TW202506779A - Negative photosensitive resin composition - Google Patents

Abstract

A negative photosensitive resin composition containing the following components (A) to (E). (A) a novolac-type phenolic resin having a molar ratio of structural units (a1) derived from m-cresol, structural units (a2) derived from catechol, structural units (a3) derived from benzaldehyde, and structural units (a4) derived from salaldehyde [(a1): (a2): (a3): (a4)] of 1: 0.25-4.0: 0.25-4.0: 0.25-4.0; (B) a polyimide containing an ethylenically unsaturated group, a polyimide precursor containing an ethylenically unsaturated group, a polyphenylene glycol containing an ethylenically unsaturated group, Azoles and polybenzoic acid containing ethylenically unsaturated groups (C) a free radical polymerizable compound; (D) a photopolymerization initiator; and (E) an organic solvent.

Description

Negative photosensitive resin composition

The present invention relates to a negative photosensitive resin composition, a hardened film and a resistance film.

Organic EL displays are attracting attention as the next generation of flat panel displays. Organic EL displays are self-luminous display devices that use electric field luminescence from organic compounds. They can display images with high-angle viewing and fast response. In addition, they can be made thinner and lighter. In recent years, as organic EL displays have become more sophisticated, there has been a demand for further miniaturization of luminous elements.

Organic EL displays use the energy of recombination between electrons injected from the cathode and holes injected from the anode to emit light. Therefore, when substances that form energy levels that hinder the recombination of electrons and holes exist, the light-emitting efficiency of the light-emitting element will decrease, and the life of the organic EL display will be reduced. On the other hand, in general, in order to divide the pixels of the light-emitting element, an insulating layer called a pixel division layer is formed between the transparent electrode on the light-emitting side and the metal electrode on the opposite side. Since this pixel division layer is formed at a position adjacent to the light-emitting element, gas desorption and outflow of ion components from the pixel division layer may become one of the reasons for the reduction in the life of the organic EL display. Therefore, heat resistance and durability are required for the pixel division layer.

Based on the viewpoint of high heat resistance, the pixel segmentation layer is made of polyimide resin and polybenzoic acid. A photosensitive resin composition of an azole resin (for example, Patent Document 1). Since the pixel division layer is required to be black, the above-mentioned photosensitive resin composition is a colorant such as carbon black added to the solid component at about 20%. [Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2022/070946

[The problem that the invention wants to solve]

In the production of fine patterns, the colorant mixed in the photosensitive resin composition may become residue during development. In addition, since carbon black is conductive, it is better to use less even if it is to improve the insulation of the cured film. As the organic EL display is becoming more refined, it is possible to produce a finer pixel division layer without generating residues, and a photosensitive resin composition having a high visible light shielding ability is being sought even if the amount of colorant added is reduced. The purpose of the present invention is to provide a photosensitive resin composition that can obtain a cured film having a high visible light shielding ability even if the amount of colorant added is reduced. [Means for solving the problem]

The inventors of the present invention have conducted careful research and examination to solve the above problems and have found that: a phenolic resin composition having a specific structural unit, a polyimide containing an ethylenically unsaturated group, and a polyphenylene oxide containing an ethylenically unsaturated group can be used to prepare a phenolic resin. The present invention is completed by using a negative photosensitive resin composition in which at least one of the above-mentioned components is used in combination with an azole, and the cured film obtained has high visible light shielding properties even if the amount of the colorant used is reduced.

That is, the present invention relates to a negative photosensitive resin composition containing the following components (A) to (E). (A) a novolac-type phenolic resin having a molar ratio of structural units (a1) derived from m-cresol, structural units (a2) derived from catechol, structural units (a3) derived from benzaldehyde, and structural units (a4) derived from salicylic aldehyde [(a1): (a2): (a3): (a4)] of 1: 0.25-4.0: 0.25-4.0: 0.25-4.0; (B) a polyimide containing an ethylenically unsaturated group, a polyimide precursor containing an ethylenically unsaturated group, a polyphenylene glycol containing an ethylenically unsaturated group, Azoles and polybenzoic acid containing ethylenically unsaturated groups (C) a free radical polymerizable compound; (D) a photopolymerization initiator; (E) an organic solvent.

The present invention further relates to a cured film obtained from the aforementioned negative photosensitive resin composition. The present invention further relates to a resistive film obtained from the aforementioned negative photosensitive resin composition. [Effect of the invention]

According to the present invention, a photosensitive resin composition can be provided, which can obtain a cured film with high visible light shielding ability even if the amount of colorant added is reduced.

The following describes the form for implementing the invention. In addition, in this specification, "x to y" represents a numerical range of "above x and below y". The upper limit and lower limit values described in the numerical range can be combined arbitrarily. In addition, a form obtained by combining two or more forms of the present invention described below is also a form of the present invention.

[Negative photosensitive resin composition] The negative photosensitive resin composition of one embodiment of the present invention contains the following components (A) to (E). (A) A novolac-type phenolic resin having a molar ratio of structural units (a1) derived from m-cresol, structural units (a2) derived from catechol, structural units (a3) derived from benzaldehyde, and structural units (a4) derived from salaldehyde [(a1): (a2): (a3): (a4)] of 1: 0.25-4.0: 0.25-4.0: 0.25-4.0; (B) A polyimide containing ethylenically unsaturated groups, a polyimide precursor containing ethylenically unsaturated groups, a polyphenylene glycol containing ethylenically unsaturated groups, Azoles and polybenzoic acid containing ethylenically unsaturated groups (C) a free radical polymerizable compound; (D) a photopolymerization initiator; (E) an organic solvent.

