JP2023140300A - Curable resin composition, cured resin film, semiconductor package and display device - Google Patents

Abstract

To provide a curable resin composition that can yield a cured film resistant to temporal yellowing when exposed to electromagnetic waves with wavelengths between 340-480 nm.SOLUTION: A curable resin composition contains (A) an unsaturated group-containing alkali-soluble resin, (B) a polymerizable compound with two or more unsaturated bonds, (C) an epoxy compound with two or more epoxy groups, and (D) a solvent. The component (A) is a resin with an energy difference of 3.7 eV or greater between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) as determined by quantum chemical computation.SELECTED DRAWING: None

Description

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

2. Description of the Related Art A protective film is used in semiconductor devices, image display devices, and the like to seal and protect each element on a substrate. As these protective films that require transparency and heat resistance, a cured film is used, which is obtained by applying a curable resin composition containing an alkali-soluble resin having an unsaturated group and a fluorene skeleton, forming a pattern, and curing it ( For example, Patent Document 1).

Japanese Patent Application Publication No. 2003-089716

It is known that a cured film prepared using an alkali-soluble resin having a fluorene skeleton as described in Patent Document 1 has excellent transparency and heat resistance. However, according to the findings of the present inventors, when the cured film absorbs electromagnetic waves with a wavelength of around 340 to 480 nm emitted by UV-LEDs and Blue-LEDs, it gradually changes in quality and yellows over time. Sometimes I put it away.

The present invention has been made in view of the above problems, and provides a curable resin composition capable of obtaining a cured film that is resistant to yellowing over time due to electromagnetic waves having a wavelength of around 340 to 480 nm, and the curable resin composition. The object is to provide a cured resin film formed from the cured resin film, and a semiconductor package and a display device having the cured resin film.

One aspect of the present invention for solving the above problems relates to the following curable resin compositions [1] to [4].
[1] (A) an unsaturated group-containing alkali-soluble resin;
(B) a polymerizable compound having two or more unsaturated bonds;
(C) an epoxy compound having two or more epoxy groups;
(D) a solvent;
including;
The component (A) is a curable resin composition in which the energy difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) is 3.7 eV or more, as calculated by quantum chemical calculation. .
[2] The curable resin composition according to [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 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar are alkyl groups having 1 to 10 carbon atoms, carbon Substitution selected from the group consisting of an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. may be substituted with a group. R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. 1 is independently a number of 0 or more and 3 or less. G is independently ( meth)acryloyl 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 It is 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. .)

(In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkylarylene group having 2 or more carbon atoms and 10 or less carbon atoms, and R ₄ is a carbon number 2 or less. (It is a saturated or unsaturated hydrocarbon group with a number of 0 to 10, p is a number of 0 to 10, and * 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 binding site.)
[3] The curable resin composition according to [1] or [2], wherein the component (A) is a resin having a weight average molecular weight of 1000 to 40000 and an acid value of 50 mgKOH to 200 mgKOH.
[4] The curable resin composition according to any one of [1] to [3], containing at least one of (E) a polymerization initiator and (F) a sensitizer.

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

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

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

According to the present invention, a curable resin composition capable of obtaining a cured film that is unlikely to yellow over time due to electromagnetic waves having a wavelength of around 340 to 480 nm, a resin cured film formed from the curable resin composition, and a cured resin film formed from the curable resin composition; A semiconductor package and display device having a cured resin film are provided.

1. Curable Resin Composition Hereinafter, a curable resin composition according to an 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, (C) an epoxy compound having two or more epoxy groups; and (D) a solvent.

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

Component (A) preferably has a polymerizable unsaturated group and an acidic group for exhibiting alkali solubility in one molecule, and more preferably has a polymerizable unsaturated group and a carboxyl group. Component (A) is not particularly limited as long as it is the above-mentioned resin, and may be various types of resins. Since component (A) has a polymerizable unsaturated group, it imparts excellent photocurability to the curable resin composition, and when cured, the molecular weight becomes large and it acts as a binder. Furthermore, since component (A) has an acidic group, it improves developability, patterning characteristics (pattern line width, pattern linearity), and the like.

