TW202337927A - Curable resin composition, cured resin material thereof, semiconductor package and display device with that cured material - Google Patents

Abstract

The present invention provides a curable resin composition which can obtain a cured film which is not prone to generation of yellowing over time caused by electromagnetic waves having wavelengths from 340 nm to 480 nm. The curable resin composition includes (A) an alkali-soluble resin containing an unsaturated group, (B) a polymerizable compound having two or more unsaturated bonds, (C) an epoxy compound having two or more epoxy groups and (D) solvents. The component (A) above is a resin having an energy difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) calculated by quantum chemical calculations is 3.7 eV or more.

Description

Curable resin compositions, resin cured films, semiconductor packages and display devices

The invention relates to a curable resin composition, a resin cured film, a semiconductor package and a display device.

A protective film is used in semiconductor devices, image display devices, and the like to seal and protect each element on a substrate. As the protective film required to have transparency or heat resistance, a cured film in which a curable resin composition containing an alkali-soluble resin having an unsaturated group and a fluorene skeleton is applied, patterned, and cured can be used. membrane (for example, Patent Document 1, etc.).

[Prior art documents] [Patent Document] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-089716

[Problem to be solved by the invention] It is known that a cured film produced using an alkali-soluble resin having a fluorene skeleton as described in Patent Document 1 has excellent transparency and heat resistance. However, based on the knowledge of the present inventors, if the cured film absorbs the wavelength emitted by an ultraviolet-Light Emitting Diode (UV-LED) or a blue light-emitting diode (Blue-LED), it is 340 nm to Electromagnetic waves around 480 nm slowly deteriorate, sometimes causing yellowing over time.

The present invention was made in view of the above problems, and an object thereof is to provide a curable resin composition, a resin cured film formed from the curable resin composition, and a semiconductor package and a display device having the resin cured film. The curable resin composition can provide a cured film that is less likely to cause yellowing over time caused by electromagnetic waves with wavelengths around 340 nm to 480 nm.

[Technical means to solve problems] One aspect of the present invention for solving the above problems relates to the curable resin compositions of the following [1] to [4]. [1] A curable resin composition containing: (A) Alkali-soluble resin containing unsaturated groups, (B) Polymeric compounds having two or more unsaturated bonds, (C) Epoxy compounds having two or more epoxy groups, and (D) Solvent, The component (A) is calculated through quantum chemical calculations. The energy difference between the highest occupied molecular orbital (Highest Occupied Molecular Orbital, HOMO) and the lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital, LUMO) is more than 3.7 eV. of resin. [2] The curable resin composition according to [1], wherein the component (A) is a resin represented by the following general formula (1).

[Chemical 1]

(In formula (1), Ar is independently an aromatic hydrocarbon group with a carbon number of 6 or more and 14 or less, and a part of the hydrogen atoms constituting Ar may be selected from an alkyl group with a carbon number of 1 or more and 10 or less, an alkyl group with a carbon number of 6 or more and In the group consisting of an aryl group or arylalkyl group with 10 or less, a cycloalkyl group or cycloalkylalkyl group with a carbon number of 3 or more and 10 or less, an alkoxy group with a carbon number of 1 or more and 5 or less, and a halogen group. Substituent substitution; R ₁ is independently an alkylene group with a carbon number of 2 or more and 4 or less; l is independently a number from 0 to 3; G is independently a (meth)acrylyl group, or the following general formula (2) or a substituent represented by the following general formula (3); Y is a tetravalent carboxylic acid residue; Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and Z is at least One is a substituent represented by the following general formula (4); n is a number with an average value of 1 or more and 20 or less)

[Chemicalization 2]

[Chemical 3]

(In formula (2) and formula (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkyl aryl group having a carbon number of 2 or more and 10 or less, and R ₄ is a carbon number 2 or more and 20. The following saturated or unsaturated hydrocarbon groups, p is a number from 0 to 10, * is the bonding site)

[Chemical 4]

(In formula (4), W is a divalent or trivalent carboxylic acid residue, m is a number of 1 or 2, and * is a bonding site) [3] The curable resin composition according to [1] or [2], wherein the component (A) has a weight average molecular weight of 1,000 or more and 40,000 or less and an acid value of 50 mgKOH/g or more and 200 mgKOH/g. The following resins. [4] The curable resin composition according to any one of [1] to [3], including at least one of (E) a polymerization initiator and (F) a sensitizer.

Another aspect of the present invention relates to the resin cured film of the following [5]. [5] A resin cured film obtained by curing the curable resin composition according to any one of [1] to [4].

Still another aspect of the present invention relates to the semiconductor package described in [6] below. [6] A semiconductor package using the resin cured film according to [5] as at least one protective film.

Still another aspect of the present invention relates to the display device described in [7] below. [7] A display device using the resin cured film according to [5] as at least one protective film.

[Effects of the invention] According to the present invention, it is possible to provide a curable resin composition, a resin cured film formed from the curable resin composition, and a semiconductor package and display device having the resin cured film. The curable resin composition can be obtained A hardened film that is less likely to cause yellowing over time caused by electromagnetic waves with wavelengths around 340 nm to 480 nm.

1. Curable resin composition Hereinafter, the curable resin composition according to one embodiment of the present invention includes (A) an alkali-soluble resin containing an unsaturated group, (B) a polymerizable compound having two or more unsaturated bonds, and (C) having two unsaturated bonds. Epoxy compounds with more than epoxy groups and (D) solvents.

[(A) Ingredient] Component (A) is an alkali-soluble resin containing unsaturated groups. Component (A) is soluble in an alkali developer and can impart patterning properties to the curable resin composition.

The component (A) preferably has a polymerizable unsaturated group and an acidic group for expressing alkali solubility in one molecule, and more preferably has a polymerizable unsaturated group and a carboxyl group. The component (A) is not particularly limited as long as it is the above-mentioned resin, and various types of resins can be used. Since the component (A) has a polymerizable unsaturated group, it imparts excellent photocurability to the curable resin composition. Also, during curing, the molecular weight increases and it functions as a binder. In addition, since component (A) has an acidic group, it improves developability, patterning characteristics (pattern line width, pattern linearity), and the like.

In this embodiment, component (A) is a resin in which the energy difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) calculated by quantum chemical calculation is 3.7 eV or more. The energy difference between the HOMO and LUMO is greater than the energy of electromagnetic waves with wavelengths of 340 nm to 480 nm. Therefore, component (A) is less likely to absorb electromagnetic waves with wavelengths around 340 nm to 480 nm, and is less likely to undergo deterioration over time due to absorption of the electromagnetic waves.

The energy difference is based on the structural unit of component (A). In the most stable structure among the structural unit structures, the energy of HOMO and the energy of LUMO are calculated by Density Functional Theory (DFT). The energy difference between energies. The most stable structure can be determined by a known structure optimization method based on the molecular structure of component (A). In this specification, the energy of the HOMO and LUMO of component (A) is set using the "Gaussian16, Revision B.01" software package (Gaussian Inc.), for ( A) Molecular structure of the component, with charge 0 and multiplicity 1, by density functional method (DFT), using B3LYP as functional function and 6-31G(d) as basis function, using (Gaussian) input line "#B3LYP/6-31G(d)OPT") The energy of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the most stable structure of the molecular structure calculated. Among them, in the calculation of DFT and Time-Dependent Density Functional Theory (TDDFT), other computational science software with the same functions can be used. In addition, when performing the quantum scientific calculation, the energies of HOMO and LUMO are respectively obtained for the partial structures of the unconjugated (A) component, and the minimum value of the energy difference between the HOMO and LUMO obtained from these partial structures is set to is the energy difference.

The energy difference is preferably from 3.7 eV to 6.0 eV. If the energy difference is 3.7 eV or more, electromagnetic waves with wavelengths around 340 nm to 480 nm are less likely to be absorbed, thereby suppressing the time-dependent deterioration of component (A) and the accompanying time-dependent yellowing of the cured film. The upper limit of the energy difference is not particularly limited, but may be 6.0 eV or less.

The component (A) may be any alkali-soluble resin as long as it satisfies the necessary conditions for the energy difference. Examples of component (A) include: (i) obtained by reacting a reaction product of an epoxy compound having two or more epoxy groups and an unsaturated group-containing monocarboxylic acid with a polybasic acid carboxylic acid or anhydride thereof An unsaturated group-containing alkali-soluble resin, (ii) an unsaturated group-containing alkali-soluble resin as an acrylic (co)polymer, (iii) an unsaturated group-containing alkali-soluble resin as a polysiloxane containing multiple siloxane bonds Based alkali-soluble resin, etc.

Examples of the unsaturated group-containing monocarboxylic acid used in the synthesis of each component (A) include (meth)acrylic acid, and a combination of (meth)acrylic acid, succinic acid, maleic acid, and phthalic acid. Compounds obtained by reacting dicarboxylic acids or their acid monoanhydrides, etc.

In addition, "(meth)acrylic acid" is the general term for acrylic acid and methacrylic acid, "(meth)acrylyl" is the general term for acrylic acid and methacrylic acid, and "(meth)acrylate" is The general terms of acrylate and methacrylate refer to one or both of these.

The unsaturated group-containing alkali-soluble resin (i) is preferably a low molecular weight resin with an average polymerization degree of polyester produced by the reaction of a hydroxyl group and a polybasic acid carboxylic acid during production, of about 2 to 500.

