate Propylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, and the like.

The amount of the thermal polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass based on 100 parts by mass of the (A) polyimine precursor.

For example, in the case of using a substrate containing copper or a copper alloy, the azole compound may be arbitrarily formulated in the negative photosensitive resin composition in order to suppress discoloration of the substrate. As an azole The compound may, for example, be 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole or 5-phenyl-1H. -Triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl 1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl- 1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethyl Benzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5- Methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-third-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5' -T-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amine Base-1H-tetrazole, 1-methyl-1H-tetrazole, and the like. More preferred are: tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Further, these azole compounds may be used alone or in combination of two or more.

The amount of the azole compound is preferably 0.1 parts by mass to 20 parts by mass based on 100 parts by mass of the (A) polyimine precursor, and more preferably 0.5 parts by mass to 5 parts by mass from the viewpoint of photosensitivity characteristics. . When the amount of the azole compound is 0.1 parts by mass or more based on 100 parts by mass of the (A) polyimide precursor, when a negative photosensitive resin composition is formed on copper or a copper alloy, copper or copper can be suppressed. On the other hand, when the content of the copper alloy is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

In the embodiment, the hindered phenol compound can be arbitrarily formulated in the negative photosensitive resin composition in order to suppress discoloration on the copper. Examples of the hindered phenol compound include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, and 3-(3,5-di - octadecyl tributyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate, 4,4' -methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene - bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylidene double [3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrogen Cinnamylamine, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-third Butylphenol), pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4 -hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1 , 3,5-three (3-hydroxy 2,6-dimethyl-4-isopropyl-benzyl) -1,3,5 -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1, 3,5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1, 3,5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl ]-1,3,5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1 , 3,5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3, 5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)- 1,3,5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl Base)-1,3,5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)- 1,3,5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl Base)-1,3,5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl Base)-1,3,5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5 -three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1, 3,5-three -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)- 1,3,5-three -2,4,6-(1H,3H,5H)-trione or the like, but is not limited thereto. Among these, it is especially preferred that 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6 (1H,3H,5H)-trione.

The amount of the hindered phenol compound is preferably 0.1 parts by mass to 20 parts by mass based on 100 parts by mass of the (A) polyimine precursor, and more preferably 0.5 parts by mass to 10 parts by mass from the viewpoint of photosensitivity characteristics. Share. When the amount of the hindered phenol compound to be added in an amount of 0.1 part by mass or more based on 100 parts by mass of the (A) polyimide precursor, for example, when a negative photosensitive resin composition is formed on copper or a copper alloy, it can be prevented. The discoloration and corrosion of copper or a copper alloy are preferable, and in the case of 20 parts by mass or less, the photosensitivity is excellent.

In the embodiment, the negative photosensitive resin composition may contain an organic titanium compound. When the organic titanium compound is contained, even when it is cured at a low temperature of about 250 ° C, a photosensitive resin layer excellent in chemical resistance can be formed.

Examples of the organic titanium compound which can be used include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

Specific examples of the organotitanium compound are shown in the following I) to VII):

I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable in terms of storage stability of a negative photosensitive resin composition and obtaining a good pattern, and specific examples thereof It is: bis(triethanolamine) titanium diisopropoxide, titanium bis(2,4-pentate) di-n-butoxide, titanium bis(2,4-pentanedioic acid) diisopropoxide, bis(tetramethyl) Pimelic acid) titanium diisopropylate, bis(acetic acid ethyl acetate) titanium diisopropylate, and the like.

II) titanium tetraalkoxide compounds: for example, titanium tetra-n-butoxide, titanium tetraethoxide, titanium tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, tetramethoxy Titanium propoxide, titanium tetramethylphenol, titanium tetra-n-sterol, titanium tetra-n-propoxide, titanium tetrastearyl alcohol, tetra [bis{2,2-(allyloxymethyl)butanol]] titanium, etc. .

III) titanocene compounds: e.g. pentamethyl cyclopentadienyl titanium trimethoxide, bis (η ⁵ -2,4- cyclopentadien-1-yl) bis (2,6-difluorophenyl) titanium Bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium or the like.