In this embodiment, by using the novolac-type phenolic resin (A) above, a cured film having high visible light shielding properties can be obtained even when the amount of colorant added is reduced. In addition, by using the resins (A) and (B) above in combination, the compatibility of the two resins is improved. This can suppress the occurrence of poor film formation (scum). In addition, a negative photosensitive resin composition is formed that has high alkali solubility in the non-exposed portion and can obtain a resistive film and a cured film with excellent elastic coefficient. Below, the components of the negative photosensitive resin composition are described.

․ Component (A) The novolac-type phenolic resin of component (A) is composed of a structural unit (a1) derived from m-cresol, a structural unit (a2) derived from catechol, a structural unit (a3) derived from benzaldehyde, and a structural unit (a4) derived from salicylic aldehyde in a molar ratio of 1:0.25-4.0:0.25-4.0:0.25-4.0.

In this embodiment, the visible light shielding property of the cured film is improved by the fact that the novolac-type phenolic resin of component (A) contains a structural unit (a2) derived from catechol. Therefore, the amount of colorant used can be reduced. The visible light shielding performance of the cured film can be adjusted by the molar ratio of the above structural unit (a2). The molar ratio [(a1): (a2): (a3): (a4)] is based on the viewpoint that in addition to high sensitivity, the resin has excellent compatibility and can obtain a cured film with visible light shielding properties, and is preferably 1: 0.3-3.5: 0.8-3.0: 0.5-2.0.

In one embodiment, the molar ratio of the total [(a1)+(a2)] of the structural unit (a1) derived from meta-cresol and the structural unit (a2) derived from catechol and the total [(a1)+(a2)] of the structural unit (a3) derived from benzaldehyde and the structural unit (a4) derived from salicylic aldehyde [(a3)+(a4)] in the component (A) is 1:0.8-1.2, preferably 1:0.9-1.1. This makes it easy to adjust the weight average molecular weight of the component (A) to a preferred range. In addition, when the negative photosensitive resin composition of this embodiment is made into a photosensitive film, the alkali solubility (sensitivity) can be improved.

In one embodiment, the molar ratio of the structural unit (a2) in the component (A) relative to the total of the structural unit (a1) derived from m-cresol and the structural unit (a2) derived from catechol [(a1) + (a2)] [(a2) / ((a1) + (a2))] is 0.01 to 0.8. The structural unit (a1) and the structural unit (a2) are both derived from a compound having a hydroxyl group. By increasing the molar ratio of the structural unit (a2), the visible light shielding property of the cured film can be improved. On the other hand, the alkali solubility can be adjusted by the molar ratio of the structural unit (a1). From the viewpoint of both alkali solubility and visible light shielding property, the molar ratio [(a2)/((a1)+(a2))] is preferably 0.1 to 0.7, more preferably 0.3 to 0.6.

In one embodiment, the molar ratio of the structural unit (a3) in component (A) relative to the total of the structural unit (a3) derived from benzaldehyde and the structural unit (a4) derived from salicylic aldehyde [(a3) + (a4)] is 0.2 to 0.8. The structural unit (a3) and the structural unit (a4) are both derived from a compound having an aldehyde group. The alkaline solubility can be appropriately adjusted by the molar ratio [(a3) / ((a3) + (a4))]. The molar ratio [(a3) / ((a3) + (a4))] is preferably 0.3 to 0.7.

Component (A) may contain structural units other than the structural units (a1) to (a4). Examples of structural units other than the structural units (a1) to (a4) include structural units derived from phenols other than m-cresol and catechol, and aldehydes other than benzaldehyde and salicylic aldehyde.

Examples of the phenols include phenol, o-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, and 3,4,5-trimethylphenol.

Examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, chloroacetaldehyde, 4-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, and the like.

The total content of the above structural units (a1), (a2), (a3) and (a4) in component (A) is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 90% by mass or more, based on the viewpoint that in addition to high sensitivity, the resin has excellent compatibility and a resistance film and a cured film with visible light shielding properties can be obtained. The total content of the above structural units (a1), (a2), (a3) and (a4) can be substantially 100% by mass. In addition, substantially 100% by mass means that structural units other than the above structural units (a1), (a2), (a3) and (a4) are inevitably included.

The weight average molecular weight of the novolac type phenolic resin belonging to component (A) is preferably 1,000 or more, more preferably 1,500 or more. Also, it is preferably 7,000 or less, more preferably 6,000 or less, and even more preferably 5,000 or less. When the weight average molecular weight is 1,000 or more, it is preferred because of high heat resistance. On the other hand, when the weight average molecular weight is 7,000 or less, it is preferred because of high sensitivity. In addition, in this specification, the weight average molecular weight is measured according to the conditions described in the examples.

Component (A) can be obtained by condensing m-cresol, catechol, benzaldehyde, and salicylic aldehyde in an organic solvent at a molar ratio of (m-cresol: catechol: benzaldehyde: salicylic aldehyde) of 1:0.25-4.0:0.25-4.0:0.25-4.0 using an acid catalyst.

The molar ratio of m-cresol, catechol, benzaldehyde, and salicylic aldehyde (m-cresol: catechol: benzaldehyde: salicylic aldehyde) is preferably in the range of 1:0.3-3.5:0.8-3.0:0.5-2.0, based on the viewpoints of high sensitivity, excellent compatibility of the resin, and obtaining a resistive film and a cured film with visible light shielding properties.

In one embodiment, the molar ratio of the sum of meta-cresol and catechol and the sum of benzaldehyde and salicylic aldehyde ((meta-cresol + catechol): (benzaldehyde + salicylic aldehyde)) is 1:0.8-1.2. Furthermore, the molar ratio of catechol relative to the sum of meta-cresol and catechol (catechol/(meta-cresol + catechol)) is 0.01-0.8. Furthermore, the molar ratio of salicylic aldehyde relative to the sum of salicylic aldehyde and benzaldehyde (salicylic aldehyde/(salicylic aldehyde + benzaldehyde)) is 0.2-0.8.

