JP2012185211A - Negative photosensitive resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem that, although a negative photosensitive resin composition contains generally a compound having two or more reactive groups as reaction diluents, and has more excellent photosensitivity the more polyfunctional it is and the more additives it has, a physical property of a cured product (film) obtained by curing the composition significantly depends on the characteristic of the compound leading to a limited flexibility in giving characteristics necessary for the cured product (film).SOLUTION: There is provided the negative photosensitive resin composition that uses, as the reaction diluent, only a compound having a weight average molecular weight of less than 1000 and one unsaturated double bond in one molecule.

Description

  The present invention relates to a negative photosensitive resin composition characterized in that only a compound having a weight average molecular weight of less than 1000 and having one unsaturated double bond per molecule is used as a reactive diluent. In particular, the present invention relates to a negative photosensitive resin composition characterized in that only a monofunctional (meth) acrylate compound having a weight average molecular weight of 800 or less is used as a reactive diluent. The negative photosensitive resin composition is particularly suitable for molding materials, film-forming materials, electrical insulating materials, and the like. That is, it can be suitably used for solder resists, interlayer insulating materials, other resist materials that can be alkali-developed, lenses, displays, optical fibers, optical waveguides, holograms, etc. in the production of printed (wiring circuit) substrates.

  Printed (wiring circuit) boards are required to have high accuracy and high density for the purpose of reducing the size and weight of portable devices and improving the communication speed. The demand for resists is increasing. For example, heat resistance to heat generation of elements during board production and operation using solder etc., insulation reliability by maintaining high insulation for a long time, resistance to chemical treatment such as plating, etc., higher performance than before, There is a demand for a film-forming material having tougher cured product performance.

  Photosensitive resin compositions used for these applications are generally reactive diluents (hereinafter sometimes referred to as reactive monomer components) in consideration of photocurability and film properties after film formation. As a compound having a weight average molecular weight of 1000 or less and having 2 or more unsaturated double bonds in one molecule (Patent Document 1).

JP 2002-72471 A

  A photosensitive resin composition used for a negative resist that obtains a pattern by curing the exposed area and lowering the solubility in a developing solution generally includes a photoreaction initiator and a unsaturated group as a reactive group. A reactive monomer component having a heavy bond or an epoxy group, and a binder polymer component are included. These reactive monomer components generally have a higher sensitivity to light as the polyfunctionality and the addition amount are larger, but the cured product (film) obtained by curing the composition has a higher sensitivity. The physical properties greatly depend on the characteristics of the reactive monomer component, and the degree of freedom for imparting the necessary characteristics to the cured product (film) is limited.

  In view of the above-mentioned problems, the present inventors have made the reactive diluent in the negative photosensitive resin composition only a compound having one unsaturated double bond in one molecule, which is manufactured through a lithography process. The present invention was completed by finding that the cured film obtained by film formation does not impair the excellent film properties of the binder polymer.

  That is, the present invention relates to a negative photosensitive resin composition characterized by using only a compound having a weight average molecular weight of less than 1000 and having one unsaturated double bond per molecule as a reactive diluent.

  Furthermore, the present invention relates to a negative photosensitive resin composition characterized by using only a monofunctional (meth) acrylate compound having a weight average molecular weight of 800 or less as a reactive diluent.

  Furthermore, it is related with the said negative photosensitive resin composition which also contains the binder polymer (A) whose weight average molecular weight is 1000-150,000, and a photoinitiator.

  Furthermore, it is related with the said negative photosensitive resin composition whose binder polymer (A) is a compound which has a polyamic-acid frame | skeleton in the frame | skeleton.

Furthermore, it is related with the said negative photosensitive resin composition which is a molding material.
Furthermore, it is related with the said negative photosensitive resin composition which is a film forming material.
Furthermore, it is related with the said negative photosensitive resin composition which is a composition for electrical insulation materials.

Furthermore, it is related with the said negative photosensitive resin composition which is a photosensitive soldering resist composition.
Furthermore, it is related with the hardened | cured material obtained by irradiating an active energy ray to the said negative photosensitive resin composition.
Furthermore, it is related with the multilayer material which has the layer of the hardened | cured material of the said negative photosensitive resin composition.