IV) titanium monoalcohol compounds: for example, tris(dioctylphosphoric acid) titanium isopropoxide, tris (dodecane) Base benzenesulfonic acid) titanium isopropoxide and the like.

V) an oxytitanium compound: for example, bis(glutaric acid) oxytitanium, bis(tetramethylpimelate)oxytitanium, phthalocyanine titanate or the like.

VI) Tetraacetyl acetonide titanium compound: for example, titanium tetraacetate or the like.

VII) Titanate coupling agent: for example, isopropyl tris(dodecylbenzenesulfonyl) titanate or the like.

In the above I) to VII), from the viewpoint of exhibiting better chemical resistance, the organotitanium compound is preferably selected from the group consisting of the above I) titanium chelate compound, II) titanium tetraalkoxide compound, and III. And at least one compound selected from the group consisting of titanocene compounds. More preferably bis(acetonitrile ethyl acetate) titanium diisopropoxide, titanium tetra-n-butoxide, and bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro -3-(1H-pyrrol-1-yl)phenyl)titanium.

The blending amount in the case of the organic titanium compound is preferably 0.05 parts by mass to 10 parts by mass, more preferably 0.1 part by mass to 2 parts by mass, per 100 parts by mass of the (A) resin. When the amount is 0.05 parts by mass or more, it exhibits excellent heat resistance and chemical resistance. On the other hand, when it is 10 parts by mass or less, the storage stability is excellent, which is preferable.

Method for manufacturing hardened embossed pattern

In the embodiment, a method for producing a cured embossed pattern comprising the following steps (1) to (4): (1) applying the negative photosensitive resin composition of the embodiment to a substrate, a step of forming a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer; (3) a step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) a pair The embossed pattern is subjected to a heat treatment to form a hardened embossed pattern.

Each step will be described below.

(1) A step of applying a negative photosensitive resin composition of the embodiment onto a substrate to form a photosensitive resin layer on the substrate

In this step, the negative photosensitive resin composition of the embodiment is applied onto a substrate, and if necessary, dried to form a photosensitive resin layer. As the coating method, a method which has been used for the coating of the photosensitive resin composition, for example, a spin coater, a bar coater, a knife coater, a curtain coater, a screen can be used. A method of coating by a printing machine or the like; a method of spray coating by a spray coater, and the like.

The coating film containing the negative photosensitive resin composition may be dried as needed, and as a drying method, for example, air drying, heating drying by an oven or a hot plate, vacuum drying, or the like may be used. Further, it is preferred that the drying of the coating film is carried out under the conditions of imidization of the (A) polyimine precursor in the negative photosensitive resin composition. Specifically, in the case of air drying or heat drying, drying can be carried out at 20 ° C to 140 ° C for 1 minute to 1 hour. The photosensitive resin layer can be formed on the substrate by the above method.

(2) a step of exposing the photosensitive resin layer

In this step, using an exposure device such as a contact aligner, a mirror projector, a stepper, or the like, via a patterned photomask or a reticle, or directly by an ultraviolet light source or the like (1) The photosensitive resin layer formed in the step is exposed.

Thereafter, it is also possible to carry out post-exposure bake (PEB, Post Exposure Bake) and/or pre-development baking in combination with any combination of temperature and time for the purpose of improving the photosensitivity or the like. The range of the baking conditions is preferably from 40 ° C to 120 ° C, and the time is preferably from 10 seconds to 240 seconds. However, as long as the various properties of the negative photosensitive resin composition are not inhibited, the temperature is not limited to the range. .

(3) a step of developing the exposed photosensitive resin layer to form a relief pattern

In this step, the unexposed portion in the photosensitive resin layer after the exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from a previously known photoresist developing method such as a rotary spray method, a dipping method, an impregnation method with ultrasonic treatment, and the like. use. Also, after development, the embossed pattern can also be adjusted. For the purpose of shape, etc., it is necessary to carry out post-development baking of any combination of temperature and time as needed. As the developer to be used for development, for example, it is preferable that the negative photosensitive resin composition is a good solvent or a combination of the good solvent and the poor solvent. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ are preferred. - Butyrolactone, α-ethinyl-γ-butyrolactone, and the like. Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water. When it is used in the case of mixing a good solvent with a poor solvent, it is preferred to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Further, two or more kinds of solvents may be used in combination, for example, several types may be used.