When the novolac type phenolic resin of component (A) is obtained by polycondensing m-cresol, catechol, benzaldehyde, and salicylic aldehyde in an organic solvent, phenols and aldehydes other than m-cresol, catechol, benzaldehyde, and salicylic aldehyde may be contained in the organic solvent as described above.

The total mass ratio of m-cresol, catechol, benzaldehyde, and salicylic aldehyde in the organic solvent relative to the total mass of all starting materials that can become structural units of component (A) is preferably 30 mass % or more, more preferably 50 mass % or more, and even more preferably substantially 100 mass % from the viewpoint of obtaining a resistive film and a cured film having visible light shielding properties in addition to high sensitivity.

Examples of organic solvents used in the preparation of component (A) include methanol, ethanol, 1-propanol, 2-propanol, butanol, hexanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc. Among them, preferably, at least one selected from ethanol, 1-propanol, and 2-propanol is used, and more preferably, ethanol is used.

The amount of the organic solvent used is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, based on 100 parts by mass of the raw material for deriving the structural unit of component (A), from the viewpoint of reaction uniformity.

As the acid catalyst used in the production of component (A), inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid; organic acids such as oxalic acid, acetic acid, and p-toluenesulfonic acid can be exemplified. Among them, in order to further promote the reaction, inorganic acids and p-toluenesulfonic acid are preferred, and p-toluenesulfonic acid is more preferred. The amount of the acid catalyst added is not particularly limited, and is preferably 5 parts by mass or more, and more preferably 20 parts by mass or more, relative to 100 parts by mass of the raw material used to derive the structural unit constituting component (A). In addition, it is preferably 150 parts by mass or less, and more preferably 100 parts by mass or less.

The reaction temperature when polymerizing the raw materials of component (A) is preferably 30°C or higher, more preferably 40°C or higher, from the perspective of promoting the reaction and effectively increasing the molecular weight. Also, it is preferably 100°C or lower, more preferably 80°C or lower. The reaction time is preferably 4 hours or higher, more preferably 12 hours or higher. Also, it is preferably 32 hours or lower, more preferably 24 hours or lower.

․ Component (B) Component (B) is selected from polyimide containing ethylenically unsaturated groups, polyimide precursor containing ethylenically unsaturated groups, polyphenylene glycol containing ethylenically unsaturated groups, Azoles and polybenzoic acid containing ethylenically unsaturated groups The component (B) is a resin for polyimide, polyimide precursor, polybenzoic acid, Polybenzoxazole or polybenzo The azole precursor is introduced with an ethylenically unsaturated group. Component (B) may be any one conventionally used in photosensitive resin compositions.

<Polyimide and polyimide precursor> Examples of polyimide precursors include those obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride or tetracarboxylic diester dichloride, etc. with diamine, corresponding diisocyanate compound or trimethylsilylated diamine, etc., and having tetracarboxylic acid and/or its derivative residues and diamine and/or its derivative residues. Examples of polyimide precursors include polyamic acid, polyamic acid ester, polyamic acid amide or polyisoimide.

Examples of polyimide include those obtained by dehydrating and ring-closing the above-mentioned polyamic acid, polyamic acid ester, polyamic acid amide or polyisoimide by heating or using an acid or base, etc., and having a tetracarboxylic acid and/or its derivative residue, and a diamine and/or its derivative residue. The tetracarboxylic dianhydride used in the synthesis of polyimide is preferably pyromelitic anhydride based on the viewpoint of heat resistance. The diamine used in the synthesis of polyimide is preferably 4,4-diaminodiphenyl ether based on the viewpoint of heat resistance.

The unsaturated group-containing polyimide and the unsaturated group-containing polyimide precursor used in the present invention have the above-mentioned polyimide or polyimide precursor and an ethylenic unsaturated group as a free radical polymerizable group. By having an ethylenic unsaturated group, the sensitivity during exposure can be improved. As the unsaturated group-containing polyimide and the unsaturated group-containing polyimide precursor, it is preferable to react the phenolic hydroxyl group and/or carboxyl group of a part of the polyimide and the polyimide precursor with the compound having an ethylenic unsaturated group described later. By the above reaction, the ethylenic unsaturated group can be introduced into the resin.

＜Polyphenylene Azoles and polybenzo Azole prodrugs as polybenzoic acid The azole precursor may be obtained by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride or a dicarboxylic acid active diester with a diaminophenol compound as a diamine, and may have a dicarboxylic acid and/or its derivative residue and a diaminophenol compound and/or its derivative residue. Examples of the azole prodromal compounds include polyhydroxyamides.

As polyphenylene Examples of the azoles include: those obtained by dehydrating and ring-closing a dicarboxylic acid and a diaminophenol compound as a diamine by reaction with polyphosphoric acid; those obtained by dehydrating and ring-closing the above-mentioned polyhydroxyamide by heating or reaction with phosphoric anhydride, alkali or carbodiimide compounds, etc., and having a dicarboxylic acid and/or its derivative residue, and a diaminophenol compound and/or its derivative residue. Polybenzoic acid The diaminophenol used in the synthesis of azole is preferably 3,3-hydroxybenzidine from the viewpoint of heat resistance. The dicarboxylic acid used in the synthesis of azole is preferably 4,4-biphenyldicarboxylic acid from the viewpoint of heat resistance.

