JP7194060B2 - Negative photosensitive resin composition - Google Patents

Description

The present invention relates to a negative photosensitive resin composition.

A photosensitive resin, which can be easily patterned by photolithography, is a material widely used in the electronics field such as semiconductors and displays.

Among these photosensitive resins, polyimide-based photosensitive resins are cited as materials having high heat resistance, and compositions using polyimide resins having acidic groups in the polymer have been proposed.
As specific technical examples, for example, Patent Documents 1 and 2 describe a photosensitive composition using a polyimide resin containing a phenol group as an alkali-soluble acidic group in the polymer molecule. Patent Documents 3 and 4 describe a photosensitive composition using a polyimide resin containing a carboxyl group as an acidic group in the polymer molecule. However, in the case of polyimide resins containing phenol groups, in order to develop solubility in an alkaline developer during pattern formation by photolithography, it is necessary to lower the acidity and use a large amount of low-molecular-weight compounds such as phenolic oligomers and cross-linking agents. Ingredients had to be added. Further, in the case of a polyimide resin having a carboxyl group, the carboxyl group itself is apt to be oxidized and thermally decomposed at high temperatures, so there is a demand for a photosensitive polyimide resin composition having excellent heat resistance.

On the other hand, a resin obtained by reacting an isocyanuric acid compound and a maleimide compound is mentioned in Patent Documents 5 and 6 as a material having excellent heat resistance, but both of them describe application as a resist material and a photosensitive resin. It has not been.

JP 2008-040273 A JP 2008-197418 A Japanese Patent No. 3972481 Japanese Patent No. 5735341 U.S. Pat. No. 4,097,545 U.S. Pat. No. 4,107,153

An object of the present invention is to provide a negative photosensitive resin composition having excellent heat resistance and electrical insulation while maintaining patterning properties.

As a result of repeated investigations in order to achieve the above object, the inventors found that by using a negative photosensitive resin composition containing as an essential component a resin reaction product of a compound having a specific structure having an acidic group and a maleimide compound, have found that a photosensitive resin composition exhibiting excellent heat resistance and electrical insulation can be obtained. The present invention consists of the following.

[1]. (A): the following general formula

(R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Negative photosensitivity having as essential components a resin reaction product of a compound represented by and a compound having at least one maleimide group in one molecule, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. Resin composition.

[2]. (A) is represented by the following general formula

(R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The reaction product of the compound represented by and a compound having at least one maleimide group in one molecule is represented by the following general formula

(R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The negative photosensitive resin composition described in [1] having a structure represented by may also be used.

[3]. The negative photosensitive resin composition according to [1] or [2] may be used, wherein (A) the compound having at least one maleimide group in one molecule is a bismaleimide compound.

[4]. The (A) resin reactant is (A) the following general formula

(R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The total molar amount X of the NH groups in the compound represented by and the total molar amount Y of the maleimide groups in the compound having at least one maleimide group in one molecule are reactants in a ratio of X>Y. It may be a type photosensitive resin composition.

[5]. The (B) photopolymerizable compound is an acrylic group-containing compound, or an alicyclic epoxy group-containing compound, a glycidyl group-containing compound, an oxetanyl group-containing compound, an alkoxysilyl group-containing compound, a maleimide group-containing compound, or a vinyl ether group-containing compound. It may be a negative photosensitive resin composition according to [1] to [4].

[6]. In the photopolymerizable compound (B), the negative photosensitive resin composition according to any one of [1] to [5], which is a compound having two or more photoreactive groups in one molecule, may also be used.

[7]. The negative photosensitive resin composition according to any one of [1] to [6] containing a photosensitizer may also be used.

[8]. The negative photosensitive resin composition according to any one of [1] to [7], which contains a silane coupling agent, may also be used.

[9]. A cured product obtained by curing the negative photosensitive resin composition according to any one of [1] to [8] may also be used.

ADVANTAGE OF THE INVENTION The negative photosensitive resin composition of this invention has the outstanding patterning property, and exhibits the outstanding heat resistance and electrical insulation.