(4) a step of heat-treating the embossed pattern to form a hardened embossed pattern

In this step, the embossed pattern obtained by the above development is heated to make the photosensitive component thin, and the (A) polyimine precursor is ruthenium imidized, thereby being converted into a polyimine. Hardened embossed pattern. As a method of heat curing, for example, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising oven capable of setting a temperature control program can be selected. Heating can be carried out, for example, at 200 ° C to 400 ° C for 30 minutes to 5 hours. As the ambient gas during heat curing, air may be used, and an inert gas such as nitrogen or argon may be used.

Semiconductor device

In the embodiment, a semiconductor device having a cured embossed pattern obtained by the above-described method for producing a cured embossed pattern is also provided. Therefore, there can be provided a semiconductor device comprising: a substrate as a semiconductor element; and a hardened relief pattern of a polyimide which is formed on the substrate by the above-described method for producing a cured relief pattern. Further, the present invention is also applicable to a method of manufacturing a semiconductor device in which a semiconductor element is used as a substrate and a method of manufacturing the above-described cured embossed pattern is included as a part of the steps. The semiconductor device of the present invention can be manufactured by forming a hardened relief pattern formed by the above-described hardened relief pattern manufacturing method as a surface protective film, an interlayer insulating film, and insulation for rewiring A protective film for a film or a flip chip device, a protective film for a semiconductor device having a bump structure, or the like is combined with a known method for manufacturing a semiconductor device.

Display device

In an embodiment, a display device including a display element and a cured film provided on an upper portion of the display element is provided, and the cured film is the hardened relief pattern. Here, the hardened relief pattern may be laminated directly in contact with the display element or may be laminated via another layer. For example, examples of the cured film include a TFT (Thin Film Transistor) liquid crystal display device and a surface protective film of a color filter element, an insulating film, a planarizing film, and MVA (Multi-Domain Vertical Alignment, A protrusion for a multi-domain vertical alignment type liquid crystal display device and a partition wall for a cathode of an organic EL (Electroluminescence) element.

The negative photosensitive resin composition of the present invention can be used for applications such as interlayer insulation of a multilayer circuit, a surface coating of a soft copper-clad laminate, a solder resist film, and a liquid crystal alignment film, in addition to the semiconductor device described above.

[Examples]

Hereinafter, the present embodiment will be specifically described by way of examples, but the embodiment is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the polymer or the negative photosensitive resin composition were measured and evaluated according to the following methods.

(1) Weight average molecular weight

The weight average molecular weight (Mw) of each polyimine precursor was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement was a serial name of Shodex 805M/806M manufactured by Showa Denko Co., Ltd., and the standard monodisperse polystyrene was selected from Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd., and the solvent was N-methyl-2. Pyrrolidone, the detector was sold under the trade name Shodex RI-930 by Showa Denko.

(2) Evaluation of transparency of photosensitive resin composition

The photosensitive resin composition was spin-coated on a quartz substrate of 3 cm square and dried to form a coating film having a thickness of 10 μm. The film thickness measurement was performed using a Tencor P-15 profiler (manufactured by KLA-Tencor Co., Ltd.). The quartz substrate was measured for absorbance at a wavelength of 365 nm using a UV measuring instrument (manufactured by Shimadzu Corporation, UV-1600PC). When the absorbance at a thickness of 10 μm is 1.5 or less, it is set to be good.