  Further, after coating the negative photosensitive resin composition on the substrate, if necessary, the solvent is dried, and then cured by irradiating with active energy rays, and if necessary, after development with an alkaline aqueous solution, heated to 100 ° C. or higher. It is related with the manufacturing method of the cured film of the negative photosensitive resin composition characterized by obtaining a cured film.

  The negative photosensitive resin composition of the present invention can be subjected to photo-patterning, and the cured product has both tough cured product performance and flexibility and flame retardancy required for a flexible substrate. Therefore, it is suitable as a film-forming material, a resist material that can be developed with an alkali, such as a solder resist used in the production of printed (wiring circuit) substrates, an interlayer insulating material, an adhesive, and a molding material. Further, since the composition has excellent insulation reliability, it can be suitably used for a material intended for electrical insulation. In particular, when a resin having a polyamic acid skeleton is used as a binder polymer, the resulting cured film has characteristics of having excellent flexibility and flame retardancy.

Hereinafter, the present invention will be described in detail.
The negative photosensitive resin composition of the present invention is characterized in that only a compound having a weight average molecular weight of less than 1000 and having one unsaturated double bond per molecule is used as a reactive diluent.

In the present invention, the reactive diluent is a reactive group that is included in the negative photosensitive resin composition and forms a crosslinked structure by active energy rays, for example, a weight average molecular weight of 1000 or less having an unsaturated double bond, an epoxy group, or the like. The so-called reactive monomer.
The reactive diluent contained in the negative photosensitive resin composition of the present invention is not particularly limited as a compound having a weight average molecular weight of less than 1000 and having one unsaturated double bond in one molecule, but the weight average A (meth) acrylate compound (monofunctional (meth) acrylate compound) having a molecular weight of 800 or less and one (meth) acryloyl group is preferred.

  Examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenylethyl (meth) ) Acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl glycidyl ether (meth) acrylate and phenylphenol glycidyl ether An epoxy (meth) acrylate compound such as (meth) acrylate or an ethylene oxide adduct thereof can be used.

The negative photosensitive resin composition of the present invention may contain a binder polymer (A) having a weight average molecular weight of 1000 to 150,000 and a photopolymerization initiator.
In the present invention, the binder polymer is used for improving the film forming property and compatibility of the negative photosensitive resin composition, and for imparting properties such as developability, curability, and cured film physical properties according to the purpose of the composition. The polymer used. Examples of the binder polymer (A) include, but are not particularly limited to, addition polymerization polymers and condensation polymerization polymers. Especially, what does not decompose | disassemble in the heating process at the time of film forming is preferable.

Examples of the addition polymerization polymer include a polymer obtained by polymerizing a monomer having an unsaturated double bond represented by one (meth) acrylate group in a known general molecule.
Examples of the condensation polymerization polymer include polyester, polyamide, polyimide, phenol resin, urea resin, melamine resin, and the like.

  In order to have physical properties such as flame retardancy, flexibility and toughness when cured while being alkali developable, which is a characteristic of the performance of the negative photosensitive resin composition of the present invention, a condensation polymerization polymer is used as the binder polymer (A). A compound having a polyamic acid skeleton in a certain skeleton is particularly preferable.

  The compound having a polyamic acid skeleton can be obtained by reacting a compound (a) having two or more amino groups in one molecule with a compound (b) having two or more acid anhydride structures in one molecule. Compounds.

  The compound (a) is appropriately selected according to the purpose of use of the negative photosensitive resin composition of the present invention, and two or more kinds of compounds can be used simultaneously. Examples of the compound (a) include monocyclic aromatic diamines such as phenylenediamine, dimethylphenylenediamine, and naphthalenediamine, C3-C20 alkyl diamines, C3-C20 polyether diamines, C3-C20 polycarbonate diamines, and the like. Chain diamines, polybiphenylenediamine, bis (hydroxyphenyl) diamine, dianisidine, bis (aminophenyl) ether, bis (methylaminophenyl) ether, bis (hydroxyaminophenyl) ether, bis (carboxyaminophenyl) ether, Bicyclic aroma such as bis (aminophenyl) sulfone, bis (aminophenyl) methane, bis (aminophenyl) propane, bis (aminophenyl) sulfide, bis (aminophenyl) hexafluoropropane Polycyclic aromatics such as diamines, bis (hydroxyaminophenyl) benzene, bis (hydroxyaminophenoxy) benzene, bisaminophenylfluorene, bis [(aminophenoxy) phenyl] propane, and bis [(aminophenoxy) phenyl] sulfone Examples include diamines or derivatives thereof.