(Negative photosensitive resin composition)
The above negative photosensitive resin composition has (A) the following general formula

(R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Negative photosensitivity having as essential components a resin reaction product of a compound represented by and a compound having at least one maleimide group in one molecule, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. It has been found that the resin composition can provide a negative photosensitive resin composition having excellent heat resistance and electrical insulation.

(Component (A): Negative photosensitive resin reaction product)
The above negative photosensitive polyimide resin composition contains, as component (A), a resin reaction product of a compound having an isocyanuric acid structure represented by the following general formula and a maleimide compound as an essential component. (R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms)

Specific examples of compounds having this isocyanuric acid structure include isocyanuric acid, monoallylisocyanuric acid, diallylisocyanuric acid, monomethylisocyanuric acid, dimethylisocyanuric acid, monoglycidylisocyanuric acid, diglycidylisocyanuric acid, monobenzylisocyanuric acid, dibenzylisocyanuric acid, ethylenebisisocyanuric acid, trimethylenebisisocyanuric acid, tetramethylenebisisocyanuric acid, and the like.

Moreover, the maleimide compound to be reacted with these isocyanuric acid derivatives is not particularly limited as long as it is a compound having a maleimide group in one molecule. For example, compounds having one maleimide group in the molecule include maleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-allylmaleimide and the like. A bismaleimide compound is preferable from the viewpoint that the heat resistance of the resulting resin composition is increased.

Specific examples of bismaleimide compounds include bis(4-maleimidophenyl)methane, bis(3-maleimidophenyl)methane, bis(4-maleimidocyclohexyl)methane, bis(3-maleimidocyclohexyl)methane, bis(3-methyl -4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane , bis(3-propyl-4-maleimidophenyl)methane, bis(3,5-dipropyl-4-maleimidophenyl)methane, bis(3-butyl-4-maleimidophenyl)methane, bis(3,5-dibutyl- 4-maleimidophenyl)methane, bis(3-ethyl-4-maleimido-5-methylphenyl)methane, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4- maleimidophenyloxy)phenyl]propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(4-maleimidophenyl)propane, 2,2-bis(4-maleimidophenyl)propane, 2 , 2-bis[4-(4-maleimidophenyloxy)phenyl]propane, bis(4-maleimidophenyl)ether, bis(3-maleimidophenyl)ether, bis(4-maleimidophenyl)ketone, bis(3-maleimide phenyl)ketone, bis(4-maleimidophenyl)sulfone, bis(3-maleimidophenyl)sulfone, bis[4-(4-maleimidophenyloxy)phenyl]sulfone, bis(4-maleimidophenyl)sulfide, bis(3- maleimidophenyl)sulfide, bis(4-maleimidophenyl)sulfoxide, bis(3-maleimidophenyl)sulfoxide, bis(4-maleimidophenyl)diphenylsilane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4- Dimaleimidonaphthalene, 2,3-dimaleimidonaphthalene, 1,5-dimaleimidonaphthalene, 1,8-dimaleimidonaphthalene, 2,6-dimaleimidonaphthalene, 2,7-dimaleimidonaphthalene, 4,4'-di maleimidobiphenyl, 3,3'-dimaleimidobiphenyl, 3,4'-dimaleimidobiphenyl, 2,5-dimaleimido-1,3-xylene, 1,5-dimaleimidoanthraquinone, 1,2-dimaleimidoanthraquinone, 2 , 7-di maleimidofluorene, 9,9-bis(4-maleimidophenyl)fluorene, 9,9-bis(4-maleimido-3-methylphenyl)fluorene, 9,9-bis(3-ethyl-4-maleimidophenyl)fluorene, 3,7-dimaleimido-2-methoxyfluorene, 9,10-dimaleimidophenanthrene, 1,2-dimaleimidoanthraquinone, 1,5-dimaleimidoanthraquinone, 2,6-dimaleimidoanthraquinone, 1,2-dimaleimidobenzene , 1,3-dimaleimidobenzene, 1,4-dimaleimidobenzene, 1,4-bis(4-maleimidophenyl)benzene, 2-methyl-1,4-dimaleimidobenzene, 2,3-dimethyl-1, 4-dimaleimidobenzene, 2,5-dimethyl-1,4-dimaleimidobenzene, 2,6-dimethyl-1,4-dimaleimidobenzene, 4-ethyl-1,3-dimaleimidobenzene, 5-ethyl- 1,3-dimaleimidobenzene, 4,6-dimethyl-1,3-dimaleimidobenzene, 2,4,6-trimethyl-1,3-dimaleimidobenzene, 2,3,5,6-tetramethyl-1 ,4-dimaleimidobenzene, 4-methyl-1,3-dimaleimidobenzene and the like.