(3) Young's modulus evaluation of hardened embossed pattern (polyimine coating)

On a 6-inch wafer, the photosensitive resin composition was spin-coated so that the film thickness after hardening became about 10 μm, and then dried, and then a temperature-increasing type curing oven (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) was used. The film was heated at 200 ° C for 1 hour in a nitrogen atmosphere and heated at 300 ° C for 2 hours to obtain a hardened embossed pattern (coating film of thermosetting polyimide). The obtained polyimine coating film was cut into a short strip of 3 mm width using a dicing saw (DAD3350 type, manufactured by DISCO Corporation), and then peeled off from the tantalum wafer using 46% hydrofluoric acid to form a polyimide film. . The Young's modulus of the obtained polyimine ribbon was measured in accordance with ASTM D882-09 using a tensile tester (UTM-II-20 model, manufactured by Orientec Co., Ltd.). If the Young's modulus is 5.0 GPa or more, it is set to be good.

(4) Evaluation of the patterning properties of polyimine patterns

The photosensitive resin composition was spin-coated on a 6-inch wafer and dried to form a coating film having a thickness of 10 μm. The coating film was irradiated with an energy of 300 mJ/cm ² by an i-ray stepper NSR1755i7B (manufactured by Nikon Co., Ltd.) using a reticle with a test pattern. Then, using a cyclopentanone, a coating film formed on the wafer was spray-developed by a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg Co., Ltd.), and washed with propylene glycol methyl ether acetate to obtain polylysine. The pattern of the ester.

The patterned wafer was subjected to heat treatment at 200 ° C for 1 hour in a nitrogen atmosphere using a temperature-increasing type curing oven (VF-2000 type, manufactured by Koyo Lindberg Co., Japan), followed by heat treatment at 300 ° C for 2 hours. Thereby, a pattern of 5 μm thick polyimine was obtained on the germanium wafer. Observing the shape of the pattern under an optical microscope for each of the obtained patterns The width of the pattern portion and the resolution are obtained.

Regarding the resolution, a pattern having an opening portion having a plurality of different areas by exposure through a reticle with a test pattern is formed by the above method, and the area of the pattern opening portion obtained is the corresponding pattern mask opening area. When it is 1/2 or more, it is regarded as a resolution, and the length of the opening side of the mask corresponding to the smallest area in the opening part of the image to be resolved is set as the resolution. When the resolution is 10 μm or less, that is, the aspect ratio (film thickness/resolution after coating and drying) is 1 or more, it is good.

(5) Accuracy evaluation of the pattern of polyimine

The accuracy of the pattern of the polyimine formed in the above (4) was evaluated based on the following criteria.

"Good": a pattern in which the pattern profile has no taper, no base etching, swelling, or bridging, and the aspect ratio is 1 or more, and the pattern shape does not change during heat curing.

"Poor": A pattern that does not satisfy at least one of the above-mentioned "good" plural conditions.

<Production Example 1> (Synthesis of Polymer A as (A) Polyimine Precursor)

155.1 g (0.5 mol) of 4,4'-oxydiphthalic anhydride (ODPA, 4, 4-oxydiphthalic anhydride) was placed in a 2 liter separable flask and placed in methacrylic acid 2- Hydroxylethyl ester (HEMA, 2-hydroxyethyl methacrylate) 65.1 g (0.5 mol), triethylene glycol monomethyl ether 82.2 g (0.5 mol) and γ-butyrolactone 400 ml, and stirred at room temperature while stirring 81.5 g of pyridine was added to obtain a reaction mixture. After the end of the exotherm caused by the reaction, it was allowed to cool to room temperature and allowed to stand for 16 hours.

Next, 206.3 g of dicyclohexylcarbodiimide (DCC, dicyclohexylcarbodiimide) was dissolved in a solution of 180 ml of γ-butyrolactone while stirring under ice cooling, and it was added to the reaction mixture over 40 minutes. Then, 50.2 g of p-phenylenediamine (PPD) was suspended in 350 ml of γ-butyrolactone while stirring, and the mixture was added for 60 minutes. Further, after stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred. The mixture was mixed for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction liquid was added to 3 liters of ethanol to produce a precipitate containing a crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was separated by filtration, followed by vacuum drying to obtain a powdery polymer (Polymer A). The molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 30,000.