  The compound (b) is appropriately selected according to the purpose of use of the negative photosensitive resin composition of the present invention, and two or more kinds of compounds can be used simultaneously. Examples of the compound (b) include monocyclic aromatic tetrabasic acid dianhydrides such as pyromellitic acid anhydride, biphenyltetracarboxylic acid anhydride, naphthyltetracarboxylic acid anhydride, and benzophenonetetracarboxylic acid dianhydride. , Diphenyl ether tetracarboxylic acid anhydride, diphenylsulfone tetracarboxylic acid anhydride, ethylene glycol bistrimellitic acid anhydride, diol bistrimellitic acid anhydrides (for example, hexanediol bistrimellitic acid anhydride, etc.) Examples thereof include polycyclic aromatic tetrabasic dianhydrides such as tetrabasic dianhydrides, fluorene anhydride of bisphthalic acid, and biphenol bistrimellitic anhydride, butanetetracarboxylic anhydride, and the like. Furthermore, the alicyclic acid anhydride by the nuclear hydrogenation reaction of the said aromatic anhydride can also be used conveniently.

  The reaction for obtaining a resin having a polyamic acid skeleton by reacting the compound (a) with the compound (b) may be carried out using a known general method and reaction conditions such as mixing and heating. In this reaction, a solvent in which the resulting polyamic acid-containing resin dissolves may be used. Since resins having a polyamic acid skeleton generally have poor solubility in low-polar solvents, examples of the solvent include amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, ester solvents such as butyrolactone, butyl So-called highly polar solvents such as glycol solvents such as diglycol are preferred.

  The photopolymerization initiator that may be contained in the negative photosensitive resin composition of the present invention is added for the purpose of generating radicals upon irradiation with active energy rays and inducing a crosslinking reaction. Thereby, for example, the active energy ray irradiated part and the non-irradiated part of the negative photosensitive resin composition of the present invention are different in solubility in a solvent or an alkaline aqueous solution, and can be patterned.

  Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy. 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-propan-1-one; anthraquino such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4, Benzophenones such as 4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, ethanone, 1- [9 Known general radical-type photoinitiators such as oximes such as -ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] and 1- (O-acetyloxime).

  The negative photosensitive resin composition of the present invention contains about 2 to 20% by weight of the reactive diluent, about 10 to 70% by weight of the binder polymer (A), and about 2 to 10% by weight of the photopolymerization initiator. Is preferred.

  The negative photosensitive resin composition of the present invention is easily cured by active energy rays. Examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser rays, and particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  The invention of the present application includes a cured product obtained by irradiating the negative photosensitive resin composition with active energy rays, and also includes a multilayer material having a layer of the cured product.

  The molding material in which the photosensitive resin composition of the present invention is used is one in which an uncured composition is put into a mold or pressed to form an object, which is cured by active energy rays and molded. For example, a sheet formed into a flat shape; a sealing material for protecting an element; a so-called nanoimprint material that performs fine forming by pressing a “mold” that has been finely processed into an uncured composition; Examples thereof include a sealing material for the purpose of electrical insulation that requires high flammability and high reliability and avoids halogen compounds.

  The film forming material in which the photosensitive resin composition of the present invention is used is used for the purpose of coating the substrate surface. For example, ink materials such as gravure ink, flexo ink, silk screen ink, offset ink; coating materials such as hard coat, top coat, overprint varnish, clear coat; various adhesives and adhesives for laminating and optical disc Adhesive materials such as: Resist materials such as solder resist, etching resist, and micromachine resist. Furthermore, so-called dry film, in which a film-forming material is temporarily applied to a peelable substrate to form a film and then bonded to a target substrate to form a film, corresponds to the film-forming material.