Also, in these compounds, the reaction ratio is determined by the following general formula

(R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms) and the total molar amount X of the NH groups in the compound represented by and at least one or more maleimide groups in one molecule When the total molar amount of the maleimide groups in the compound is Y, it is preferable to react at a ratio of X>Y so that all the NH groups, which are acidic groups, do not react, and the ratio of X and Y is adjusted. By doing so, it becomes easy to control the solubility of the resulting photosensitive resin composition in an alkaline developer. The ratio of X and Y (X/Y) is preferably 1.05<X/Y<5. .1<X/Y<3 is more preferable, and 1.1<X/Y<2 is more preferable from the viewpoint of increasing the mechanical strength of the cured product.

(Component (B): photopolymerizable compound)
The above negative photosensitive resin composition contains a photopolymerizable compound having at least one photopolymerizable functional group in one molecule as an essential component. The photopolymerizable functional group is polymerized and crosslinked by an acidic active substance generated by a photoacid generator, or a radical species or cationic species generated by a photopolymerization initiator when an active energy ray is irradiated from the outside. means a functional group. Active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays and i-rays. The reaction mode and cross-linking mode of the photopolymerizable functional group are not particularly limited. Among them, from the viewpoint of reactivity, the photopolymerizable functional group is preferably a (meth)acryloyl group, an epoxy group, an oxetanyl group, an alkoxysilyl group, a maleimide group, or a vinyloxy group. Among the above epoxy groups, alicyclic epoxy groups and glycidyl groups are preferable from the viewpoint of stability, and alicyclic epoxy groups are particularly preferable from the viewpoint of excellent cationic polymerizability by light and heat. Examples of the above alkoxysilyl groups include those in which the silicon-bonded functional group is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group or tert-butoxy group. . From the viewpoint that residual components are less likely to remain after curing, the functional group that bonds to silicon is preferably a methoxy group or an ethoxy group.

Specific examples of the above epoxy compounds and oxetane compounds as photopolymerizable compounds include novolac phenol type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, cyclohexyl epoxy group-containing polyorganosiloxanes (cyclic or linear), glycidyl group-containing polyorganosiloxane (cyclic or linear), bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2′-bis(4-glycidyloxycyclohexyl)propane, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5- Spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl)adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanate Nurate, diallyl monoglycidyl isocyanurate, 1,4-bis {(3-ethyl-3-oxetanyl) methoxy} methyl} benzene, bis {1-ethyl (3-oxetanyl)} methyl ether, 3-ethyl-3-( phenoxymethyl)oxetane and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane.

Specific examples of alkoxysilane compounds as examples of photopolymerizable cross-linking agents include tetramethoxy(ethoxy)silane and its condensates, methyltrimethoxy(ethoxy)silane and its condensates, and dimethyldimethoxy(ethoxy)silane and its condensates. etc.

Specific examples of the (meth)acrylate compounds include allyl (meth)acrylate, vinyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (meth)acrylic acid modified allyl glycidyl ether (manufactured by Nagase ChemteX, trade name: Denacol Acrylate DA111), urethane (meth)acrylates, epoxy (meth)acrylates, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane (meth)tetraacrylate, dipentaerythritol hexa(meth)acrylate, butanediol di(meth)acrylate, nonanediol di(meth)acrylate, polypropylene glycol-based (meth)acrylate, bisphenol A di(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, (meth)acrylate group-containing polyorganosiloxane, and the like.