<Production Example 2> (Synthesis of Polymer B as (A) Polyimine Precursor)

22.6 g (0.25 mol) of 2-hydroxyethyl methacrylate (HEMA) and 123.3 g (0.75 mol) of triethylene glycol monomethyl ether were used instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 of Production Example 1, respectively. Polymer B was obtained in the same manner as in the method described in Production Example 1 except that g (0.5 mol) and 82.3 g (0.5 mol) of triethylene glycol monomethyl ether were used. The molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 32,000.

<Production Example 3> (Synthesis of Polymer C as (A) Polyimine Precursor)

27.7 g (0.75 mol) of 2-hydroxyethyl methacrylate (HEMA) and 41.1 g (0.25 mol) of triethylene glycol monomethyl ether were used instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 of Production Example 1, respectively. Polymer C was obtained in the same manner as in the method described in Production Example 1 except that g (0.5 mol) and 82.3 g (0.5 mol) of triethylene glycol monomethyl ether were used. The molecular weight of the polymer C was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 32,000.

<Production Example 4> (Synthesis of Polymer D as (A) Polyimine Precursor)

Using 2-hydroxyethyl methacrylate (HEMA) 130.2 g (1.0 mol) instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 g (0.5 mol) and triethylene glycol monomethyl ether 82.2 g of Production Example 1. (0.5 mol), otherwise, in the same manner as the method described in the above Production Example 1. The reaction was carried out to obtain a polymer D. The molecular weight of the polymer D was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 29,000.

<Production Example 5> (Synthesis of Polymer E as (A) Polyimine Precursor)

65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate (HEMA) and 23.0 g (0.5 mol) of ethanol were used instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 g (0.5 mol) of Production Example 1. Polymer E was obtained in the same manner as in the above-described Production Example 1 except that 82.2 g (0.5 mol) of triethylene glycol monomethyl ether was used. The molecular weight of the polymer E was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 27,000.

<Production Example 6> (Synthesis of Polymer F as (A) Polyimine Precursor)

25.1 g (0.5 mol) of 2-hydroxyethyl methacrylate (HEMA) and 44.0 g (0.5 mol) of neopentyl alcohol were used instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 g (0.5 mol) of Production Example 1. The polymer F was obtained in the same manner as in the method described in the above Production Example 1, except that 82.2 g (0.5 mol) of triethylene glycol monomethyl ether was used. The molecular weight of the polymer F was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 28,000.

<Production Example 7> (Synthesis of Polymer G as (A) Polyimine Precursor)

Instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 g (0.5), 2-hydroxyethyl methacrylate (HEMA) 65.1 g (0.5 mol) and 1-octanol 65.0 g (0.5 mol) were used, respectively. Polymer G was obtained in the same manner as in the method described in the above Production Example 1, except that 82.2 g (0.5 mol) of triethylene glycol monomethyl ether was used. The molecular weight of the polymer G was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 33,000.

<Production Example 8> (Synthesis of Polymer H as (A) Polyimine Precursor)

Instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 of Production Example 1, 65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate (HEMA) and 54.0 g (0.5 mol) of benzyl alcohol were used, respectively. Polymer H was obtained in the same manner as in the above-described Production Example 1 except that g (0.5 mol) and triethylene glycol monomethyl ether (82.2 g (0.5 mol)) were used. The molecular weight of the polymer H was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 35,000.

<Production Example 9> (Synthesis of Polymer I as (A) Polyimine Precursor)

Instead of the 2-hydroxyethyl methacrylate (HEMA) 65.1 of Production Example 1, 104.1 g (0.8 mol) of 2-hydroxyethyl methacrylate (HEMA) and 32.8 g (0.2 mol) of triethylene glycol monomethyl ether were used, respectively. Polymer I was obtained in the same manner as in the above-described Production Example 1 except that g (0.5 mol) and triethylene glycol monomethyl ether (82.2 g (0.5 mol)) were used. The molecular weight of the polymer I was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 32,000.