The polyphenylene oxide containing ethylenically unsaturated groups used in the present invention is Azoles and polybenzoic acid containing ethylenically unsaturated groups The azole precursor has an ethylenically unsaturated group as a free radical polymerizable group. By having an ethylenically unsaturated group, the sensitivity during exposure can be improved. Azoles and polybenzoic acid containing ethylenically unsaturated groups Azole prodrug, preferably polybenzo Azoles and polybenzo The oxazole precursor is obtained by reacting a part of the phenolic hydroxyl group and/or carboxyl group of the precursor with the compound having an ethylenically unsaturated group as described below. By the above reaction, an ethylenically unsaturated group can be introduced into the resin.

<Compounds having ethylenically unsaturated groups> Examples of compounds having ethylenically unsaturated groups include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thialdehyde compounds, ketone compounds, thioketone compounds, acetate compounds, carboxylic acid chlorides, carboxylic acid anhydrides, carboxylic acid active ester compounds, carboxylic acid compounds, halogenated alkyl compounds, alkyl nitride compounds, trifluoromethanesulfonate alkyl compounds, methanesulfonate alkyl compounds, toluenesulfonate alkyl compounds, or cyanide alkyl compounds.

＜Polyimide, polybenzo Azoles, polyimide precursors or polybenzo Synthesis of azole precursors> Polyimide, polyimide precursors, polybenzo Polybenzoxazole or polybenzo The azole precursor can be synthesized by a known method. As a specific method, for example, a diamine or a diaminophenol compound is first dissolved in a reaction solvent, and a substantially equimolar amount of a carboxylic anhydride is slowly added to the solution. A mechanical stirrer is used to stir the mixed solution at a temperature of preferably 0 to 200° C., more preferably 40 to 150° C., preferably for 0.5 to 50 hours, more preferably 2 to 24 hours. In the case of using a capping agent, after adding the carboxylic anhydride, the mixture is stirred at a predetermined temperature for a predetermined time, and then the capping agent is slowly added and stirred.

The reaction solvent used in the polymerization reaction can dissolve the diamines or diaminophenol compounds and carboxylic anhydrides that are the raw materials, and a polar solvent is preferred. Examples of the reaction solvent include amides such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone or α-methyl-γ-butyrolactone, carbonates such as ethyl carbonate or propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol or p-cresol, or other solvents such as acetophenone, 1,3-dimethyl-2-imidazoledione, cyclobutane sulfone, and dimethyl sulfoxide. The amount of the reaction solvent is preferably 100 to 1900 parts by mass, more preferably 150 to 950 parts by mass, based on 100 parts by mass of the total amount of the diamine or diaminophenol compound and the carboxylic anhydride.

Selected from polyimide, polybenzo Azoles, polyimide precursors and polybenzo Preferably, at least one of the azole precursors is reacted with methanol and water after the polymerization reaction to obtain a bis(vinylpyrrolidone) selected from polyimide, polybenzoic acid, Azoles, polyimide precursors and polybenzo One or more azole precursors are obtained by precipitation in a poor solvent, followed by washing and drying. By reprecipitation, low molecular weight components can be removed, so that the mechanical properties (elastic modulus) of the cured film are greatly improved.

＜Polyimide containing ethylenically unsaturated groups, polyimide precursor containing ethylenically unsaturated groups, polyphenylene glycol containing ethylenically unsaturated groups Polybenzoxazole or polybenzoyl containing ethylenically unsaturated groups Synthesis method of oxazole precursor＞ Polyimide containing ethylenically unsaturated group, polyimide precursor containing ethylenically unsaturated group, polybenzoic acid containing ethylenically unsaturated group Polybenzoxazole or polybenzoyl containing ethylenically unsaturated groups The azole precursor can be synthesized by a known method. Azoles, polyimide precursors or polybenzo The reaction conditions of the azole precursor are preferably such that the reaction container is fully substituted with nitrogen by, for example, air or bubbling, decompression degassing, etc., and then polyimide, polyimide precursor, polybenzoic acid, and polyimide precursor are added to the reaction solvent. Polybenzoxazole The azole precursor and the compound having an ethylenically unsaturated group are reacted at 20 to 110° C. for 30 to 500 minutes. In addition, a polymerization terminator such as a phenol compound, an acid catalyst or an alkaline catalyst may be used as needed.

In the component (B), polyimide, polyimide precursor, polybenzoic acid Azoles, polybenzo Azole precursor, polyimide containing ethylenically unsaturated groups, polyimide precursor containing ethylenically unsaturated groups, polybenzophenone containing ethylenically unsaturated groups Azoles and polybenzoic acid containing ethylenically unsaturated groups For the specific description of the azole prodromal, reference may be made to paragraphs [0074] to [0210] of International Publication No. 2017/159876.

The weight average molecular weight of component (B) is preferably 5,000 or more, more preferably 10,000 or more. Also, it is preferably 50,000 or less, more preferably 40,000 or less. When the weight average molecular weight is 5,000 or more, it is preferred because of high heat resistance. On the other hand, when the weight average molecular weight is 50,000 or less, it is preferred from the viewpoint of solvent solubility.

The amount of component (B) added is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and preferably 2,000 parts by mass or less, more preferably 1,000 parts by mass or less, based on 100 parts by mass of component (A) in order to obtain good sensitivity and a cured film having excellent visible light shielding properties.

․ Component (C) Component (C) is a free radical polymerizable compound. A free radical polymerizable compound refers to a compound having multiple ethylenically unsaturated groups in the molecule. By containing a free radical polymerizable compound, the curing of the exposed part is promoted, and the sensitivity during exposure can be improved. In addition, the crosslinking density after thermal curing can be increased, and the hardness (elastic coefficient) of the cured film can be improved.