(Component (C): photopolymerization initiator)
In the photosensitive resin composition of the present invention, a photopolymerization initiator is an essential component, and depending on the type of the polymerized compound, a photocationic polymerization initiator, a photoradical polymerization initiator, etc. may be appropriately selected and used, and the type is particularly limited. can be used in combination.

The photocationic polymerization initiator that can be used is not particularly limited and can be used. Metal fluoroboron complex salts and boron trifluoride complex compounds described in US Pat. bis(perfluoroalkylsulfonyl)methane metal salts such as, aryldiazonium compounds as described in US Pat. No. 3,708,296; aromatic onium salts of Group VIa elements as described in US Pat. No. 4,058,400; aromatic onium salts of Group Va elements as described in US Pat. No. 4,069,055; dicarbonyl chelates of Group IIIa-Va elements, as described in US Pat. No. 4,068,091; Thiopyrylium salts, such as those described in US Pat. No. 4,161,478, Group VIa elements in the form of MF ₆ ^-anions , where M is selected from phosphorus, antimony and arsenic, as described in US Pat. No. 4,231,951. aryl sulfonium complex salts such as those described in US Pat. R. Bis[4-(diphenylsulfonio)phenyl]sulfide-bishexafluoro as described by Watt et al., Journal of Polymer Science, Polymer Chemistry Edition, Vol. 22, p. 1789 (1984). Metal salts (eg, phosphates, arsenates, antimonates, etc.), aromatic iodonium complex salts and aromatic sulfonium complex salts whose anion is B(C ₆ F ₅ ) ₄ ^- , and the like.

Preferred photocationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium salts and iodonium salts of halogen-containing complex ions, and aromatic onium salts, sulfonate esters and carboxylic acid esters of group II, group V and group VI elements. , are mentioned. Some of these salts are FX-512 (3M), UVR-6990 and UVR-6974 (Union Carbide), UVE-1014 and UVE-1016 (General Electric), KI-85 (manufactured by Degussa), and SP-152 and SP-172 (manufactured by Asahi Denka).

Examples of sulfonium salts include CPI-210S (manufactured by San-Apro). It can be used alone or in combination of two or more.

The content of the photocationic polymerization initiator in the negative photosensitive resin composition is not particularly limited, but from the viewpoint of curability, it is 0.01 to 10 parts by weight per 100 parts by weight of component (A). is preferred. If the amount of the photoacid generator is small, it may take a long time for curing, or a sufficiently cured product may not be obtained. Further, if the amount of the photoacid generator is large, the color may remain in the cured product, or the rapid curing may result in coloring or loss of heat resistance or light resistance, which may not be preferable.

Moreover, the photoradical polymerization initiator that can be used can also be used according to the photopolymerizable compound to be used, and the type is not particularly limited.

Acetophenone compounds include Irgacure 184, manufactured by BASF), 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, 1-(4′-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2′-hydroxyethoxy)phenyl (2 -hydroxy-2-propyl)ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-(4′-methylthiophenyl)-2-morpholinopropan-1-one, 2- benzyl-2-dimethylamino-1-(4′-morpholinophenyl)butan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one and 2-hydroxy -1-[4-[4-(2-Hydroxy-2-methyl-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one and the like.

(photosensitizer)
The negative photosensitive resin composition may contain a photosensitizer. By adding a photosensitizer, the sensitivity to visible light or the like can be improved in the negative photosensitive resin composition, and furthermore, g-line (436 nm), h-line (405 nm) and i-line (365 nm), etc. Sensitivity can be imparted to high-wavelength light. By using these sensitizers in combination with the above-described cationic polymerization initiator, radical polymerization initiator, photoacid generator, etc., it is possible to adjust the curability of the negative photosensitive resin composition. can. Examples of the sensitizer include anthracene-based compounds and thioxanthone-based compounds.