Examples of the epoxy compound having two or more epoxy groups include: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, bisnaphthol fluorene type ring Oxygen compounds, diphenylfluorene type epoxy compounds, phenol novolak type epoxy compounds, o-cresol novolak type epoxy compounds, m-cresol novolak type epoxy compounds, p-cresol novolac type epoxy compounds, Phenol aralkyl type epoxy compounds, biphenyl type epoxy compounds (for example, jER YX4000: manufactured by Mitsubishi Chemical Co., Ltd., "jER" is a registered trademark of the said company), phenol novolac compounds containing a naphthalene skeleton (for example, , NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compound, trisphenolmethane type epoxy compound (for example, EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetraphenol B Examples of epoxy compounds with aromatic structures such as alkyl epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, and copolymers of methacrylic acid and glycidyl methacrylate include (methyl ) A copolymer of a monomer having a (meth)acrylyl group as a unit of glycidyl acrylate, hydrogenated bisphenol A diglycidyl ether (for example, Rikaresin) HBE-100: New Nippon Physics Co., Ltd. Manufactured by the company, "Rikaresin" is a registered trademark of the company) and other epoxy compounds with glycidyl groups, 1,4-cyclohexanedimethanol-bis-3,4-epoxycyclohexane Alkanecarboxylates, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175: manufactured by Huntsman, "Araldite" is a registered trademark of said company), bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128: manufactured by Dow Chemical Company), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (for example, Celloxide 2021P: manufactured by Daicel Co., Ltd. "Celloxide" is a registered trademark of the company), butanetetracarboxylic acid tetrakis(3,4-epoxy) cyclohexylmethyl) modified ε-caprolactone (for example, EPOLEAD GT401: manufactured by Daicel Co., Ltd., "EPOLEAD" is a registered trademark of the company), Epoxy compounds with an epoxy cyclohexyl group (for example, HiREM-1: manufactured by Shikoku Chemical Industry Co., Ltd.), multifunctional epoxy compounds with a dicyclopentadiene skeleton (for example, HP7200 series: DIC ) Co., Ltd.), 1,2-epoxy-4-(2-oxanyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g. , EHPE3150: manufactured by Daicel Co., Ltd.) and other alicyclic epoxy compounds, epoxylated polybutadiene (for example, NISSO)-PB·JP-100: manufactured by Nippon Soda Co., Ltd. , "NISSO-PB" is the registered trademark of the company), epoxy compounds with silicone skeleton, etc.

Examples of the unsaturated group-containing alkali-soluble resin as the acrylic (co)polymer in (ii) include (meth)acrylic acid, (meth)acrylate, etc. copolymers having (meth)acrylic acid. Resins with acyl and carboxyl groups. Examples of the resin include polymerizable unsaturated group-containing alkali-soluble resins obtained by copolymerizing (meth)acrylates containing glycidyl (meth)acrylate in a solvent. The obtained copolymer is reacted with (meth)acrylic acid and finally reacted with anhydride of dicarboxylic acid or tricarboxylic acid. The copolymer can be referred to: Japanese Patent Application Laid-Open No. 2014-111722, which contains a repeating unit of 20 moles derived from diester glycerol derived from esterifying the hydroxyl groups at both ends with (meth)acrylic acid. % to 90 mol%, and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds that can be copolymerized therewith, and the number average molecular weight (Mn) is 2000 to 20000 and the acid value is A copolymer of 35 mgKOH/g to 120 mgKOH/g; and a copolymer containing a unit derived from a (meth)acrylate compound and having a (meth)acryl group as shown in Japanese Patent Application Laid-Open No. 2018-141968 Polymers containing units of dicarboxylic acid residues or tricarboxylic acid residues, a weight average molecular weight (Mw) of 3000 to 50000, and an acid value of 30 mgKOH/g to 200 mgKOH/g contain polymerizable unsaturated groups. Alkali soluble resin.

Examples of the unsaturated group-containing alkali-soluble resin as the polysiloxane in (iii) include polysiloxane compounds having a (meth)acrylyl group and a carboxyl group. Examples of the compound include siloxane-modified acrylic resin obtained by reacting epoxy acrylate, siloxane diamine, and aromatic acid dianhydride (Japanese Patent Laid-Open No. 2002-226549, etc.); Siloxane-containing polyamide resin obtained by reacting siloxane diamine, aromatic diamine having an ethylenically unsaturated bond, and aromatic tetracarboxylic dianhydride (International Publication No. 2009/075217, etc.); Siloxane-containing polyamide resin obtained by reacting a diamine containing siloxane diamine and aromatic tetracarboxylic dianhydride (Japanese Patent Laid-Open No. 2008-070477, International Publication No. 2006/109514 , Japanese Patent Application Laid-Open No. 2010-204590, etc.); an alkali-soluble resin having a substituent in which a polymerizable double bond and a carboxyl group are bonded to an isocyanurate ring skeleton, obtained by: An epoxy silicone compound having an isocyanurate ring skeleton is reacted with a carboxylic acid containing a polymerizable double bond to obtain a polyol compound, and the obtained polyol compound is reacted with a dicarboxylic acid or its acid monoanhydride (Japanese Patent Special Publication No. 2011-141518, etc.).

For these resins, the energy difference between the energy of the HOMO and the energy of the LUMO can be increased, for example, by reducing the number of aromatic rings. Specifically, aromatic dicarboxylic acids, aromatic tricarboxylic acids, aromatic tetracarboxylic acids or their anhydrides, etc. used in the synthesis of conventional alkali-soluble resins are used by converting at least part of them into non-aromatic carboxylic acids. The acid or its anhydride can increase the energy difference between the energy of HOMO and the energy of LUMO to the above range.

From the viewpoint of suppressing decomposition of the resin cured film due to heat and raising the glass transition temperature to suppress deformation due to heat, component (A) preferably has a plurality of aromatic rings, and further improves the density. From the viewpoint of compatibility and solvent resistance, component (A) more preferably has a repeating unit containing a fluorene structure, and further preferably has a repeating unit containing a bisarylfluorene skeleton. For example, component (A) is preferably a resin represented by the following general formula (1).

[Chemistry 5]

In formula (1), Ar is independently an aromatic hydrocarbon group having a carbon number of 6 to 14, and a part of the hydrogen atoms constituting Ar may be an alkyl group having a carbon number of 1 to 10 or less, or an alkyl group having a carbon number of 6 to 10. Substituted by an aryl group or arylalkyl group, a cycloalkyl group or cycloalkylalkyl group having 3 or more carbon atoms and 10 or less carbon atoms, an alkoxy group or a halogen group having 1 or more carbon atoms and 5 or less carbon atoms. R ₁ is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3. G is independently a (meth)acrylyl group or a substituent represented by the following general formula (2) or the following general formula (3). Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one of Z is a substituent represented by the following general formula (4). n is a number whose average value is 1 or more and 20 or less.

[Chemical 6]

[Chemical 7]

In formula (2) and formula (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkyl aryl group having a carbon number of 2 to 10, and R ₄ is a carbon number of 2 to 20. A saturated or unsaturated hydrocarbon group, p is a number from 0 to 10, and * is a bonding site.

[Chemical 8]

In formula (4), W is a divalent or trivalent carboxylic acid residue, m is a number of 1 or 2, and * is a bonding site.

The resin represented by general formula (1) can be synthesized by the following method.

First, an epoxy compound (a-1) having a bisarylfluorene skeleton represented by the following general formula (5) and having several alkylene oxide modified groups in one molecule (hereinafter also referred to as "Epoxy compound (a-1)") and (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (6) and (methyl) represented by the following general formula (7) ) at least one reaction of an acrylic acid derivative to obtain a diol compound as (meth)acrylic acid epoxy ester. In addition, the bisarylfluorene skeleton is preferably a bisnaphtholfluorene skeleton or a bisphenolfluorene skeleton.

[Chemical 9]

In the formula (5), Ar is each independently an aromatic hydrocarbon group having a carbon number of 6 to 14. Part of the hydrogen atoms constituting Ar may be an alkyl group having a carbon number of 1 to 10 or less, or an alkyl group having a carbon number of 6 to 10. Substituted by an aryl group or arylalkyl group, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group or halogen group having 1 to 5 carbon atoms. R ₁ is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3.

[Chemical 10]

[Chemical 11]

In formula (6) and formula (7), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkyl aryl group having a carbon number of 2 or more and 10 or less, and R ₄ is a carbon number 2 or more and 20 or less. saturated or unsaturated hydrocarbon group, p is a number from 0 to 10.

A known method can be used for the reaction between the epoxy compound (a-1) and (meth)acrylic acid or a derivative thereof. For example, Japanese Patent Application Laid-Open No. 4-355450 describes that by using approximately 2 moles of (meth)acrylic acid per 1 mole of an epoxy compound having two epoxy groups, a polymerizable polymer-containing compound can be obtained. Unsaturated glycol compounds. In this embodiment, the compound obtained by the reaction is a polymerizable unsaturated group-containing diol (d) represented by the following general formula (8) (hereinafter, also simply referred to as "diol (d)" ).