  In general, a composition used for an electrical insulating material is formed by forming a film layer of the composition on a substrate and applying a large voltage to an electrical resistance between two locations targeted by an electronic circuit or its components. Also make sure that no current flows. The negative photosensitive resin composition of the present invention includes an overcoat material for a flexible wiring board, an interlayer insulating film for a multilayer substrate, a molding material for an insulating film or a passivation film for a solid element in the semiconductor industry, a semiconductor integrated circuit, and a multilayer printed wiring. Used for interlayer insulation materials such as plates, solder resists for electrical insulation used for substrate protection, and the like. Among them, it is particularly suitable for a flexible wiring board that also requires high flame retardancy. That is, high flame retardancy and long-term stability of insulation performance can be exhibited.

  In general, a substrate has a portion that requires insulation and a portion that requires conduction. Even if this is patterned by a printing method, fine patterning is difficult, and the printing method is not suitable for the production of a substrate having a high wiring density. On the other hand, the negative photosensitive resin composition of the present invention is used as an insulating material to form a coating layer on the substrate, and then irradiated partially with active energy rays such as ultraviolet rays, By drawing using the difference in physical properties, fine patterning becomes possible, and a high-density substrate can be created.

Patterning using the negative photosensitive resin composition of the present invention can be performed, for example, as follows, and a method for producing such a cured film is also included in the present invention. First, the negative photosensitive resin composition of the present invention with a film thickness of 0.5 to 200 μm by a screen printing method, spray method, roll coating method, electrostatic coating method, curtain coating method, spin coating method or the like on a substrate. The coating is formed by drying the solvent at a temperature of preferably 50 to 110 ° C, particularly preferably 60 to 100 ° C. Thereafter, the coating film is directly or indirectly irradiated with an active energy ray such as ultraviolet rays with an intensity of about 10 to 2000 mJ / cm ² through a photomask having an exposure pattern, and the irradiated portion is cured, preferably the development described later. Using the liquid, a desired pattern is obtained, for example, by spraying, vibration dipping, paddle, brushing or the like.

  Examples of the alkaline aqueous solution used as the developer include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, and potassium phosphate, Organic alkaline aqueous solutions such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine are listed.

  In addition, the negative photosensitive resin composition of the present invention can also be used as an optical waveguide for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the examples, unless otherwise specified, “parts” represents parts by weight and “%” represents% by weight. For measuring the viscosity at 25 ° C., an E-type viscometer was used.

The GPC measurement conditions are as follows.
Model: TOSOH HLC-8220GPC
Column: Super HZM-N
Eluent: NMP (N-methylpyrrolidone); 0.35 ml / min 40 ° C.
Detector: Differential refractometer Molecular weight standard: Polystyrene

Synthesis Example 1: Synthesis of polyamic acid (A-1) 4,4′-oxydianiline as a compound having two or more amino groups in one molecule in a 300 ml reactor equipped with a stirrer, a thermometer and a condenser 18.00 g (90.00 mmol) and 74.70 g of N-methylpyrrolidone as a solvent were added and dissolved by stirring at 80 ° C. for 1 hour. Thereafter, 19.63 g (90.00 mmol) of pyromellitic acid anhydride was charged as a compound having two or more acid anhydride structures in one molecule, and further reacted at 80 ° C. for 5 hours to obtain a polyamic acid (A-1 ) Was obtained. The viscosity (25 ° C.) was 63 Pa · s, and the weight average molecular weight of the polyamic acid (A-1) was 70000.

Synthesis Example 2: Synthesis of polyamic acid (A-2) 1,3-bis (3-as a compound having two or more amino groups in one molecule was added to a 300 ml reactor equipped with a stirrer, a thermometer and a condenser. Aminophenoxy) benzene (12.00 g, 41.05 mmol) and 47.80 g of N-methylpyrrolidone as a solvent were added and stirred at 80 ° C. for 1 hour to dissolve. Thereafter, 12.08 g (41.05 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride was charged as a compound having two or more acid anhydride structures in one molecule, and further heated to 80 ° C. For 5 hours to obtain a resin solution containing 33.5% of polyamic acid (A-2). The viscosity (25 ° C.) was 30 Pa · s, and the polyamic acid (A-2) had a weight average molecular weight of 65,000.