Specific examples of the anthracene compounds include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10- Diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di -tert-butylanthracene and the like. From the viewpoint of easy availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, and the like are preferable as the anthracene-based compound.

As the anthracene-based compound, anthracene is preferable from the viewpoint of excellent transparency of the cured product, and 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene and 9,10-dipropoxyanthracene are preferred from the viewpoint of excellent compatibility with the curable composition. , 10-diethoxyanthracene and the like are preferred.

Specific examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone and 2,5-diethyldioxanthone.

As these sensitizers, one type may be used, or two or more types may be used in combination.

The content of the sensitizer in the curable composition of the present invention is not particularly limited as long as it is an amount that can exhibit a sensitizing effect, but the added initiator (photoacid generator, cationic polymerization initiator or radical polymerization initiator agent) is preferably 0.01 to 300 mol, more preferably 0.1 to 100 mol, per 1 mol. If the amount of the sensitizer is too small, a sensitizing effect cannot be obtained, and curing may take a long time, or the developability may be adversely affected. On the other hand, if the amount of the sensitizer is too large, the cured product may remain colored, may be colored due to rapid curing, or may deteriorate in heat resistance or light resistance.

(Silane coupling agent)
The negative photosensitive resin composition may contain a silane coupling agent for the purpose of improving adhesion.

(filler)
You may add a filler to the said negative photosensitive resin composition as needed.

(Antiaging agent)
An antioxidant may be added to the negative photosensitive resin composition.

(Ultraviolet absorber)
An ultraviolet absorber may be added to the negative photosensitive resin composition.

(solvent)
The solvent to be used is not particularly limited. Specifically, hydrocarbon solvents such as benzene, toluene, hexane and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and diethyl ether; Solvents; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA) and ethylene glycol diethyl ether; Chloroform, methylene chloride and 1,2 -Halogen solvents such as dichloroethane.

(others)
The negative photosensitive resin composition includes a coloring agent, a release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, an anti-repellent agent, an ion trapping agent (antimony-bismuth etc.), thixotropic agents, tackifiers, storage stability improvers, antiozonants, light stabilizers, thickeners, plasticizers, reactive diluents, antioxidants, heat stabilizers, electrical conductivity Imparting agents, antistatic agents, radiation shielding agents, nucleating agents, phosphorus-based peroxide decomposers, lubricants, pigments, metal deactivators, thermal conductivity imparting agents, physical property modifiers, etc. are used for the purposes and effects of the present invention. can be added within a range that does not impair the

(Regarding the pattern formation method)
A layered product (substrate/photosensitive resin composition) obtained by applying the above negative photosensitive resin composition to a thickness of 1 to 5 μm on a substrate and drying the composition is exposed, followed by an alkaline developer. A pattern can be formed by developing with.

As a light source for photocuring (exposing) the negative photosensitive resin composition, a light source that emits light at an absorption wavelength of the polymerization initiator and sensitizer used may be used, usually in the range of 200 to 450 nm. Light sources that contain wavelengths (eg, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, high power metal halide lamps, xenon lamps, carbon arc lamps or light emitting diodes, etc.) can be used.

The amount of exposure for photocuring the negative photosensitive resin composition is not particularly limited, but is preferably 1 to 10,000 mJ/cm ² , more preferably 1 to 3,000 mJ/cm ² . If the amount of exposure is too small, the negative photosensitive resin composition may not be cured. If the amount of light exposure is large, the color may change due to rapid curing. The curing time range is preferably 1-600 seconds, more preferably 1-150 seconds. If the curing time is long, the rapid curing characteristic of photocuring cannot be utilized.

For the purpose of removing the solvent and improving physical properties of the cured product, heat may be applied before and after photocuring for pre-baking and after-baking. The curing temperature can be set as appropriate, preferably 40 to 400°C, more preferably 60 to 350°C.

There is no particular limitation for patterning formation with an alkaline developer, and the desired pattern can be formed by dissolving and removing the unexposed areas by a commonly used development method such as an immersion method or a spray method.