[Chemical 12]

In the formula (8), Ar is each independently an aromatic hydrocarbon group having a carbon number of 6 or more and 14 or less. A part of the hydrogen atoms constituting Ar may be an alkyl group having a carbon number of 1 or more and 10 or less, or an alkyl group having a carbon number of 6 or more and 10 or less. Substituted by an aryl group or arylalkyl group, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group or halogen group having 1 to 5 carbon atoms. G is each independently a (meth)acrylyl group, a substituent represented by general formula (2) or general formula (3), and R ₁ is independently an alkylene group having 2 or more carbon atoms and 4 or less carbon atoms. l is independently a number from 0 to 3.

[Chemical 13]

[Chemical 14]

In formula (2) and formula (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkyl aryl group having a carbon number of 2 or more and 10 or less, and R ₄ is a carbon number 2 or more and 20 or less. A saturated or unsaturated hydrocarbon group, p is a number from 0 to 10, and * is a bonding site.

Secondly, the obtained diol (d), dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b) and tetracarboxylic acid or its acid dianhydride (c) are reacted to obtain the general formula (1) It represents an unsaturated group-containing curable resin having a carboxyl group and a polymerizable unsaturated group in one molecule.

The acid component is a polybasic acid component that can react with the hydroxyl group in the diol (d) molecule. In order to obtain the resin represented by the general formula (1), it is necessary to use dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) together with a tetracarboxylic acid or its acid dianhydride (c). The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, these carboxylic acid residues may also contain bonds containing foreign elements such as -O-, -S-, and carbonyl groups.

Examples of the dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) include: chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon Dicarboxylic acid or tricarboxylic acid and their acid monoanhydrides, etc.

Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include: succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid , malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc., and these dicarboxylic acids with optional substituents introduced Or tricarboxylic acid, etc.

Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include: cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid Hydrophthalic acid, methylendomethyltetrahydrophthalic acid, chlorobacteric acid, hexahydrotrimellitic acid, norbornane dicarboxylic acid, and these dicarboxylic acids with optional substituents introduced Or tricarboxylic acid, etc.

Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include: phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid and trimellitic acid etc., and these dicarboxylic acids or tricarboxylic acids introduced with optional substituents.

Among these, the dicarboxylic acid or tricarboxylic acid is preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid, and more preferably amber acid, itaconic acid and tetrahydrophthalic acid.

The dicarboxylic acid or tricarboxylic acid is preferably its acid monoanhydride.

In addition, from the viewpoint of being able to form a finer pattern, these dicarboxylic acids or tricarboxylic acids preferably have a cyclic structure. More specifically, it is preferable to use alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or their acid monoanhydrides. If dicarboxylic acid or tricarboxylic acid having a cyclic structure is used, the cyclic structure is introduced at the terminal and the fluidity of the resin is reduced. Therefore, the peeling of the coating film during pattern formation can be suppressed, so it is considered that a fine pattern can be formed. .

Examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid and their acid dianhydride, and the like. Among these, chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids and their acid dianhydrides are preferred.

Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and these chain formulas in which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups are introduced. Hydrocarbon tetracarboxylic acids, etc.

Examples of the alicyclic hydrocarbon tetracarboxylic acid include: cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid and norbornane tetracarboxylic acid, and these alicyclic tetracarboxylic acids in which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups are introduced.

Examples of the aromatic hydrocarbon tetracarboxylic acid include: pyromellitic acid, benzophenone tetracarboxylic acid, diphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl tetracarboxylic acid, naphthalene tetracarboxylic acid -1,4,5,8-tetracarboxylic acid and naphthalene-2,3,6,7-tetracarboxylic acid, etc. From the viewpoint of increasing LUMO to further increase the energy difference between HOMO and LUNO, these aromatic hydrocarbon tetracarboxylic acids are preferably prepared by introducing electron-donating atoms such as oxygen into the aromatic ring of the acid anhydride part or dispersing them in the acid anhydride skeleton. Aromatic hydrocarbon tetracarboxylic acid in unconjugated multiple aromatic rings. For example, the tetracarboxylic acid is preferably diphenyl ether tetracarboxylic acid.

As the tetracarboxylic acid, its acid dianhydride is preferably used.

In addition, trimellitic anhydride aryl esters may be used instead of the tetracarboxylic acid or its acid dianhydride (c). The so-called trimellitic anhydride aryl esters are compounds produced by the method described in International Publication No. 2010/074065, for example, and are structurally aromatic diols (naphthalenediol, biphenol and terphenyldiol). It is an acid dianhydride in the form in which two hydroxyl groups of two molecules of trimellitic anhydride react with each other and form an ester bond with the carboxyl groups of two molecules of trimellitic anhydride.

The reaction method of the diol (d), the acid component (b) and the acid component (c) is not particularly limited, and a known method can be used. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method of reacting (meth)acrylic acid epoxy ester and tetracarboxylic dianhydride at a reaction temperature of 90°C to 140°C.

In this case, in order to make the terminal of the compound a carboxyl group, it is preferable to use (meth)acrylic acid epoxy ester (diol (d)), dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) and tetracarboxylic acid. The reaction is carried out so that the molar ratio of the acid dianhydride (c) becomes (d): (b): (c) = 1.0: 0.01 to 1.0: 0.2 to 1.0.

For example, when using acid monoanhydride (b) or acid dianhydride (c), it is preferable to use the molar amount of the acid component [(b)/2+(c)] relative to the diol (d). The reaction is carried out so that the ratio [[(b)/2+(c)]/(d)] is greater than 0.5 and 1.0 or less. If the molar ratio is 1.0 or less, the terminal of the unsaturated group-containing curable resin represented by the general formula (1) will not become an acid anhydride, so the content of unreacted acid dianhydride can be suppressed from increasing, thereby improving hardening. Stability of sexual compositions over time. In addition, if the molar ratio is greater than 0.5, the remaining amount of unreacted components in the polymerizable unsaturated group-containing diol (d) can be suppressed from increasing, thereby improving the stability of the curable composition over time. In addition, for the purpose of adjusting the acid value and molecular weight of the unsaturated group-containing curable resin represented by the general formula (1), the molar ratio of each component (b), (c) and (d) can be adjusted to the desired value. Any changes may be made within the above range.

In addition, the synthesis of the diol (d) and the subsequent reaction of the polycarboxylic acid or its anhydride are usually carried out in a solvent using a catalyst if necessary.

Examples of the solvent include: cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, diethylene glycol dimethyl ether, ethyl carbitol acetate, butyl High-boiling ether or ester solvents such as carbitol acetate and propylene glycol monomethyl ether acetate, and ketone solvents such as cyclohexanone and diisobutyl ketone. In addition, the reaction conditions of the solvent, catalyst, etc. used are not particularly limited. For example, it is preferable to use a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

In addition, the reaction between the epoxy group and the carboxyl group or hydroxyl group is preferably carried out using a catalyst. As the catalyst, Japanese Patent Application Laid-Open No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine and tris(2,6-dimethyl Phosphines such as oxyphenyl)phosphine, etc.

When the resin represented by the general formula (1) is used as the component (A), from the viewpoint of suppressing thermal decomposition of the resin cured film and increasing the glass transition temperature to suppress thermal deformation. , the energy of the LUMO of component (A) is preferably -2.0 eV or more. If the energy of LUMO is -2.0 eV or more, it can be achieved by appropriately increasing the aromatic ring in the resin (specifically, derived from dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), or tetracarboxylic acid or its acid dianhydride (aromatic ring of c)) to improve the heat resistance of the resin cured film.

The component (A) is preferably a compound with a weight average molecular weight (Mw) of 1,000 or more and 40,000 or less, and more preferably a compound with a weight average molecular weight (Mw) of 2,000 or more and 20,000 or less. The higher the Mw of the component (A) is, the more the adhesiveness and flexibility of the resin cured film are improved, and the easier it is to adjust the crosslinking density. On the other hand, the lower the Mw of the component (A) is, the more the solubility of the component (A) in the solvent is improved, the compatibility with the component (B) is improved, and the white turbidity suppression property of the resin cured film is improved. , flatness and patterning. From the viewpoint of further improving the compatibility with component (B), the Mw of component (A) is preferably from 1,000 to 30,000, and more preferably from 1,500 to 25,000. When the resin represented by the general formula (1) is used as the component (A), the Mw of the component (A) is preferably from 1,000 to 6,000, more preferably from 2,000 to 4,000. In this embodiment, a compound having a relatively large acrylic acid group equivalent and a large molecular weight is used as the component (B). For example, when the molecular weight (Mw) of component (B) is 3,000 or more, the compatibility of these components can be sufficiently improved by setting the Mw of component (A) to 6,000 or less.

From the same viewpoint, the acid value of component (A) is preferably 30 mgKOH/g or more and 200 mgKOH/g or less.

In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) of each component can be determined using a gel permeation chromatograph (GPC) (for example, "HLC-8220GPC" (Tosoh) Styrene conversion value calculated from Tosoh Co., Ltd.). In addition, the acid value can be a value obtained using a potentiometric titration device (for example, "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.)). For compounds whose molecular weight can be calculated based on the structure, such as monomers, the value calculated based on the structure can be used as the molecular weight of the compound.

The content of component (A) is preferably not less than 10% by mass and not more than 90% by mass, more preferably not less than 20% by mass and not more than 80% by mass, relative to the total mass of solid components. When the patterning characteristics are important, furthermore, Preferably it is 40 mass % or more and 80 mass % or less. If the content of component (A) is 10% by mass or more, a high-resolution pattern can be formed.