The radical polymerizable compound is not particularly limited, and known radical polymerizable compounds can be used. Preferably, the compound has a (meth)acrylic group that is easy to be radically polymerized. From the viewpoint of improving the sensitivity during exposure and improving the hardness of the cured film, a compound having two or more (meth)acrylic groups in the molecule is more preferred.

Examples of the radical polymerizable compound include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trihydroxymethylpropane di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ethoxylated trihydroxymethylpropane di(meth)acrylate, ethoxylated trihydroxymethylpropane tri(meth)acrylate, di-trihydroxymethylpropane tri(meth)acrylate, di-trihydroxymethylpropane tetra(meth)acrylate, Acrylate, 1,3-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dihydroxymethyl tricyclodecane di(meth)acrylate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undec(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3-( 1,3,5-bis((meth)acryloyloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloyloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)phenyl]fluorene or 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene or their acid-modified, ethylene oxide-modified or propylene oxide-modified forms.

The amount of the radical polymerizable compound is preferably 1 part by mass or more, more preferably 10 parts by mass or more, still more preferably 30 parts by mass or more, and particularly preferably 50 parts by mass or more relative to 100 parts by mass of component (A). On the other hand, the content of the radical polymerizable compound is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, still more preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less. When the content is within the above range, the sensitivity during exposure can be improved.

The radical polymerizable compound as component (C) may be used alone or in combination of two or more.

․ Component (D) Component (D) is a photopolymerization initiator. A photopolymerization initiator is a compound that generates free radicals by bond cleavage and/or reaction by exposure. By containing a photopolymerization initiator, the exposed part of the film of the negative photosensitive resin composition is insoluble in the alkaline developer, so a negative pattern can be formed. In addition, the curing of the exposed part can be promoted to improve the sensitivity.

The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include benzil ketal-based photopolymerization initiators, α-hydroxy ketone-based photopolymerization initiators, α-amino ketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, acridine-based photopolymerization initiators, titanocene-based photopolymerization initiators, diphenyl ketone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, aromatic ketoester-based photopolymerization initiators, and benzoate-based photopolymerization initiators.

The photopolymerization initiator may be used alone or in combination of two or more. The amount of the photopolymerization initiator is preferably 1 part by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of component (A), in order to obtain good sensitivity and the desired pattern. Also, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less.

․ Component (E) Examples of organic solvents that belong to component (E) include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dimethicone, etc. Ethers such as alkanes, propylene glycol monomethyl ether, and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.

The amount of component (E) blended in the negative photosensitive resin composition of this embodiment is preferably 5% by mass or more in terms of the fluidity of the composition and the ability to obtain a uniform coating by a coating method such as spin coating. In addition, it is preferably 65% by mass or less.

․ Others In one embodiment, in addition to the above-mentioned components (A) to (E), various additives may be blended into the negative photosensitive resin composition within the scope that does not hinder the efficacy of the present invention. Examples of additives include fillers, surfactants such as leveling agents, adhesion enhancers, dissolution promoters, etc.

The cured film obtained from the negative photosensitive resin composition of this embodiment has visible light shielding properties, so there is no need to add a colorant. However, in the case of requiring higher visible light shielding properties, the negative photosensitive resin composition of this embodiment may further contain a colorant. As colorants, there are: benzofuran black pigments, perylene black pigments, azo black pigments, anthraquinone black pigments, aniline black pigments, methine azo black pigments, carbon black, graphite and other organic pigments, silver-tin alloys, titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal (alloy) oxides, complex oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, nitrogen oxides and other inorganic pigments.

In one embodiment, the amount of the colorant blended is 0 to 30 parts by mass relative to 100 parts by mass of the solid content of the negative photosensitive resin composition. The negative photosensitive resin composition of this embodiment has visible light shielding properties, so the amount of the colorant blended can be suppressed more than the conventional method. The negative photosensitive resin composition may not contain a colorant, but may also contain a colorant. In the case of containing a colorant, the amount may be more than 0 parts by mass or more than 0.1 parts by mass relative to 100 parts by mass of the solid content of the negative photosensitive resin composition.

The negative photosensitive resin composition of this embodiment can be prepared by stirring and mixing the above-mentioned components (A) to (E) and various additives as needed to form a uniform liquid using a conventional method. When solid materials such as fillers and pigments are blended into the composition, it is preferred to use a dispersing device such as a dissolver, a homogenizer, and a three-roll grinder to disperse and mix them. In addition, in order to remove coarse particles and impurities, the composition can also be filtered using a screen filter, a membrane filter, etc.

The negative photosensitive resin composition of the present embodiment can be appropriately used in, for example, negative photoresist, organic underlayer film, thick film resist (protrusion forming resist), interlayer insulating film, liquid crystal alignment film, heat resistance imparting agent, polyimide, polybenzoic acid, Azole-based resists or the formation of pixel division layers in display devices such as organic EL displays.

[Curing film ․ Impedance film] The curing film of one embodiment of the present invention can be obtained by curing the negative photosensitive resin composition of the present invention. Specifically, the negative photosensitive resin composition of the present invention is applied to an object to be subjected to photolithography, and a film (photosensitive film) of the photosensitive resin composition from which the solvent has been removed is obtained by pre-baking.

Examples of coating methods include spin coating, roll coating, blow coating, dip coating, spray coating, and blade coating. Prebaking may be performed, for example, at a temperature of 60° C. to 150° C. for a period of 30 seconds to 600 seconds.