Synthesis Example 3: Synthesis of energy ray-curable polyamic acid (A-3) A-3-1: Synthesis of terminal acid anhydride polyamic acid In a 300 ml reactor equipped with a stirrer, a thermometer and a condenser, 2 in one molecule Add 12.00 g (60.5 mmol) of 4,4′-bis (aminophenyl) methane as a compound having at least one amino group and 95.97 g of N-methylpyrrolidone as a solvent, and stir at 80 ° C. for 1 hour. Dissolved. Thereafter, 19.99 g (100.9 mmol) of butanetetracarboxylic anhydride was added as a compound having two or more acid anhydride structures in one molecule, and further reacted at 80 ° C. for 5 hours to react with polyamic acid (A- A resin solution containing 25% of 3-1) was obtained. The viscosity (25 ° C.) was 0.3 Pa · s, and the polyamic acid (A-3-1) had a weight average molecular weight of 3,500.

A-3-2: Synthesis of terminal hydroxyl energy ray-curable resin In a 300 ml reactor equipped with a stirrer, thermometer and condenser, RE310S (bifunctional bisphenol A type epoxy resin, epoxy equivalent 184 g / eq.) 18.40 g Then, 7.21 g of acrylic acid, 0.03 g of 2,6-di-t-butyl-p-cresol and 0.03 g of triphenylphosphine were charged and reacted at 100 ° C. for 20 hours to obtain an epoxy carboxylate compound (theoretical). Molecular weight 512.1) was obtained. Next, 32.94 g of γ-butyrolactone and 7.27 g of pyromellitic anhydride are added to this reaction solution as a reaction solvent and reacted at 100 ° C. for 12 hours to obtain a terminal hydroxyl energy beam curable resin (A-3-2). A resin solution containing 50% of was obtained. The solid content acid value of the resin thus obtained (based on JIS K5601-2-1: 1999) was 114 mgKOH / g.

A-3: Synthesis of energy ray curable polyamic acid (A-3) 65.88 g of a terminal hydroxyl energy ray curable resin (A-3-2) solution was added to a 300 ml reactor equipped with a stirrer, a thermometer and a condenser. Then, 127.96 g of a polyamic acid (A-3-1) solution was charged and reacted at 80 ° C. for 22 hours. In this way, a resin solution containing 33.5% of energy beam curable polyamic acid (A-3) was obtained.

Examples 1-3, Comparative Examples 1-3
The amic acid obtained in Synthesis Examples 1 to 3 and other components were mixed in the composition shown in Table 1 below to obtain resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3. Resins A-1 and A-3 are not compatible with TMPTA.

[Table 1]

OXE02: Ethanone manufactured by BASF, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)
R-128H: Nippon Kayaku Phenylglycidyl ether acrylate PEG400DA: Nippon Kayaku polyethylene glycol diacrylate TMPTA: Nippon Kayaku trimethylolpropane triacrylate SPH-100: Otsuka Chemical phosphazene flame retardant

Evaluation of Cured Material of Negative Photosensitive Resin Composition (1) Patterning Evaluation Each photosensitive resin composition is formed with a comb pattern of L / S = 50 μm / 50 μm so as to have a thickness of 25 μm by screen printing. The coating was applied onto the Espanex M series (manufactured by Nippon Steel Chemical Co., Ltd .: base imide thickness: 25 μm, Cu thickness: 18 μm), and the coating film was dried in a hot air dryer at 80 ° C. for 60 minutes. Next, a mask film on which a hole pattern of 100 μm was drawn was brought into close contact, and irradiated with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multilight). Next, spray development (spray pressure: 0.2 MPa) was performed for 120 seconds using a 1% sodium carbonate aqueous solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed for 60 minutes in a hot air dryer at 200 ° C., and the pattern formed on the copper wiring and the imide was observed with a metal microscope. The results are shown in Table 2.
○ The hole pattern of 100 μm is clearly resolved.
Δ: A hole pattern is obtained, but the pattern edge portion is jagged.
× ... 100 μm hole pattern does not resolve.