In addition, only one type of component (A) may be used alone, or two or more types may be used in combination.

[(B)Component] The component (B) is a polymerizable compound having two or more unsaturated bonds. Examples of the component (B) include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. (meth)acrylate, tetramethylglycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane Alkane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol triacrylate (meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphorus (Meth)acrylates such as alkylene oxide-modified hexa(meth)acrylate of nitrile (phosphazene) and caprolactone-modified dipentaerythritol hexa(meth)acrylate. Only one type of these polymerizable compounds may be used alone, or two or more types may be used in combination. The component (B) only needs to function to cross-link the molecules of the component (A). From the viewpoint of further fully exerting the above function, it is preferable to use a component having three or more unsaturated bonds. Moreover, the acrylic acid group equivalent weight calculated by dividing the molecular weight of the polymerizable compound by the number of (meth)acrylyl groups in one molecule is preferably 50 to 300, and the acrylic acid group equivalent weight is more preferably 80 to 200. In addition, component (B) does not have free carboxyl groups.

Examples of the component (B) include dendritic polymers having (meth)acrylyl groups. An example of a dendritic polymer having a (meth)acrylyl group is the addition of a polyvalent thiol group to a part of the carbon-carbon double bond in the (meth)acrylyl group of a polyfunctional (meth)acrylate. dendrimers obtained from compounds. Specifically, it includes: obtained by reacting the (meth)acrylyl group of the polyfunctional (meth)acrylate represented by the following general formula (9) and the polyvalent thiol compound represented by the following general formula (10) dendrimers, etc.

[Chemical 15]

(In formula (9), R ₅ is a hydrogen atom or a methyl group, and R ₆ is the residual portion after q hydroxyl groups among the k hydroxyl groups of R ₇ (OH) _k are supplied to the ester bond in the formula; preferably R ₇ (OH) _k is a polyol having a non-aromatic linear or branched hydrocarbon skeleton with a carbon number of 2 to 8, or multiple molecules of the polyol are condensed through dehydration of alcohol through ether bonds Linked polyol ethers, or esters of these polyols or polyol ethers and hydroxy acids; k and q independently represent integers from 2 to 20, but k≧q)

[Chemical 16]

(In formula (10), R ₈ is a single bond or a divalent to hexavalent hydrocarbon group having 1 to 6 carbon atoms. When R ₈ is a single bond, r is 2, and R ₈ is a divalent to hexavalent hydrocarbon group. When , r is the same number as the valence of R ₈ )

Examples of the polyfunctional (meth)acrylate represented by the general formula (9) include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and trimethylolpropane. Tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate (meth)acrylate, dipentaerythritol hexa(meth)acrylate and caprolactone-modified pentaerythritol tri(meth)acrylate. Only one type of these compounds may be used alone, or two or more types may be used in combination.

Examples of the polyvalent mercapto compound represented by the general formula (10) include: trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(mercaptoacetate) ), pentaerythritol tris(mercaptoacetate), pentaerythritol tetrakis(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate) and dipentaerythritol hexa(mercaptopropionate), etc. Only one type of these compounds may be used alone, or two or more types may be used in combination.

Here, the Michael addition of the polyvalent thiol compound represented by the general formula (10) to the polyfunctional (meth)acrylate represented by the general formula (9) is preferably such that the compound represented by the general formula (9) is When the total amount of carbon-carbon double bonds present is set to 100 mol%, the carbon-carbon double bonds are retained in the range of 0.1 mol% to 50 mol% so that the obtained dendritic polymer is Radiation polymerization based on carbon-carbon double bonds can then be carried out.

For example, regarding the thiol group of the polyvalent thiol compound represented by the general formula (10) and the carbon-carbon double bond of the polyfunctional (meth)acrylate represented by the general formula (9) (in the general formula (9), it means The addition ratio of the double bond represented by CH ₂ =C(R ₅ )- (called double bond when calculating the molar ratio), the molar ratio of mercapto group/double bond is preferably 1/100 to 1/3 , better is 1/50～1/5, particularly best is 1/20～1/8.

In addition, the dendritic polymer preferably has an amount of functional groups sufficient to carry out radiation polymerization. Therefore, the acrylic acid group equivalent weight of the dendritic polymer is preferably in the range of 100 to 10,000. In addition, the dendritic polymer having a (meth)acrylyl group has a large molecular weight, so it can prevent the developer from penetrating into the exposed part of the coating film during pattern formation, and can prevent the resin from penetrating into the exposed part of the coating film during actual hardening (post-baking). Yellowing of sclerotic membrane. For example, the weight average molecular weight (Mw) of the dendritic polymer having a (meth)acrylyl group is preferably in the range of 1,000 or more and 20,000 or less, more preferably in the range of 7,000 or more and 20,000 or less, and still more preferably It is in the range of above 8,000 and below 15,000.

The blending ratio of component (A) and component (B) is preferably 30/70 to 90/10, more preferably 60/40 to 80/20 in terms of mass ratio (A)/(B). If the blending ratio of component (A) is 30/70 or more, the cured product after photocuring is less likely to become brittle, and the acid value of the coating film in the unexposed portion is less likely to become low, so dissolution in the alkali developer can be suppressed. Decrease in sex. Therefore, disadvantages such as burrs at the edges of the pattern or blurring are less likely to occur. In addition, when the blending ratio of component (A) is 90/10 or less, the photoreactive functional group occupies a sufficient proportion in the resin, and therefore the desired crosslinked structure can be formed. In addition, since the acid value of the resin component is not too high, the solubility of the exposed portion in an alkali developer is less likely to increase, thereby suppressing the formed pattern from becoming thinner than the target line width or the pattern from being missing.

[(C)Component] (C) The component is an epoxy compound having two or more epoxy groups. (C) The component can improve the chemical resistance of the resin cured film and improve the moisture resistance and adhesion of the resin cured film. This is thought to be because the carboxyl group of component (A) and the epoxy group of component (C) are protected by reacting during the actual hardening (post-baking), thereby reducing moisture absorption of component (A) due to the carboxyl group. sex.

Examples of the component (C) include the epoxy compound having two or more epoxy groups described for the component (A). In addition, only one type of these compounds may be used, or two or more types may be used in combination.

Among these, preferred are a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol fluorene type epoxy compound, a bisnaphthol fluorene type epoxy compound, a phenol novolak type epoxy compound, and a cresol novolac type epoxy compound. Varnish type epoxy compound, biphenyl type epoxy compound, more preferably biphenyl type epoxy compound. Biphenyl-type epoxy compounds can achieve both mechanical strength and chemical resistance of cured products that meet required characteristics.

The epoxy equivalent of the component (C) is preferably from 100 g/eq to 300 g/eq, more preferably from 100 g/eq to 250 g/eq. In addition, the number average molecular weight (Mn) of component (C) is preferably from 100 to 5,000. If the epoxy equivalent of component (C) is 100 g/eq or more, the solvent resistance of the cured film will be improved. If the epoxy equivalent of component (C) is 300 g/eq or less, sufficient alkali resistance can be maintained even when an alkaline chemical solution is used in the subsequent process. In addition, if the Mn of component (C) is 5000 or less, sufficient alkali resistance can be maintained even when an alkaline chemical solution is used in a subsequent process.

In addition, the epoxy equivalent of component (C) can be determined by titrating with a 1/10N-perchloric acid solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

The content of component (C) is preferably 1 mass% or more and 30 mass% or less, more preferably 3 mass% or more and 25 mass% or less relative to the total mass of solid components. If the content of the component (C) is 1% by mass or more, the chemical resistance and moisture-resistant adhesion of the resin cured film can be further improved. If the content of the component (C) is 30% by mass or less, the adhesiveness of the resin cured film to the substrate can be further improved.

[(D)Component] (D) Component is a solvent.

Examples of component (D) include: methanol, ethanol, n-propanol, isopropyl alcohol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy- Alcohols such as 2-butanone and diacetone alcohol; terpenes such as α-terpineol or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone Class; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol Glycol ethers such as alcohol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; ethyl acetate , butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate Acid ester, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate , propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other acetate esters. (D) Only one of the components may be used alone, or two or more may be used in combination.

The content of component (D) changes depending on the target viscosity, but is preferably 30 mass% or more and 90 mass% or less based on the total mass of the curable resin composition. If the content of component (D) is 30% by mass or more, the viscosity can be set to be easy to apply the curable resin composition to the substrate. If it is 90% by mass or less, the time required to apply the curable resin composition to the substrate can be shortened. The time required for drying after application.

[(E) component, (F) component] Component (E) is a polymerization initiator, and component (F) is a sensitizer.

The component (E) is not particularly limited as long as it is a compound that can initiate polymerization of a compound that has a polymerizable unsaturated bond and is capable of addition polymerization. Examples of the component (E) include photopolymerization initiators such as acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and oxime compounds. In addition, in this specification, a photopolymerization initiator is used in the meaning including a sensitizer.

Examples of acetophenone compounds include: acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethyl ketal, 2-Hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholinyl -1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2- Oligomers of hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc.

Examples of triazine compounds include: 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)- 1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis (Trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2 -(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis (Trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5 -Triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(propynyl)-4,6- Bis(trichloromethyl)-1,3,5-triazine, etc.

Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-tert-butyl ether, and the like.