Also, the developer used in the alkali development can be used without any particular limitation as long as it is generally used. Specific examples of the developer include organic alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution. Inorganic alkali aqueous solution etc. are mentioned. The aqueous solution may contain an alcohol, a surfactant, and the like for adjusting the dissolution rate and the like. The concentration of the aqueous solution is preferably 25% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, from the viewpoint that the contrast between the exposed area and the unexposed area is easily obtained. .

(Application)
The negative photosensitive resin composition and its cured product of the present invention can be used for various purposes. Examples include transparent materials, optical materials, optical lenses, optical films, optical sheets, optical component adhesives, optical waveguide coupling optical adhesives, optical waveguide peripheral member fixing adhesives, DVD bonding adhesives, adhesives, Dicing tapes, electronic materials, insulating materials (including printed circuit boards, wire coatings, etc.), high-voltage insulating materials, interlayer insulating films, passivation films for TFTs, gate insulating films for TFTs, interlayer insulating films for TFTs, transparent planarization for TFTs Film, insulating packing, insulating coating material, adhesive, high heat resistant adhesive, high heat dissipation adhesive, optical adhesive, LED element adhesive, various substrate adhesive, heat sink adhesive, paint, UV powder Body paints, inks, colored inks, UV inkjet inks, coating materials (including hard coats, sheets, films, release paper coats, optical disc coats, optical fiber coats, etc.), molding materials (sheets, films, FRP, etc.) including), sealing materials, potting materials, sealing materials, sealing materials for light-emitting diodes, optical semiconductor sealing materials, hollow structures for CMOS/CCD sensors, hollow structures for MEMS devices, liquid crystal sealants, display devices Sealants, sealing materials for electrical materials, sealing materials for various solar cells, highly heat-resistant sealing materials, resist materials, liquid resist materials, colored resist materials, dry film resist materials, solder resist materials, binder resins for color filters, color filters transparent flattening material for black matrix, binder resin for black matrix, photospacer material for liquid crystal cell, transparent sealing material for OLED element, stereolithography, material for solar cell, material for fuel cell, display material, recording material, anti-vibration material, Waterproof materials, moisture-proof materials, heat shrinkable rubber tubes, O-rings, photosensitive drums for copiers, solid electrolytes for batteries, gas separation membranes, concrete protection materials, linings, soil injection agents, cold and heat storage materials, sealing materials for sterilization equipment, Examples include contact lenses and oxygen-permeable membranes. Moreover, the negative photosensitive resin composition may be used as an additive to other resins.

EXAMPLES The present invention will be described in more detail based on examples below, but the present invention is not limited to the following examples.

(Patterning property evaluation)
Using the resin compositions obtained in Examples and Comparative Examples, patternsability evaluation samples were produced. First, the resin compositions obtained in Examples and Comparative Examples were spin-coated on a glass substrate to a film thickness of 2 μm, and heated on a hot plate heated to 100° C. for 2 minutes. Next, using an exposure device (high-pressure mercury lamp, manual exposure machine, manufactured by Dai Nippon Kaken Co., Ltd.), each resin composition is exposed with an optimal integrated light amount through a mask engraved with a 50 μm line and space pattern (software contact exposure) and allowed to stand for 1 minute after exposure. Thereafter, the substrate was immersed in an alkaline developer (2.38% aqueous solution of TMAH) for 180 seconds and washed with water for 30 seconds to form a pattern. Then, it was heated on a hot plate at 230° C. for 30 minutes to obtain a patterning property evaluation sample.

The pattern shape of the obtained patterning property evaluation sample was observed using a 3D measurement laser microscope (LEXT OLS4000, manufactured by Olympus) and a stylus type surface profiler (Dektak150, manufactured by Veeco). The condition was evaluated according to the following criteria.

<Evaluation Criteria>
○: Practical level (no residual film in 50 μm line and space)
×: Not suitable for practical use (50 μm line and space with residual film)

(Heat resistance evaluation)
Using a thermogravimetric analyzer (TGA, manufactured by Shimadzu Corporation), the temperature was raised from room temperature to 500°C at a rate of 10°C/min, and the temperature at which the weight decreased by 1% was used as an index for evaluation.