By exposing the photosensitive film, the solubility of the exposed part in the alkaline developer is greatly reduced. As the light source used for exposure, for example, infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams can be listed. Among these light sources, ultraviolet light is preferred, and g-rays (wavelength 436nm) and i-rays (wavelength 365nm) of high-pressure mercury lamps are suitable. After exposure, the crosslinking reaction with components (A), (B), and (C) is promoted by the catalytic reaction of the acid generated by exposure, and a heat treatment is performed at around 100°C.

The photosensitive film obtained from the negative photosensitive resin composition of the present invention has high alkali solubility, so the difference in alkali solubility between the exposed part and the exposed part is large, so it can be patterned with high resolution. Therefore, it can be appropriately used as a resistance film.

Alkaline developers used for development after exposure include: inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; alkaline aqueous solutions of cyclic amines such as pyrrole and piperidine. In the alkaline developer, alcohols, surfactants, etc. may be appropriately added as needed. The alkaline concentration of the alkaline developer is usually in the range of 2-5 mass %, and a 2.38 mass % tetramethylammonium hydroxide aqueous solution is generally used.

After developing with an alkaline developer, a cured film in which the exposed portion is crosslinked can be obtained by heating at a low temperature of, for example, 150°C to 200°C. The cured film of this embodiment has excellent visible light shielding properties. The cured film of this embodiment can be used, for example, on a pixel division layer in a display device such as an organic EL display. [Example]

The present invention is further described in detail below by giving specific examples. In addition, the weight average molecular weight (Mw) of the synthesized resin is measured according to the following GPC measurement conditions. [GPC measurement conditions] Measurement device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd. Column: "Shodex KF802" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm + "Shodex KF802" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm + "Shodex KF803" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm + "Shodex KF804" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm Column temperature: 40℃ Detector: RI (differential refractometer) Data processing: "GPC-8020 Mode II Version 4.30" manufactured by Tosoh Co., Ltd. Dissolution solvent: tetrahydrofuran Flow rate: 1.0mL/min Sample: A tetrahydrofuran solution converted to 0.5% by mass based on the resin solid content was filtered through a microfilter Injection volume: 0.1 mL Standard sample: The following monodisperse polystyrene (Standard sample: monodisperse polystyrene) "A-500" manufactured by Tosoh Co., Ltd. "A-2500" manufactured by Tosoh Co., Ltd. "A-5000" manufactured by Tosoh Co., Ltd. "F-1" manufactured by Tosoh Co., Ltd. "F-2" manufactured by Tosoh Co., Ltd. "F-4" manufactured by Tosoh Co., Ltd. "F-10" manufactured by Tosoh Co., Ltd. "F-20" manufactured by Tosoh Co., Ltd.

[Component (A)] Synthesis Example 1 (Synthesis of Novolac-type Phenolic Resin (A-1)) In a 2000 mL four-necked flask equipped with a cooling tube, 82 g (0.76 mol) of m-cresol, 84 g (0.76 mol) of catechol, 103 g (0.97 mol) of benzaldehyde, 74 g (0.61 mol) of salicylic aldehyde, and 8 g of p-toluenesulfonic acid were added and dissolved in 300 g of ethanol as a reaction solvent. Thereafter, the mixture was heated to 80°C in a mantle heater and stirred under reflux for 16 hours to allow the reaction to proceed. After the reaction was completed, ethyl acetate and water were added and the mixture was washed by separation 5 times. After the solvent was removed from the remaining resin solution by decompression, vacuum drying was performed to obtain 279 g of a light red powder of a novolac-type phenolic resin (A-1). The Mw of the novolac-type phenolic resin (A-1) obtained by the GPC method was 3,820.

Synthesis Example 2 (Synthesis of Novolac-type Phenolic Resin (A-2)) Except that the amount of starting materials added was set to 82g (0.76mol) of m-cresol, 84g (0.76mol) of catechol, 80g (0.75mol) of benzaldehyde, and 92g (0.75mol) of salaldehyde, the same operation as Synthesis Example 1 was performed to obtain 283g of powder of Novolac-type Phenolic Resin (A-2). The Mw of Novolac-type Phenolic Resin (A-2) obtained by GPC method was 3,270.

Synthesis Example 3 (Synthesis of Novolac-type Phenolic Resin (A-3)) Except that the amount of starting materials added was set to 82g (0.76mol) of m-cresol, 84g (0.76mol) of catechol, 117g (1.10mol) of benzaldehyde, and 58g (0.47mol) of salaldehyde, the same operation as Synthesis Example 1 was performed to obtain 279g of powder of Novolac-type Phenolic Resin (A-3). The Mw of Novolac-type Phenolic Resin (A-3) was 3,620.

Synthesis Example 4 (Synthesis of Novolac-type Phenolic Resin (A-4)) Except that the amount of starting materials added was set to 82g (0.76mol) of m-cresol, 84g (0.76mol) of catechol, 67g (0.63mol) of benzaldehyde, and 115g (0.94mol) of salicylic aldehyde, the same operation as Synthesis Example 1 was performed to obtain 286g of powder of Novolac-type Phenolic Resin (A-4). The Mw of the phenol-novolac resin (A-4) obtained by GPC method was 3,540.

Synthesis Example 5 (Synthesis of Novolac-type Phenolic Resin (A-5)) Except that the amount of starting materials added was set to 123g (1.14mol) of m-cresol, 42g (0.38mol) of catechol, 103g (0.97mol) of benzaldehyde, and 74g (0.61mol) of salicylic aldehyde, the same operation as Synthesis Example 1 was performed to obtain 282g of powder of Novolac-type Phenolic Resin (A-5). The Mw of the phenol-novolac resin (A-5) obtained by the GPC method was 3,210.