Examples of benzophenone compounds include: benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl Sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(N, N-diethylamino) benzophenone, etc.

Examples of thioxanthone compounds include: thioxanthone, 2-chlorothioxanthone, 2-methylthianthrone, 2-isopropylthianthrone, 4-isopropylthianthrone Anthrone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxy thioxanthone, etc.

Examples of imidazole compounds include: 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl) Imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2 , 4,5-triarylimidazole dimer, etc.

Examples of oxime compounds include: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-oxazol-3-yl]-bicycloheptyl-1-one oxime -O-acetate, 1-[9-ethyl-6-(2-methylbenzyl)-9H-oxazol-3-yl]-adamantylmethane-1-one oxime-O- Benzoate, 1-[9-ethyl-6-(2-methylbenzyl)-9H-oxazol-3-yl]-adamantylmethane-1-one oxime-O-acetic acid Ester, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-oxazol-3-yl]-tetrahydrofurylmethane-1-oxime-O-benzoate, 1 -[9-ethyl-6-(2-methylbenzoyl)-9H-terazol-3-yl]-tetrahydrofurylmethane-1-one oxime-O-acetate, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-oxazol-3-yl]-thiophenylmethane-1-one oxime-O-benzoate, 1-[9-ethyl -6-(2-methylbenzoyl)-9H-oxazol-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6- (2-methylbenzoyl)-9H-oxazol-3-yl]-morpholinylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2 -Methylbenzoyl)-9H-triazol-3-yl]-morpholinylmethane-1-oxime-O-acetate, 1-[9-ethyl-6-(2-methyl Benzyl)-9H-oxazol-3-yl]-ethane-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzene Formyl)-9H-oxazol-3-yl]-ethane-1-oxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzyl) Benzyl)-9H-oxazol-3-yl]-ethane-1-one oxime-O-adamantane carboxylate, 1-[4-(phenylhydrogenthio)phenyl]octane-1, 2-diketone=2-O-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)oxazol-3-yl]ethanone-O-acetyl oxime Oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethyl ketone, 1-[7-(2-methyl Benzyl benzyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(O-acetyl oxime), ethanone, 1-(9,9-dibutyl-7 -Nitro-9H-fluoren-2-yl)-1-O-acetyl oxime, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-oxazole -3-yl]-,1-(O-acetyl oxime), 1,2-octadiene, 1-[4-(phenylthio)-,2-(O-benzyl oxime)] , Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-triazol-3-yl]-, 1-(O-acetyl oxime), 1-( 4-Phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiophenyl)butane-1,2 -Diketone-2-oxime-O-acetate, 1-(4-methylhydrothiophenyl)butane-1-oxime-O-acetate, 4-ethoxy-2-methyl Phenyl-9-ethyl-6-nitro-9H-triazolo-3-yl-O-acetyl oxime, 5-(4-isopropylphenylthio)-1,2-indane Dione, 2-(O-acetyl oxime), etc. Only one type of the photopolymerization initiator may be used alone, or two or more types may be used in combination.

Other examples of the acyl oxime-based photopolymerization initiator include an O-acyl oxime-based photopolymerization initiator represented by the general formula (11) or the general formula (12).

[Chemical 17]

In formula (11), R ₉ and R ₁₀ each independently represent an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an alkyl group having 4 to 12 carbon atoms. Heterocyclic group, R ₁₁ represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group may be substituted by an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene group may contain an unsaturated bond. , ether bond, thioether bond, ester bond. In addition, the alkyl group may be any linear, branched or cyclic alkyl group.

[Chemical 18]

(In formula (12), R ₁₂ and R ₁₃ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group, cycloalkylalkyl group having 4 to 10 carbon atoms, or Alkylcycloalkyl, or phenyl which may be substituted by an alkyl group having 1 to 6 carbon atoms; R ₁₄ is each independently a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and the Part of the -CH ₂ - group in the alkyl or alkenyl group may be substituted with an -O- group; furthermore, part of the hydrogen atoms in these R ₁₂ to R ₁₄ groups may also be substituted with a halogen atom)

In addition, the component (E) preferably has a molar absorption coefficient at 365 nm of 10,000 L/mol·cm or more. Since this type of photopolymerization initiator has high sensitivity, it can ensure sufficient photosensitivity even for curable resin compositions containing component (B) with a relatively large acrylic acid group equivalent, and can fully improve the development of the curable resin composition. properties (resolution). Examples of such photopolymerization initiators include: Omnirad 1312 (manufactured by IGM Resins B.V., "Omnirad" is a registered trademark of the company) and ADEKA ARKLS NCI-831 (manufactured by ADEKA Co., Ltd., "ADEKA ARKLS" is a registered trademark of the company), etc.

In this specification, the molar absorption coefficient of the photopolymerization initiator can be set to the following value using a UV-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.), The value obtained by measuring the absorbance of an acetonitrile solution with a concentration of 0.001% by weight in a quartz unit with an optical path length of 1 cm.

In addition, as (E) component, a thermal polymerization initiator can also be used. As examples of thermal polymerization initiators, benzoyl peroxide, lauryl peroxide, di-tert-butyl hexahydroterephthalate, tert-butyl peroxy-2-ethylhexanoate, 1, 1-tert-butylperoxy-3,3,5-trimethylcyclohexane and other organic peroxides; azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethyl Valeronitrile, azobiscyclohexanone-1-carbonitrile, azobibenzylcarbonate, 1,1'-azobis(1-acetyloxy-1-phenylethane), 2,2'- Azo compounds such as azobis(methyl isobutyrate); water-soluble catalysts such as potassium persulfate and ammonium persulfate; and redox catalysts obtained by combining peroxides or persulfates with reducing agents. Common free radical polymerization Any of the compounds that can be used. The thermal polymerization initiator can be selected taking into account the storage stability of the thermosetting resin composition of the present invention or the formation conditions of the cured product.

In addition, as the component (E), an active radical generator or an acid generator can also be used.

Examples of active free radical generators include: 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5, 5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9,10-phenanthrenequinone, camphorquinone, phenyl Methyl glyoxylate, titanocene compounds, etc.

Examples of acid generators include: 4-hydroxyphenyldimethylsulfonate p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonate hexafluoroantimonate, and 4-acetyloxyphenyldimethyl Sulfonium p-toluenesulfonate, 4-acetyloxyphenyl-methyl-benzylsonium hexafluoroantimonate, triphenylsonium p-toluenesulfonate, triphenylsonium hexafluoroantimonate, diphenyl Onium salts such as p-toluene sulfonate, diphenyl iodonium hexafluoroantimonate, nitrobenzyl toluene sulfonate, benzoin toluene sulfonate, etc.

Examples of (F) sensitizers include: triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, benzophenone, 4,4'-bisdimethylaminobenzophenone ( Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, acetophenone, Acetophenones such as 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butylacetophenone Ketones; Benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid methyl ester, 4-dimethyl Ethyl aminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, N,N-dimethyl p-toluidine, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 4-benzoyl-4'-methyl-di Phenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone and 3,3'-dimethyl-4-methoxy benzophenone series such as methyl benzophenone; 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone and 2,4- Thioxanthone series such as dichlorothioxanthone; 4,4'-bis(dimethylamino)benzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'- Amino benzophenone series such as bis(ethylmethylamino)benzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone, etc. .

The content of component (E) is preferably not less than 1 part by mass and not more than 30 parts by mass, more preferably not less than 2 parts by mass and not more than 10 parts by mass, based on 100 parts by mass of the total of component (A) and (B). In addition, when using a acyl oxime-based photopolymerization initiator as the component (D), the content of the component (E) is preferably 0.5 mass parts with respect to 100 parts by mass of the total of the component (A) and the component (B). Part by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less. If the content of the component (E) is equal to or higher than the lower limit, the photopolymerization speed will be moderate and sufficient sensitivity can be ensured. In addition, when the content of component (E) is below the upper limit, line widths faithful to the mask can be reproduced and pattern edges can be made clear.

When the total mass of component (E) is 100 parts by mass, the content of component (F) is preferably from 0.5 parts by mass to 400 parts by mass, more preferably from 1 part by mass to 300 parts by mass. If the content of the photosensitizer is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be increased and the speed of photopolymerization can be accelerated. In addition, if the content of the photosensitizer is 400 parts by mass or less, an excessive increase in sensitivity can be suppressed, and burning, peeling residue, etc. are less likely to occur during light irradiation.

[Other ingredients] Other resin components, hardeners, hardening accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers, leveling agents, defoaming agents, ultraviolet absorbers, surface coatings, etc. can also be blended into the curable resin composition as needed. Additives such as active agents, coupling agents and viscosity adjusters.

Examples of other resin components include vinyl resin, polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, and melamine resin.

Examples of the hardener include amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamine, Lewis acid complex compounds, and the like that contribute to hardening of the epoxy resin.

Examples of hardening accelerators include: tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organic metal compounds, and imidazoles that contribute to hardening acceleration of epoxy resins. wait.

Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, and the like.

Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of fillers include: glass fiber, silica, mica, alumina, etc.

Examples of leveling agents and defoaming agents include silicone-based, fluorine-based, and acrylic-based compounds.

Examples of ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, and the like.

Examples of surfactants include: anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; Amphoteric surfactants such as lauryldimethylamine oxide, laurylcarboxymethylhydroxyethylimidazolium betaine, etc.; nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, etc. Surfactants; silicone surfactants with polydimethylsiloxane as the main skeleton; fluorine surfactants, etc.