<Production Example 10> (Synthesis of Polymer J as (A) Polyimine Precursor)

26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (HEMA) and 131.4 g (0.8 mol) of triethylene glycol monomethyl ether were used instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 of Production Example 1, respectively. Polymer J was obtained in the same manner as in the above-described Production Example 1 except that g (0.5 mol) and 82.3 g (0.5 mol) of triethylene glycol monomethyl ether were used. The molecular weight of the polymer J was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 33,000.

<Production Example 11> (Synthesis of Polymer K as (A) Polyimine Precursor)

23.0 g (0.9 mol) of 2-hydroxyethyl methacrylate (HEMA) and 147.8 g (0.1 mol) of triethylene glycol monomethyl ether were used instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 of Production Example 1, respectively. Polymer K was obtained in the same manner as in the method described in Production Example 1 except that g (0.5 mol) and 82.3 g (0.5 mol) of triethylene glycol monomethyl ether were used. The molecular weight of the polymer K was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 30,000.

<Production Example 12> (Synthesis of Polymer L as (A) Polyimine Precursor)

Instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 of Production Example 1, 117.1 g (0.1 mol) of 2-hydroxyethyl methacrylate (HEMA) and 16.4 g (0.9 mol) of triethylene glycol monomethyl ether, respectively. Polymer L was obtained in the same manner as in the above-described Production Example 1 except that g (0.5 mol) and 82.3 g (0.5 mol) of triethylene glycol monomethyl ether were used. The molecular weight of the polymer L was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 33,000.

<Production Example 13> (Synthesis of Polymer M as (A) Polyimine Precursor)

Instead of 2-hydroxyethyl methacrylate (HEMA) 65.1 g (0.5), 2-hydroxyethyl methacrylate (HEMA) 65.1 g (0.5 mol) and 1-butanol 37.1 g (0.5 mol) were used, respectively. The polymer M was obtained in the same manner as in the method described in the above Production Example 1, except that 82.2 g (0.5 mol) of triethylene glycol monomethyl ether was used. The molecular weight of the polymer M was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 32,000.

<Example 1>

Using the polymer A, a negative photosensitive resin composition was prepared by the following method, and evaluation of the prepared composition was performed. 100 g of polymer A as a polyimide precursor ((A) polyimine precursor) and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime ((B) photopolymerization initiator) 4 g, benzotriazole 0.15 g, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1 , 3,5-three -2,4,6-(1H,3H,5H)-trione 1.5g, N-phenyldiethanolamine 10g, methoxymethylated urea resin (MX-290) 4g, tetraethylene glycol dimethyl 8 g of acrylate, 1.5 g of N-[3-(triethoxydecyl)propyl]phthalic acid, and 0.05 g of 2-nitroso-1-naphthol are dissolved together in the presence of N- A mixed solvent of 80 g of methyl-2-pyrrolidone (hereinafter referred to as NMP (N-methylpyrrolidone)) and 20 g of ethyl lactate. Further, a small amount of the mixed solvent was added, whereby the viscosity of the obtained solution was adjusted to about 35 poise to prepare a negative photosensitive resin composition.

The composition was evaluated according to the above method, and the absorbance was 1.36, Young's modulus. The number is 5.6 GPa and is good, the resolution is 8 μm and the pattern accuracy is also good.

<Example 2>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer B, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.29, the Young's modulus was 5.5 GPa, and the resolution was 8 μm, and the pattern accuracy was also good.

<Example 3>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer C, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.40, the Young's modulus was 5.4 GPa, and the resolution was 8 μm, and the pattern accuracy was also good.

<Example 4>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer F, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.48, the Young's modulus was 5.6 GPa, and the resolution was 8 μm, and the pattern accuracy was also good.

<Example 5>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer G, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.50, the Young's modulus was 6.0 GPa, and the resolution was 8 μm, and the pattern accuracy was also good.

<Example 6>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer H, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.48, the Young's modulus was 5.6 GPa, and the resolution was 8 μm, and the pattern accuracy was also good.

<Example 7>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer I, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.50, the Young's modulus was 5.0 GPa, and the resolution was 8 μm, and the pattern accuracy was also good.

<Example 8>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer J, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.27, the Young's modulus was 5.6 GPa, and the resolution was 8 μm, and the pattern accuracy was also good.