(electrical insulation evaluation)
A molybdenum thin film-coated glass substrate was spin-coated with the resin compositions obtained in Examples and Comparative Examples to a film thickness of ◯, and heated on a hot plate heated to 100° C. for 2 minutes. Next, after exposure to 300 mJ/cm ² using an exposure device (high-pressure mercury lamp, manual exposure machine, manufactured by Dai Nippon Kaken Co., Ltd.), the composition is heated on a hot plate at 230° C. for 30 minutes to form a film of a photosensitive resin composition. An aluminum electrode (3 mmΦ) was formed on this film using a vacuum deposition machine to prepare a capacitor. A semiconductor parameter analyzer (Agilent 4156) was used to measure the leak current between the upper and lower electrodes with a voltage of 30 V applied.

(Synthesis Example 1: (A))
2.5 g of isocyanuric acid and 20 g of N,N-dimethylformamide were placed in a 100 mL flask and stirred under nitrogen until the internal temperature reached 150°C. A solution was prepared by dissolving 4.2 g of N,N-1,3-phenylenebismaleimide in 20 g of N,N-dimethylformamide, charged into a flask in 5 batches, and reacted at 150° C. for 8 hours, Cooled to room temperature. Further, 500 mL of isopropyl alcohol was added, the precipitate was collected, and the target resin reaction product A1 was obtained. (X=58.1 mmol, Y=31.3 mmol)
(Synthesis Example 2: (A))
1.5 g of isocyanuric acid, 1.0 g of monoallyl isocyanuric acid, and 20 g of N,N-dimethylformamide were put into a 100 mL flask and stirred under nitrogen until the internal temperature reached 150°C. A solution was prepared by dissolving 4.2 g of N,N-1,3-phenylenebismaleimide in 20 g of N,N-dimethylformamide, charged into a flask in 5 batches, and reacted at 150° C. for 8 hours, Cooled to room temperature. 500 mL of isopropyl alcohol was added and the precipitate was collected to obtain the target resin reaction product A2. (X=46.7mmol, Y=31.3mmol)

(Synthesis Example 3: (B))
40 g of diallyl isocyanuric acid and 29 g of diallyl monomethyl isocyanuric acid were dissolved in 264 g of dioxane to obtain a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3% by weight of platinum, manufactured by Yumico Precious Metals Japan, Pt-VTSC-3X). 143 μL was added. 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane was heated to 105° C. in a nitrogen atmosphere containing 3% oxygen. It was added dropwise over 3 hours to a solution in which 88 g was dissolved in 176 g of toluene.

After 30 minutes from the end of dropping, it was confirmed by ¹ H-NMR that the reaction rate of the alkenyl group was 95% or more. Thereafter, a solution prepared by dissolving 62 g of 1-vinyl-3,4-epoxycyclohexane in 62 g of toluene was added dropwise to the above solution over 1 hour. After 30 minutes from the end of dropping, it was confirmed by ¹ H-NMR that the reaction rate of the alkenyl group was 95% or more, and then the reaction was terminated by cooling. After the toluene and dioxane solvents were distilled off under reduced pressure, the solvent was substituted with propylene glycol 1-monomethyl ether 2-acetate to obtain "Modified Siloxane B1", which is a colorless and transparent 75% by weight cationic polymerizable resin.

(Example 1)
0.50 g of the resin reaction product A1 described in Synthesis Example 1 as component (A), 0.10 g of tris(2-acryloyloxyethyl) isocyanurate as component (B), and a photopolymerization initiator Irgacure 184 as component (C). (manufactured by Ciba Specialty Chemicals) and 0.025 g of 9,10-dibutoxyanthracene were dissolved in 3.5 g of PGMEA (propylene glycol monomethyl ether acetate) as a solvent to prepare a photosensitive composition 1.