Examples of the coupling agent include silane coupling agents. The silane coupling agent is preferably a silane coupling agent having an amino group, an isocyanate group, a urea group, an epoxy group, a vinyl group, a (meth)acrylyl group, a mercapto group, etc. as a reactive group, and more preferably a silane coupling agent having an epoxy group, Silane coupling agent with isocyanate group and (meth)acrylyl group as reactive groups. Specific examples of the coupling agent include: 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-isocyanatopropyltriethyl Oxysilane, 3-ureidopropyltriethoxysilane, etc.

[Manufacturing method] The curable resin composition can be obtained by mixing the respective components.

2.Use The curable resin composition can form a resin cured film by irradiation with radiation, and can be used as a liquid crystal display, an organic electroluminescence (EL) display device, a micron light emitting diode (μLED) display device, and Protective layer in various display devices such as display devices using quantum dots; insulating films for printed wiring boards and semiconductor packages, such as solder resist layers, plating resist layers, etching resist layers and other resist layers, multi-layer Interlayer insulating layers and gas barrier films such as printed wiring boards; sealing materials for semiconductor light-emitting components such as lenses and light-emitting diodes (LEDs); top coats of paint or ink; hard coatings of plastics; anti-rust films of metals wait. In addition, in this specification, the semiconductor package refers to a flip chip package, a wafer level package, etc., and also refers to a package formed to include a semiconductor such as a flip chip package stacked on an interposer. A package containing a chip that can be mounted on a printed circuit board. It is particularly useful for optical semiconductor packages combined with light-emitting elements (preferably LEDs such as UV-LED and Blue-LED). In addition, the thermosetting resin composition itself can also be molded and applied to the production of films, substrates, plastic parts, optical lenses, etc.

In particular, since the resin cured film is less likely to cause yellowing over time caused by electromagnetic waves with wavelengths around 340 nm to 480 nm, it is suitable for use in light sources that emit the electromagnetic waves (such as UV-LED or Blue-LED). etc.), the disadvantages caused by yellowing over time can be suppressed. From this point of view, the resin cured film is preferably disposed closer to the light source, especially when used as a protective film (sealing material) for arranging and sealing the light source on a mounting substrate. When compared with other materials, the effect of suppressing the disadvantages caused by yellowing over time is remarkable.

The resin cured film can be produced, for example, by applying the curable resin composition to a substrate or the like, drying it, and curing it by irradiating (exposure) light (including ultraviolet rays, radiation, etc.). In this case, by using a photomask or the like to set up portions irradiated with light and portions not irradiated with light, curing only the portion irradiated with light, and dissolving other portions with an alkali solution, a cured product with a desired pattern can be obtained.

When applying the curable resin composition to the substrate, known solution dipping methods, spray methods, methods using a roll coater, a land coater machine, a slit coater, or a rotary machine can also be used. Either way.

After the curable resin composition is applied to a desired thickness by these methods, the solvent is removed (prebaking) to form a film. Prebaking is performed by heating using an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in the pre-baking can be appropriately selected according to the solvent used. For example, it is performed at a temperature of 80°C to 120°C for 1 minute to 10 minutes.

Examples of radiation used for exposure include visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc., and radiation with a wavelength in the range of 250 nm to 450 nm is preferred.

Alkali development can be performed using, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. as a developer. These developers can be selected according to the characteristics of the resin layer, and surfactants can also be added if necessary. Development is preferably performed at a temperature of 20°C to 35°C. By using commercially available developing machines, ultrasonic cleaning machines, etc., fine images can be formed precisely. In addition, after alkali development, water washing is usually performed. Examples of the development treatment method include a shower development method, a spray development method, a dip development method, a puddle development method, and the like.

After developing in the above manner, heat treatment (post-baking) is performed at a temperature of 180°C to 250°C for 20 minutes to 100 minutes. The post-baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. Post-baking can be performed by heating with an oven, a hot plate, etc., similarly to pre-baking.

Thereafter, polymerization or curing (sometimes both are collectively referred to as curing) is completed by heat, and a cured film such as an insulating film can be obtained. The hardening temperature at this time is preferably in the range of 160°C to 250°C.

In addition, when producing a resin cured film by thermal curing using a thermal polymerization initiator, the curable resin composition may be applied to a substrate or the like, dried and heat-treated. The conditions for coating, drying (prebaking), and heat treatment (postbaking) at this time can be the same as those described for the method including the exposure and alkali development.

[Example] Hereinafter, embodiments of the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to these.

First, description will be given starting with synthesis examples of the unsaturated group-containing alkali-soluble resin as component (A). However, unless otherwise specified, the evaluation of the resins in these synthesis examples is performed as follows.

In addition, for various measuring equipment, when the same model is used, the name of the equipment manufacturer is omitted from the second place. In addition, in the Examples, all the glass substrates used in the production of the resin cured film-attached substrate for measurement were subjected to the same treatment before use. In addition, regarding the content of each component, when the first decimal place is 0, the description below the decimal point may be omitted.

[Solid content concentration] The weight [W 1 (g)] after impregnating 1 g of the resin solution obtained in the synthesis example into a glass filter [weight: W ₀ (g)] and weighing it at 160° _C The weight [W ₂ (g)] after heating for 2 hours was calculated using the following formula. Solid content concentration (weight%) =100×(W ₂ -W ₀ )/(W ₁ -W ₀ )

[acid value] The acid value was determined by dissolving the resin solution in dioxane, titrating with a 1/10N-KOH aqueous solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[Molecular weight] Molecular weight was measured using gel permeation chromatograph (GPC) "HLC-8220GPC" (manufactured by Tosoh Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 pieces) + TSKgelSuper H -3000 (1 stick) + TSKgelSuper H-4000 (1 stick) + TSKgelSuper H-5000 (1 stick) (manufactured by Tosoh Co., Ltd., temperature: 40°C, speed: 0.6 ml/min) for measurement , and calculated the weight average molecular weight (Mw) as a converted value for standard polystyrene (PS-oligomer set manufactured by Tosoh Co., Ltd.).

The abbreviations used in synthesis examples are as follows. BPFE: bisphenol fluorene type epoxy resin (in the general formula (5), Ar is a benzene ring and l is 0 epoxy resin, epoxy equivalent 256 g/eq) TPP: triphenyl phosphine (TPP) AA: acrylic acid (AA) PGMEA: propylene glycol monomethyl ether acetate (PGMEA) HPMDA: 1,2,4,5-cyclohexane tetracarboxylic dianhydride (1,2,4,5-cyclohexane tetracarboxylic dianhydride) ODPA: 4,4'-oxydiphthalic dianhydride (ODPA) THPA: 1,2,3,6-tetrahydrophthalic anhydride (THPA) PA: phthalic anhydride (PA) SA: succinic anhydride (SA) DCPMA: dicyclopentanyl methacrylate (DCPMA) GMA: glycidyl methacrylate (GMA) St: styrene (St) AIBN: azobisisobutyronitrile (AIBN) TDMAMP: tris-dimethyl amino methyl phenol (TDMAMP) HQ: hydroquinone (HQ) TEA: triethyl amine (TEA) BPDA: 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA) BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) PMDA: benzene 1,2,4,5-tetracarboxylic dianhydride (PMDA) DPHA: dipentaerythritol hexaacrylate (DPHA) PTMA: pentaerythritol tetra(mercaptoacetate), PTMA) BzDMA: benzyl dimethyl amine (BzDMA)

(Alkali-soluble resin containing unsaturated groups) [Synthesis example 1] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added and the solid content was adjusted to 50% by mass.

Then, HPMDA (10.95 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and stirred at 115°C to 120°C for 6 hours to obtain an alkali-soluble resin containing unsaturated groups ( A)-1. The solid content concentration of the obtained resin solution was 56.0 mass%, the acid value (solid content conversion) was 105 mgKOH/g, and the Mw based on GPC analysis was 4000.

[Synthesis example 2] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added and the solid content was adjusted to 50% by mass.

Then, 1,2,3,4-butanetetracarboxylic dianhydride (9.67 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and the mixture was heated at 115°C to 120°C. Stir for 6 hours to obtain unsaturated group-containing alkali-soluble resin (A)-2. The solid content concentration of the obtained resin solution was 55.6 mass%, the acid value (solid content conversion) was 106 mgKOH/g, and the Mw based on GPC analysis was 3300.

[Synthesis example 3] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added and the solid content was adjusted to 50% by mass.

Then, 1,2,3,4-butanetetracarboxylic dianhydride (9.67 g, 0.05 mol) and PA (7.23 g, 0.05 mol) were added to the obtained reaction product, and the mixture was heated at 115°C to 120°C. Stir for 6 hours to obtain unsaturated group-containing alkali-soluble resin (A)-3. The solid content concentration of the obtained resin solution was 55.9 mass%, the acid value (solid content conversion) was 110 mgKOH/g, and the Mw based on GPC analysis was 2500.

[Synthesis Example 4] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added and the solid content was adjusted to 50% by mass.

Then, 1,2,3,4-butanetetracarboxylic dianhydride (9.67 g, 0.05 mol) and SA (4.89 g, 0.05 mol) were added to the obtained reaction product, and the mixture was heated at 115°C to 120°C. Stir for 6 hours to obtain unsaturated group-containing alkali-soluble resin (A)-4. The solid content concentration of the obtained resin solution was 54.8 mass%, the acid value (solid content conversion) was 110 mgKOH/g, and the Mw based on GPC analysis was 4000.