(2) HAST evaluation (migration evaluation)
Espanex M series (manufactured by Nippon Steel Chemical Co., Ltd .: base imide thickness: 25 μm) each photosensitive resin composition was formed with a comb pattern of L / S = 50 μm / 50 μm so as to have a thickness of 25 μm by screen printing. (Cu thickness: 18 μm), and the coating film was dried in a hot air dryer at 80 ° C. for 60 minutes. Next, the entire surface of the coating film was cured by irradiating with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multi-light). Next, spray development (spray pressure: 0.2 MPa) was performed for 120 seconds using a 1% sodium carbonate aqueous solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed for 60 minutes in a hot air dryer at 200 ° C. to obtain a test substrate for HAST evaluation. The electrode part of the obtained substrate is connected by soldering, placed in an environment of 120 ° C./85% RH (relative humidity), a voltage of 100 V is applied, and the time until the resistance value becomes 10 ⁷ Ω or less is set. It was measured. The results are shown in Table 2.
○ ... 250 hours or more △ ... 30-250 hours × ... 30 hours or less

(3) Fracture evaluation Espanex M series (Nippon Steel) in which each photosensitive resin composition was formed with a comb pattern of L / S = 50 μm / 50 μm so as to have a thickness of 25 μm by screen printing. Chemical: Base imide thickness 25 μm Cu thickness 18 μm), and the coating film was dried with a hot air drier at 80 ° C. for 60 minutes. Next, the entire surface of the coating film was cured by irradiating with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multi-light). Next, spray development (spray pressure: 0.2 MPa) was performed for 120 seconds using a 1% sodium carbonate aqueous solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed in a hot air dryer at 200 ° C. for 60 minutes to obtain a substrate for a folding test. The substrate is bent 180 ° with the resist surface facing outward, and a 200 g weight is placed on the bent portion for 5 seconds. Next, fold it to the opposite side and put a 200g weight in the same way. This was one cycle, and the number of cycles at which the abnormality occurred on the substrate was visually confirmed. Less than 1 cycle was set to 0 times. The results are shown in Table 2.

(4) Flame Retardancy Evaluation Each photosensitive resin composition was applied onto Kapton (manufactured by Toray DuPont: imide thickness 25 μm) to a thickness of 25 μm by screen printing, and the coating film was heated with hot air at 80 ° C. It was dried for 60 minutes with a dryer. Subsequently, the whole surface of the coating film was cured by irradiating with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multi-light). Next, spray development (spray pressure: 0.2 MPa) was performed for 120 seconds using a 1% sodium carbonate aqueous solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed for 60 minutes in a hot air dryer at 200 ° C. to prepare a sample for a flame retardant test.
The sample prepared as described above was subjected to a test based on ASTM D4804. The results are shown in Table 2.
○ VTM-0
△ VTM-1
× VTM-2 or lower

[Table 2]

  As is clear from the above results, a negative photosensitive resin composition using only a compound having a weight average molecular weight of less than 1000 and having one unsaturated double bond per molecule as the reactive diluent of Examples 1 to 3. Is a photosensitive resin composition that is excellent in each performance as compared with the photosensitive resin compositions of Comparative Examples 1 to 3 using other compounds as reactive diluents and does not impair the properties of the binder polymer.

Claims (11)

A negative photosensitive resin composition characterized by using only a compound having a weight average molecular weight of less than 1000 and having one unsaturated double bond per molecule as a reactive diluent. The negative photosensitive resin composition according to claim 1, wherein only a monofunctional (meth) acrylate compound having a weight average molecular weight of 800 or less is used as the reactive diluent. Furthermore, the negative photosensitive resin composition of Claim 1 or 2 containing the binder polymer (A) with a weight average molecular weight of 1000-150,000, and a photoinitiator. The negative photosensitive resin composition according to claim 3, wherein the binder polymer (A) is a compound having a polyamic acid skeleton in its skeleton. It is a molding material, The negative photosensitive resin composition as described in any one of Claims 1-4. The negative photosensitive resin composition according to any one of claims 1 to 4, which is a film forming material. The negative photosensitive resin composition according to any one of claims 1 to 4, which is a material for electrical insulation. It is a photosensitive solder resist composition, The negative photosensitive resin composition as described in any one of Claims 1-4. Hardened | cured material obtained by irradiating an active energy ray to the negative photosensitive resin composition as described in any one of Claims 1-8. A multilayer material having a layer of a cured product of the negative photosensitive resin composition according to claim 9. After applying the negative photosensitive resin composition according to any one of claims 1 to 8 on a substrate, if necessary, the solvent is dried, and then cured by irradiating with active energy rays, and if necessary with an alkaline aqueous solution. A method for producing a cured film of a negative photosensitive resin composition, wherein a cured film is obtained by heating to 100 ° C. or higher after development.