Synthesis Example 6 (Synthesis of Novolac-type Phenolic Resin (A-6)) Except that the amount of starting materials added was set to 41g (0.38mol) of m-cresol, 126g (1.14mol) of catechol, 103g (0.97mol) of benzaldehyde, and 74g (0.61mol) of salicylic aldehyde, the same operation as Synthesis Example 1 was performed to obtain 281g of powder of Novolac-type Phenolic Resin (A-6). The Mw of the phenol-novolac resin (A-6) obtained by the GPC method was 3,790.

Comparative Synthesis Example 1 (Synthesis of Novolac-type Phenolic Resin (A-7)) Except that the amount of starting materials added was set to 164g (1.52mol) of m-cresol, 103g (0.97mol) of benzaldehyde, and 74g (0.61mol) of salaldehyde, the same operation as Synthesis Example 1 was performed to obtain 281g of powder of Novolac-type Phenolic Resin (A-7). The Mw of Novolac-type Phenolic Resin (A-7) obtained by GPC method was 3,100.

[Component (B)] Synthesis Example 7 (Synthesis of polyimide precursor (B-1) containing ethylenically unsaturated groups) Under a dry nitrogen flow, in a 2000 mL four-necked flask equipped with a cooling tube, 125 g (0.023 mol) of pyrohexadecene anhydride and 115 g (0.023 mol) of 4,4-diaminodiphenyl ether were dissolved in 1602 g of N-methyl-2-pyrrolidone, and stirred at 100°C for 4 hours to react. After the reaction was completed, the solution was added to 2000 g of water, and the precipitate of the polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 80°C for 72 hours to obtain a polymer solid powder. 32.8 g of the obtained solid powder was dissolved in 76.5 g of 3-methoxy-n-butyl acetate. After cooling the mixed solution to 0°C, a solution obtained by dissolving 3.2 g of 2-methacryloyloxyethyl isocyanate in 3.2 g of 3-methoxy-n-butyl acetate was added dropwise. After the addition was completed, the mixture was stirred at 80°C for 1 hour to obtain a polymer solution containing ethylenically unsaturated groups. After the reaction was completed, the obtained solution was added to 1000 g of water, and the precipitate of the polymer solid containing ethylenically unsaturated groups was collected by filtration. The precipitate of the polymer solid was collected by filtration. The polymer solid containing ethylenically unsaturated groups was dried in a vacuum dryer at 80°C for 72 hours to obtain a polymer powder of a polyimide precursor (B-1) containing ethylenically unsaturated groups.

[Negative photosensitive resin composition] Example 1 A negative photosensitive resin composition (F-1) was obtained by dissolving 4.2 g of the phenol-novolac resin (A-1) powder obtained in Synthesis Example 1 as component (A), 1.8 g of the polymer powder of the polyimide precursor (B-1) containing an ethylenically unsaturated group obtained in Synthesis Example 7 as component (B), 4.0 g of a radical polymerizable compound (dopentatriol hexaacrylate: manufactured by Nippon Kayaku Co., Ltd.) as component (C), and 0.9 g of a photopolymerization initiator (NCI-831: manufactured by ADEKA Co., Ltd.) as component (D) in 98 g of γ-butyrolactone as component (E).

Examples 2 to 6, Comparative Examples 1 and 2 In Examples 2 to 6 and Comparative Example 1, except that the phenol-novolac resin (A-2) to (A-7) powders shown in Tables 1 and 2 are used as component (A), the same operation as in Example 1 is performed to obtain negative photosensitive resin compositions (F-2) to (F-7). In Comparative Example 2, the phenol-novolac resin (A-7) shown in Table 2 was used as component (A), and 3.4 g of benzofuran black pigment (BASF: Bk-S0100CF) and 1.3 g of dispersant (BYK Japan Co., Ltd.: BYK-167 DISPERBYK) were dissolved in 140 g of γ-butyrolactone solvent (E). The same operation as in Example 1 was performed to obtain a negative photosensitive resin composition (F-8).

[Evaluation] Using the negative photosensitive resin composition prepared in the embodiment and the comparative example, the resin compatibility, alkali solubility before exposure, visible light shielding property and elastic coefficient of the cured film were evaluated. (1) Evaluation of resin compatibility (film forming property) The negative photosensitive resin composition was applied to a silicon wafer with a diameter of 5 inches using a spin coater in a manner to a thickness of about 5 μm. Thereafter, the negative photosensitive resin composition was pre-baked at 120°C for 180 seconds to obtain a wafer with a photosensitive film formed thereon. The photosensitive film formed on the surface of the wafer was observed using an optical microscope to evaluate the presence or absence of depressions and unevenness. For the photosensitive film, the one without depressions and unevenness was considered to have good resin compatibility (™), and the one with depressions and unevenness was considered to have insufficient resin compatibility (Í). The evaluation results are shown in Tables 1 and 2.

(2) Alkali solubility before exposure A negative photosensitive resin composition was applied to a silicon wafer with a diameter of 5 inches using a spin coater in a manner to a thickness of about 5 μm. Thereafter, the wafer was pre-baked at 120°C for 180 seconds to obtain a wafer having a photosensitive film formed thereon. The obtained wafer was immersed in a vessel filled with 250 mL of a developer (2.38 wt% tetramethylammonium hydroxide aqueous solution (TMAH)) for 10 seconds. The wafer removed from the vessel was rinsed with pure water for 10 seconds, and the residue of the photosensitive film on the wafer was observed to evaluate the alkali solubility. The wafer without residue of the photosensitive film was rated as good (™), and the wafer with residue was rated as insufficient (Í). The evaluation results are shown in Table 1 and Table 2.