<Comparative Example 1>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer D, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.68, the Young's modulus was 4.8 GPa, and the pattern accuracy was poor, and the criteria were not satisfied.

<Comparative Example 2>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer E, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.57, the Young's modulus was 4.9 GPa, and the pattern accuracy was poor, and the criteria were not satisfied.

<Comparative Example 3>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer K, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.58, the Young's modulus was 4.9 GPa, and the pattern accuracy was poor, and none of them satisfied the standard.

<Comparative Example 4>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer L, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.25, the Young's modulus was 5.6 GPa, and the pattern accuracy was poor.

<Comparative Example 5>

The negative photosensitive resin composition similar to that of Example 1 was prepared except that the (A) polyimine precursor of the present invention in Example 1 was changed to the polymer M, and the same procedure as in Example 1 was carried out. Evaluation. As a result, the absorbance was 1.63, the Young's modulus was 4.9 GPa, and the pattern accuracy was poor, and none of them satisfied the standard.

[Industrial availability]

The negative photosensitive resin composition of the present invention can be suitably used, for example, in the field of photosensitive materials which can be used for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (9)

A negative photosensitive resin composition comprising: (A) having the following general formula (1): In the formula, X ₁ is a tetravalent organic group having a carbon number of 6 to 40, Y ₁ is a divalent organic group having a carbon number of 6 to 40, n is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom. Or the following general formula (2) or (3): (wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a carbon number of 1 to 3, and m is an integer of 2 to 10) - R ₆ (3) (wherein R ₆ a one-valent organic group represented by a valent group selected from an aliphatic group having 5 to 30 carbon atoms which may have a hetero atom, and a monovalent organic group represented by the above formula (2) and the above formula ( 3) one represented by the sum of the monovalent organic group with respect to the ratio of the entire R ₁ and R ₂ of less than 80 mole%, and the general formula (3) represents a divalent organic group with respect to one of R ₁ and R ₂ The polyimine precursor of the structure represented by the ratio of 20 mol% to 80 mol% is 100 parts by mass; and (B) the photopolymerization initiator: 0.1 part by mass to 20 parts by mass. The term negative photosensitive resin composition of 1 above wherein R ₆ is a glycol having a structure of carbon aliphatic group having 5 to 30 of the request. The negative photosensitive resin composition of claim 1, wherein in the above formula (1), the monovalent organic group represented by the above formula (2) and the one-valent organic group represented by the above formula (3) The ratio of the total of R ₁ and R ₂ is 90 mol% or more, and the ratio of the monovalent organic group represented by the above formula (3) to all of R ₁ and R ₂ is 25 mol%. ~75 mol%. The negative photosensitive resin composition of claim 2, wherein in the above formula (1), the monovalent organic group represented by the above formula (2) and the one-valent organic group represented by the above formula (3) The ratio of the total of R ₁ and R ₂ is 90 mol% or more, and the ratio of the monovalent organic group represented by the above formula (3) to all of R ₁ and R ₂ is 25 mol%. ~75 mol%. The negative photosensitive resin composition according to any one of claims 1 to 4, which further comprises (C) a thermal crosslinking agent: 0.1 parts by mass based on 100 parts by mass of the above (A) polyimine precursor. ~30 parts by mass. A method for producing a hardened embossed pattern, comprising the steps of: (1) applying a negative photosensitive resin composition according to any one of claims 1 to 5 to a substrate, and forming a photosensitive property on the substrate a step of exposing the photosensitive resin layer; (2) a step of exposing the photosensitive resin layer; (3) a step of developing the exposed photosensitive resin layer to form a relief pattern; and (4) performing the embossed pattern The step of heat treatment to form a hardened relief pattern. A hardened relief pattern produced by the method of claim 6. A semiconductor device including a semiconductor element and a semiconductor element A cured film of the upper portion of the member, and the cured film is a hardened relief pattern as claimed in claim 7. A display device comprising a display body element and a cured film provided on an upper portion of the display element, and the cured film is a hardened relief pattern as claimed in claim 7.