[Synthesis Example 5] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added and the solid content was adjusted to 50% by mass.

Then, ODPA (15.15 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain an alkali-soluble resin containing unsaturated groups ( A)-5. The solid content concentration of the obtained resin solution was 57.2 mass %, the acid value (solid content conversion) was 96 mgKOH/g, and the Mw based on GPC analysis was 3500.

[Synthesis example 6] PGMEA (300 g) was placed in a 1 L four-necked flask equipped with a reflux cooler, and the flask system was replaced with nitrogen, and then the temperature was raised to 120°C. The following mixture was added dropwise from the dropping funnel into the flask over 2 hours, that is, AIBN (10 g) was dissolved in the monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol)) and stirred at 120°C for 2 hours to obtain a copolymer solution.

Next, after replacing the flask system with air, AA (24.0 g, 95% of the molar number of glycidyl groups), TDMAMP (0.8 g), and HQ (0.15 g) were added to the obtained copolymer solution. Stir at 120° C. for 6 hours to obtain a copolymer solution containing polymerizable unsaturated groups. Add SA (30.0 g, 90% of the molar number of AA added) and TEA (0.5 g) to the obtained copolymer solution containing polymerizable unsaturated groups, and react at 120°C for 4 hours to obtain polymerizable unsaturated group-containing copolymer solution. Saturated alkali-soluble copolymer resin solution (A)-6. The solid content concentration of the resin solution is 46.0 mass%, the acid value (solid content conversion) is 76 mgKOH/g, and the Mw based on GPC analysis is 5300.

[Synthesis Example 7] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added and the solid content was adjusted to 50% by mass.

Then, BPDA (14.37 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain an alkali-soluble resin containing unsaturated groups ( A)'-7. The solid content concentration of the obtained resin solution was 57.0 mass%, the acid value (solid content conversion) was 96 mgKOH/g, and the Mw based on GPC analysis was 3600.

[Synthesis example 8] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added and the solid content was adjusted to 50% by mass.

Next, BTDA (15.73 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain an alkali-soluble resin containing unsaturated groups ( A)'-8. The solid content concentration of the obtained resin solution was 57.4% by mass, the acid value (solid content conversion) was 105 mgKOH/g, and the Mw based on GPC analysis was 3200.

[Synthesis Example 9] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added and the solid content was adjusted to 50% by mass.

Then, PMDA (10.65 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain an alkali-soluble resin containing unsaturated groups ( A)'-9. The solid content concentration of the obtained resin solution was 55.9 mass %, the acid value (solid content conversion) was 105 mgKOH/g, and the Mw based on GPC analysis was 3600.

[Synthesis Example 10] Add PTMA (20.00 g, 0.19 mol of thiol group), DPHA (212.00 g, 2.12 mol of acrylic acid group), PGMEA (58.00 g), HQ (0.1 g) and BzDMA (0.01 g) into a 1 L four-necked flask. React at ℃ for 12 hours to obtain dendritic polymer solution (B)-2. The obtained dendrimer was confirmed to have disappeared using the iodine quantitative method. The solid content concentration of the obtained dendrimer solution was 80.0% by mass, and the Mw based on GPC analysis was 10,000.

The curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were prepared in the amounts described in Table 1 (unit: mass %). The formulation ingredients used in Table 1 are as follows.

(Alkali-soluble resin containing unsaturated groups) (A)-1: Resin solution obtained in Synthesis Example 1 (solid content concentration 56.0 mass%) (A)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration 55.6 mass%) (A)-3: Resin solution obtained in Synthesis Example 3 (solid content concentration 55.9 mass%) (A)-4: Resin solution obtained in Synthesis Example 4 (solid content concentration 54.8 mass%) (A)-5: Resin solution obtained in Synthesis Example 5 (solid content concentration 57.2 mass%) (A)-6: Resin solution obtained in Synthesis Example 6 (solid content concentration 46.0 mass%) (A)'-7: Resin solution obtained in Synthesis Example 7 (solid content concentration 57.0 mass%) (A)'-8: Resin solution obtained in Synthesis Example 8 (solid content concentration 57.4 mass%) (A)'-9: Resin solution obtained in Synthesis Example 9 (solid content concentration 55.9 mass%)

(polymeric compound) (B)-1: Dipentaerythritol penta/hexaacrylate mixture (KAYARAD) DPHA, molecular weight 740, manufactured by Nippon Kayaku Co., Ltd., "KAYARAD" is the registered company trademark) (B)-2: Dendrimer solution obtained in Synthesis Example 10 (solid content concentration 80.0 mass%)

(epoxy compound) (C): Biphenyl-type epoxy resin (jER YX4000, manufactured by Mitsubishi Chemical Co., Ltd.)

(solvent) (D): Propylene glycol monomethyl ether acetate (PGMEA)

(polymerization initiator) (E): 2-[4-(Methylthio)benzoyl]-2-(4-morpholinyl)propane ("Omnirad 907" IGM Resins) manufactured by B.V. , "Omnirad" is a registered trademark of the company mentioned)

(sensitizer) (F): Michler's ketone

[Table 1] Example Example Example Example Example Example Example Example Example Example Comparative example Comparative example Comparative example 1 2 3 4 5 6 7 8 9 10 1 2 3 (A), (A)'Alkali-soluble resin (A)-1 56.9 (A)-2 57.3 55.6 55.6 (A)-3 57.0 55.3 (A)-4 58.2 56.4 (A)-5 55.7 (A)-6 69.3 (A)'-7 55.9 (A)'-8 55.5 (A)'-9 57.0 (B) Polymeric compound (B)-1 10.6 10.6 10.6 10.6 10.6 10.6 10.3 10.3 10.3 10.6 10.6 10.6 (B)-2 12.9 (C) Epoxy compound (C) 7.5 7.5 7.5 7.5 7.5 7.5 7.3 7.3 7.3 7.3 7.5 7.5 7.5 (E) Polymerization initiator (E) 1.5 1.5 1.5 1.5 (F) Sensitizer (F) 0.1 0.1 0.1 0.1 (D) Solvent (D) 25.0 24.6 24.9 23.7 26.2 12.6 25.2 25.5 24.4 22.6 26.0 26.4 24.9

[evaluation] [Calculation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO)] The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (HOMO) of alkali-soluble resins containing unsaturated groups ((A)-1 to (A)-5 and (A)'-7 to (A)'-9) The energy of LUMO) is determined through quantum chemical calculation based on the structural units of these resins represented by the following general formula (13). The "Gaussian16, Revision B.01" software package (Gaussian Inc.) was used in quantum chemical calculations. Specifically, for the molecular structure (molecular coordinates) of the structural unit (terminal hydrogen-substituted) of these resins represented by the general formula (13), with a charge of 0 and a multiplicity of 1, density functional method (DFT) was used. The most stable structure of the structural unit calculated by B3LYP as a functional function and using 6-31G(d) as a basis function is the energy of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in this structure ( Gaussian input line "#B3LYP/6-31G (d) OPT").

[Chemical 19] (In Formula (13), Y is a residue derived from the tetracarboxylic dianhydride used in the synthesis of each resin, and Z is a residue derived from the dicarboxylic anhydride used in the synthesis of each resin)

The energy of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the unsaturated group-containing alkali-soluble resin ((A)-6) is the structural unit of these resins represented by the following general formula (14) Based on this, it is calculated in the same way as (A)-1 to (A)-5 and (A)'-7 to (A)'-9.

[Chemistry 20] (In formula (14), a, b and c are the molar ratios of each structural unit, and are set to a:b:c=1:1:1 during calculation)

(Preparation of a substrate with a resin cured film for transmittance evaluation after the initial transmittance/light resistance test) The photosensitive resin composition shown in Table 1 was applied using a spin coater to a film thickness after heat curing treatment to become 10.0 μm is applied to the following glass substrate "#1737", which is a 125 mm × 125 mm glass substrate that has been previously irradiated with ultraviolet light with a wavelength of 254 nm and an illumination of 1000 mJ/cm ² using a low-pressure mercury lamp and the surface is cleaned "#1737 ”, use a hot plate to pre-bake at 90°C for 3 minutes to make a dry film. Subsequently, the resin cured film-bearing substrates of Examples 1 to 10 and Comparative Examples 1 to 3 were obtained by using a hot air dryer for final curing (post-baking) at 230° C. for 30 minutes.

[Initial transmittance evaluation] Using a UV-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.), the substrate with the cured film after formal curing and before the light resistance test was measured at a wavelength of 400 nm. The transmittance is measured below.

[Transmittance evaluation after light resistance test] Place a blue filter "IEB400" (manufactured by Isuzu Seiko Glass Co., Ltd., 50 mm × 50 mm × 5 mmt, below 340 nm/above 480 nm) on the officially cured substrate with the cured film. The transmittance of the wavelength is less than 10%), and the Xe test chamber "Q-SUN Xe-1" (manufactured by Q-Lab Corporation) was used for 500 hours of light irradiation. For the area where the blue filter in the substrate with the resin cured film was irradiated with light, a UV-visible-infrared spectrophotometer "UH4150" (Hitachi High-Tech Science Co., Ltd. company) to measure the transmittance at a wavelength of 400 nm.