(Example 2)
0.50 g of resin reaction product A1 described in Synthesis Example 2 as component (A), 0.10 g of tris(2-acryloyloxyethyl) isocyanurate as component (B), and photopolymerization initiator Irgacure 184 as component (C). (manufactured by Ciba Specialty Chemicals) and 0.025 g of 9,10-dibutoxyanthracene were dissolved in 3.5 g of PGMEA (propylene glycol monomethyl ether acetate) as a solvent to prepare a photosensitive composition 2.

(Example 3)
0.50 g of the resin reactant A1 described in Synthesis Example 1 as component (A), and 1.5 g of 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (Celoxide 2021P, manufactured by Daicel Organic Synthesis Company), and as the component (C), 0.045 g of a photocationic polymerization initiator CPI-210S (manufactured by San-Apro Co., Ltd.), 0.025 g of 9,10-dibutoxyanthracene, and PGMEA (propylene glycol monomethyl ether Acetate) was dissolved in 3.5 g to prepare a photosensitive composition 3.

(Example 4)
0.50 g of the resin reactant A described in Synthesis Example 1 as component (A), 0.50 g of modified siloxane B1, which is a cationic polymerizable resin described in Synthesis Example 3 as component (B), and component (C) , Photocationic polymerization initiator CPI-210S (manufactured by San-Apro Co., Ltd.) 0.045 g, 9,10-dibutoxyanthracene 0.025 g is dissolved in 3.5 g of solvent PGMEA (propylene glycol monomethyl ether acetate) to prepare a photosensitive composition. 4 was prepared.

(Comparative example 1)
For comparison with component (A), 0.50 g of phenol group-containing resin Marukalinker M (polyvinylphenol resin, manufactured by Maruzen Petrochemical Co., Ltd.) as an acidic group, and 0.5 g of tris(2-acryloyloxyethyl) isocyanurate as component (B). 10 g. As component (C), 0.025 g of a photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty Chemicals) and 0.025 g of 9,10-dibutoxyanthracene were added to 3.5 g of PGMEA (propylene glycol monomethyl ether acetate) solvent. By dissolving, a photosensitive composition 5 was prepared.

(result)
The above evaluation was performed on the photosensitive resin compositions obtained in Examples and Comparative Examples. Table 1 shows the results.

INDUSTRIAL APPLICABILITY The present invention can be used in various fields such as insulating interlayer films, adhesives, coating agents and sealing agents for electronic devices such as semiconductors and displays.

Claims (9)

(A) the following general formula

(R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Negative photosensitivity having as essential components a resin reaction product of a compound represented by and a compound having at least one maleimide group in one molecule, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. Resin composition. (A) is represented by the following general formula

(R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A compound represented by
A reaction product with a compound having at least one maleimide group in one molecule has the following general formula

(R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The negative photosensitive resin composition according to claim 1, characterized by having a structure represented by: 3. The negative photosensitive resin composition according to claim 1, wherein (A) the compound having at least one maleimide group in one molecule is a bismaleimide compound. The (A) resin reactant is (A) the following general formula

(R in the formula is a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The total molar amount X of NH groups in the compound represented by and the total molar amount Y of maleimide groups in a compound having at least one maleimide group in one molecule are reactants in a ratio of X>Y Item 4. The negative photosensitive resin composition according to any one of Items 1 to 3. The (B) photopolymerizable compound is an acrylic group-containing compound, or an alicyclic epoxy group-containing compound, a glycidyl group-containing compound, an oxetanyl group-containing compound, an alkoxysilyl group-containing compound, a maleimide group-containing compound, or a vinyl ether group-containing compound. The negative photosensitive resin composition according to any one of claims 1 to 4, which is any one of. 6. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein (B) the photopolymerizable compound is a compound having two or more photoreactive groups in one molecule. The negative photosensitive resin composition according to any one of claims 1 to 6, which contains a photosensitizer. 8. The negative photosensitive resin composition according to any one of claims 1 to 7, further comprising a silane coupling agent. A cured product obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 8.