(3) Visible light shielding property of resin composition The negative photosensitive resin composition was diluted with γ-butyrolactone to a solid content concentration of 1%, and the visible light shielding property was evaluated using UV-vis (SolidSpec-3700 DUV manufactured by Shimadzu Corporation). The transmittance at 650nm was set to be good (™) if it was less than 10%, and it was set to be insufficient (Í) if it was more than 10%. The evaluation results are shown in Tables 1 and 2.

(4) Elastic coefficient of cured film A negative photosensitive resin composition was applied to a 5-inch diameter silicon wafer using a spin coater to a thickness of about 5 μm. Thereafter, the wafer was pre-baked at 120°C for 180 seconds to obtain a wafer having a photosensitive film formed thereon. The obtained wafer was irradiated with 200 mJ of ghi rays (g rays: wavelength 436 nm, h rays: wavelength 405 nm, i rays: wavelength 365 nm) using a USHIO multilight, and then pre-development baking (PEB) was performed on a 130°C hot plate for 120 seconds. Thereafter, the coated wafer was heated at 200°C for 1 hour in an inert gas environment. When the temperature of the heating device becomes below 50°C, the wafer is taken out and the film thickness is measured. The film hardness is measured by the nanoindentation method (ENT-2100: manufactured by ELIONIX Co., Ltd.). The indentation elastic coefficient of 8 GPa or more is set as good (™), and the one less than 8 GPa is set as insufficient (Í). The evaluation results are shown in Tables 1 and 2.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Ingredients (A) A-1 A-2 A-3 A-4 (a1):(a2):(a3):(a4) (Morr ratio) 1:1.01:1.28:0.80 1:1.01:0.99:0.99 1:1.01:1.45:0.63 1:1.01:0.83:1.24 (a1)+(a2):(a3)+(a4) (Morr ratio) 1:1.04 1:0.99 1:1.04 1:1.03 (a1):(a2) (Morr ratio) 0.50:0.50 0.50:0.50 0.50:0.50 0.50:0.50 (a3):(a4) (Morr ratio) 0.62:0.38 0.50:0.50 0.70:0.30 0.40:0.60 Black pigment without without without without Resin compatibility ™ ™ ™ ™ Alkaline solubility ™ ™ ™ ™ Visible light shielding ™ ™ ™ ™ Film hardness determination ™ ™ ™ ™

[Table 2] Embodiment 5 Embodiment 6 Comparison Example 1 Comparison Example 2 Ingredients (A) A-5 A-6 A-7 A-7 (a1):(a2):(a3):(a4) (Morr ratio) 1:0.33:0.85:0.53 1:3.02:2.56:1.60 1:0:0.64:0.40 1:0:0.64:0.40 (a1)+(a2):(a3)+(a4) (Morr ratio) 1:1.04 1:1.03 1:1.04 1:1.04 (a1):(a2) (Morr ratio) 0.75:0.25 0.25:0.75 1:0 1:0 (a3):(a4) (Morr ratio) 0.62:0.38 0.62:0.38 0.62:0.38 0.62:0.38 Black pigment without without without have Resin compatibility ™ ™ ™ ™ Alkaline solubility ™ ™ ™ Í Visible light shielding ™ ™ Í ™ Film hardness determination ™ ™ ™ ™

In Table 1 and Table 2, (a1), (a2), (a3), and (a4) respectively represent the structural unit (a1) derived from m-cresol, the structural unit (a2) derived from catechol, the structural unit (a3) derived from benzaldehyde, and the structural unit (a4) derived from salicylic aldehyde in the (A) phenol-novolac resin.

As can be seen from Table 1 and Table 2, the photosensitive film obtained from the negative photosensitive resin composition of the present invention has excellent compatibility and does not produce depressions and unevenness. In addition, it can be confirmed that it has alkaline solubility. In addition, it can be confirmed that it has excellent visible light shielding properties without adding black pigment.

without

without.

without.

Claims (7)

A negative photosensitive resin composition comprises the following components (A) to (E): (A) a novolac-type phenolic resin having a molar ratio of structural units (a1) derived from meta-cresol, structural units (a2) derived from catechol, structural units (a3) derived from benzaldehyde, and structural units (a4) derived from salaldehyde [(a1): (a2): (a3): (a4)] of 1: 0.25-4.0: 0.25-4.0: 0.25-4.0; (B) a polyimide containing ethylenically unsaturated groups, a polyimide precursor containing ethylenically unsaturated groups, a polyphenylene glycol containing ethylenically unsaturated groups, Azoles and polybenzoic acid containing ethylenically unsaturated groups (C) a free radical polymerizable compound; (D) a photopolymerization initiator; (E) an organic solvent. The negative photosensitive resin composition of claim 1, wherein the component (A) is a phenolic resin obtained by polycondensing m-cresol, catechol, benzaldehyde, and salicylic aldehyde in an organic solvent in a molar ratio of m-cresol:catechol:benzaldehyde:salicylic aldehyde=1:0.25-4.0:0.25-4.0:0.25-4.0 using an acid catalyst. The negative photosensitive resin composition of claim 1 or 2, wherein the total content of the structural unit (a1) derived from m-cresol, the structural unit (a2) derived from catechol, the structural unit (a3) derived from benzaldehyde, and the structural unit (a4) derived from salicylic aldehyde in the component (A) is 30 mass % or more. The negative photosensitive resin composition of claim 1 or 2, wherein the weight average molecular weight of the component (A) is not less than 1,000 and not more than 7,000. The negative photosensitive resin composition of claim 1 or 2, wherein the negative photosensitive resin composition contains 0 to 30 parts by weight of a colorant relative to 100 parts by weight of a solid component. A cured film is obtained from the negative photosensitive resin composition of claim 1 or 2. A resistive film is obtained from the negative photosensitive resin composition of claim 1 or 2.