(Preparation of resin cured film powder for thermal decomposition resistance evaluation) The photosensitive resin composition shown in Table 1 was coated on the glass substrate "#1737" using a spin coater so that the film thickness after heat hardening treatment became 10.0 μm, and preheating was performed at 90°C for 3 minutes using a hot plate. Bake to make a dry film. Thereafter, the resin cured film-bearing substrates of Examples 1 to 10 and Comparative Examples 1 to 3 were obtained by using a hot air dryer for final hardening (post-baking) at 230° C. for 30 minutes. The obtained cured film is cut into a powder form and used for measurement of thermogravimetry/differential thermal analysis (TG/DTA).

[Evaluation of thermal decomposition resistance] (evaluation method) The obtained powder of the resin cured film was heated from 30°C to 400°C in air at a heating rate of 5°C/min using a TG-DTA device "TG/DTA6200" (manufactured by Seiko Instruments Co., Ltd.). , measure the temperature when the weight of the test object decreases by 5%. In addition, △ or more was considered a pass.

(Evaluation criteria) ◎: 5% weight loss temperature is 320℃ or above ○: 5% weight loss temperature is above 300℃ and less than 320℃ △: 5% weight loss temperature is above 280℃ and less than 300℃ ×: 5% weight loss temperature is less than 280℃

(Preparation of resin cured film for glass transition temperature evaluation) The photosensitive resin composition shown in Table 1 was coated on the release aluminum foil "Sepanium" (manufactured by Toyo Aluminum Co., Ltd.) using a spin coater so that the film thickness after heat hardening became 30.0 μm. ), use a hot plate to pre-bake at 90°C for 3 minutes to make a dry film. Thereafter, formal hardening (post-baking) is performed at 230°C for 30 minutes using a hot air dryer. Finally, the resin cured film was peeled off from the release aluminum foil, and the resin cured films of Examples 1 to 10 and Comparative Examples 1 to 3 were obtained.

[Evaluation of glass transition temperature] A dynamic viscoelasticity (Dynamic Mechanical Analysis (DMA)) measurement device (RSA-G2 manufactured by TA Instrument Co., Ltd.) was used, and the width was set to 5 so that the length between the chucks was 22 mm. mm of cured film, the glass transition temperature is measured in the temperature range of 30°C to 300°C. In addition, △ or more was considered a pass.

(Evaluation criteria) ◎: Glass transition temperature is above 180℃ ○: Glass transition temperature is 160℃ or more and less than 180℃ △: Glass transition temperature is 140℃ or more and less than 160℃ ×: Glass transition temperature is less than 140℃

(Preparation of a substrate with a resin cured film for evaluation of development adhesion/initial pattern transmittance) The photosensitive resin composition shown in Table 1 was heated and cured using a spin coater so that the film thickness became 10.0 μm. Apply on the glass substrate "#1737", use a hot plate to pre-bake at 90°C for 3 minutes to produce a dry film. Then, the dry film was irradiated with ultraviolet light of 500 mJ/cm ² using an ultra-high-pressure mercury lamp with an i-ray illumination of 30 mW/cm ² to perform a photohardening reaction of the dry film.

Then, the exposed film was developed using 2.38% tetramethylammonium hydroxide (TMAH) at 23°C and a spray pressure of 1 kgf/cm ² for 60 seconds, and then 5 kgf / ^cm2 spray water washing to remove the unexposed parts and form a 10 μm dot pattern. Finally, the resin cured film-bearing substrates of Examples 1 to 10 and Comparative Examples 1 to 3 were obtained by using a hot air dryer for formal hardening (post-baking) at 230° C. for 30 minutes.

[Development Adhesion] The 10 μm dot pattern of the resin cured film of the obtained resin cured film-attached substrate was observed using an optical microscope, and the presence or absence of peeling of the pattern was determined. In addition, △ or more was considered a pass.

(Evaluation criteria) ○: Pattern peeling is not observed △: A very small part of the pattern is observed to peel off. ×: Most of the pattern is peeled off

[Initial pattern transmittance evaluation] Using the ultraviolet visible infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.), the transmittance of the substrate with the cured film after development/main curing was measured at a wavelength of 400 nm. Rate is measured.

The evaluation results are shown in Table 2.

[Table 2] Example Example Example Example Example Example Example Example Example Example Comparative example Comparative example Comparative example 1 2 3 4 5 6 7 8 9 10 1 2 3 Energy difference between HOMO and LUMO (eV) 3.91 3.82 4.11 4.17 3.90 5.35 3.82 4.11 4.17 3.82 3.56 3.09 3.15 Energy of LUMO (eV) -1.70 -1.70 -1.55 -1.63 -1.78 -1.11 -1.70 -1.55 -1.63 -1.70 -2.02 -2.63 -2.41 Initial transmittance 97% 97% 97% 97% 97% 99% 97% 97% 97% 97% 93% 92% 94% Transmittance after light resistance test 95% 95% 93% 94% 93% 99% 95% 95% 95% 95% 54% 45% 47% Thermal decomposition resistance ◎ ◎ ◎ ◎ ◎ △ ◎ ◎ ◎ ◎ ◎ ◎ ◎ glass transition temperature ◎ ◎ ◎ ◎ ◎ △ ◎ ◎ ◎ ◎ ◎ ◎ ◎ development adhesion - - - - - - ○ ○ △ ○ - - - Initial transmittance of pattern - - - - - - 92% 92% 92% 96% - - -

As shown in Table 2, it can be seen that when the resin cured films of Examples 1 to 10 obtained from the photosensitive resin composition of the present invention are irradiated with light having a wavelength of 340 nm to 480 nm, the transmittance of the coating film changes little and Can inhibit the yellowing of coating films. The reason for this is considered to be that by setting the energy difference between the HOMO and LUMO of component (A) to 3.7 eV or more, absorption of light in the wavelength region can be suppressed, thereby suppressing deterioration of the resin cured film.

By using the unsaturated group-containing thermosetting resin represented by the general formula (1) as the component (A), the thermal decomposition resistance can be improved, and the glass transition temperature can be increased. Therefore, the dimensional stability during temperature rise can be improved. This is considered to be because the unsaturated group-containing thermosetting resin represented by the general formula (1) has a plurality of aromatic rings and therefore has excellent thermal stability.

As shown in Examples 7 to 9, it was found that by using a resin containing a dicarboxylic acid or tricarboxylic acid having a cyclic structure or an acid monoanhydride thereof as the component (A), peeling during pattern formation can be suppressed and it is possible to Forms a fine pattern of resin cured film.

As shown in Examples 7 to 10, it was found that by using a dendritic polymer as the component (B), penetration of the developer solution into the photocured portion can be suppressed, thereby suppressing resin hardening during main curing (post-baking). Yellowing of the membrane.

[Industrial availability] The present invention can provide a photosensitive resin composition that can be used when manufacturing various products. In particular, a resin cured film suitable for fixing and sealing an optical semiconductor to a mounting substrate can be provided.

without.

without.

Claims (7)

A hardening resin composition containing: (A) Alkali-soluble resin containing unsaturated groups, (B) Polymeric compounds having two or more unsaturated bonds, (C) Epoxy compounds having two or more epoxy groups, and (D) Solvent, The component (A) is a resin in which the energy difference between the highest occupied molecular orbital and the lowest unoccupied molecular orbital calculated by quantum chemical calculation is 3.7 eV or more. The curable resin composition according to claim 1, wherein the component (A) is a resin represented by the following general formula (1); In formula (1), Ar is independently an aromatic hydrocarbon group having a carbon number of 6 to 14, and a part of the hydrogen atoms constituting Ar may be selected from an alkyl group having a carbon number of 1 to 10, an alkyl group having a carbon number of 6 to 10 Substitution in the group consisting of the following aryl or arylalkyl groups, cycloalkyl groups or cycloalkylalkyl groups having 3 to 10 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, and halogen groups group substitution; R1 is independently an alkylene group with a carbon number of 2 to 4; l is independently a number from 0 to 3; G is independently a (meth)acrylyl group, or the following general formula (2 ) or a substituent represented by the following general formula (3); Y is a tetravalent carboxylic acid residue; Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one of Z is A substituent represented by the following general formula (4); n is a number with an average value of 1 to 20, In formula (2) and formula (3), R2 is a hydrogen atom or a methyl group, R3 is an alkylene group or alkyl aryl group having 2 or more carbon atoms and 10 or less carbon atoms, and R4 is a saturated or alkyl aryl group having 2 or more carbon atoms and 20 or less carbon atoms. Unsaturated hydrocarbon group, p is a number from 0 to 10, * is a bonding site, In formula (4), W is a divalent or trivalent carboxylic acid residue, m is a number of 1 or 2, and * is a bonding site. The curable resin composition according to claim 1 or claim 2, wherein the component (A) is a resin with a weight average molecular weight of 1,000 to 40,000 and an acid value of 50 mgKOH/g to 200 mgKOH/g. . The curable resin composition according to Claim 1 or 2, including at least one of (E) a polymerization initiator and (F) a sensitizer. A resin cured film obtained by curing the curable resin composition according to any one of claims 1 to 4. A semiconductor package using the resin cured film according to claim 5 as at least one protective film. A display device using the resin cured film according to claim 5 as at least one protective film.