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

The above energy difference is the energy between the HOMO energy and the LUMO energy determined by density functional theory (DFT) in the most stable structure of the structural unit based on the structural unit of component (A). It's the difference. The most stable structure can be determined from the molecular structure of component (A) by a known structure optimization method. In this specification, the HOMO and LUMO energies of component (A) are determined using the "Gaussian 16, Revision B.01" software package (Gaussian Inc.), and the energy of the HOMO and LUMO of component (A) is calculated using the 0 charge and multiplicity for the molecular structure of component (A). 1, the molecule was calculated by density functional theory (DFT) using B3LYP as the functional and 6-31G(d) as the basis function (Gaussian input line "#B3LYP/6-31G(d)OPT"). Let it be the energy of the highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO) in the most stable structure. However, other computational science software with similar functionality may be used to calculate the DFT and TDDFT. In addition, when performing the above quantum scientific calculations, the energies of HOMO and LUMO are determined for each partial structure of the unconjugated component (A), and the energy difference between the HOMO and LUMO obtained from these partial structures is calculated. The minimum value of may be taken as the above energy difference.

The energy difference is preferably 3.7 eV or more and 6.0 eV or less. If the energy difference is 3.7 eV or more, it becomes difficult to absorb electromagnetic waves with a wavelength of around 340 to 480 nm, thereby suppressing the deterioration of component (A) over time and the accompanying yellowing of the cured film over time. can. Although the upper limit of the energy difference is not particularly limited, it can be 6.0 eV or less.

Component (A) may be any alkali-soluble resin as long as it satisfies the above energy difference requirements. Examples of component (A) include (i) a product 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 its anhydride; (ii) an unsaturated group-containing alkali-soluble resin which is an acrylic (co)polymer, (iii) an unsaturated group-containing alkali-soluble resin which is a polysiloxane containing a plurality of siloxane bonds, etc. is included.

Examples of unsaturated group-containing monocarboxylic acids used in the synthesis of each component (A) above include (meth)acrylic acid, dicarboxylic acids such as succinic acid, maleic acid, and phthalic acid, and their acids. It includes compounds obtained by reacting monoanhydrides and the like.

In addition, "(meth)acrylic acid" is a generic term for acrylic acid and methacrylic acid, "(meth)acryloyl group" is a generic term for acryloyl group and methacryloyl group, and "(meth)acrylate" is a generic term for acrylic acid and methacrylic acid. and methacrylate, and each refers to one or both of these.

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

Examples of the epoxy compounds having two or more epoxy groups include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol fluorene epoxy compounds, bisnaphthol fluorene epoxy compounds, diphenylfluorene epoxy compounds, and phenol novolac epoxy compounds. Compounds, (o,m,p-)cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, biphenyl type epoxy compounds (for example, jERYX4000: manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the company), naphthalene skeleton Phenol novolac compounds (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetrakisphenolethane type Epoxy compounds with an aromatic structure such as epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polyhydric carboxylic acids, and glycidyl (meth)acrylates such as copolymers of methacrylic acid and glycidyl methacrylate are used as units. Copolymers of monomers having (meth)acryloyl groups containing glycidyl groups, such as hydrogenated bisphenol A diglycidyl ether (for example, Ricaresin HBE-100: manufactured by Shinnihon Rika Co., Ltd., "Ricaresin" is a registered trademark of the company) 1,4-cyclohexanedimethanol-bis3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (For example, Araldite CY175: Manufactured by Huntsman, "Araldite" is a registered trademark of that company), Bis(3,4-epoxycyclohexylmethyl)adipate (For example, CYRACURE UVR-6128: Manufactured by Dow Chemical Company), 3',4 '-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (for example, Celoxide 2021P: manufactured by Daicel Corporation, “Celoxide” is a registered trademark of the same company), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε - Caprolactone (e.g., Epolead GT401: manufactured by Daicel Corporation; “Epolead” is a registered trademark of the company), an epoxy compound having an epoxycyclohexyl group (e.g., HiREM-1: manufactured by Shikoku Kasei Kogyo Co., Ltd.), a dicyclopentadiene skeleton polyfunctional epoxy compounds (for example, HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol (for example, Alicyclic epoxy compounds such as EHPE3150 (manufactured by Daicel Corporation), epoxidized polybutadiene (for example, NISSO-PB/JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of that company), and silicone skeletons. This includes epoxy compounds with

Examples of the unsaturated group-containing alkali-soluble resin that is an acrylic (co)polymer in (ii) above include copolymers of (meth)acrylic acid, (meth)acrylic acid ester, etc. and carboxy group-containing resins. Examples of the above resin include copolymerizing (meth)acrylic esters containing glycidyl (meth)acrylate in a solvent, reacting (meth)acrylic acid, and finally dicarboxylic acid. Alternatively, an alkali-soluble resin containing a polymerizable unsaturated group obtained by reacting an anhydride of tricarboxylic acid is included. The above-mentioned copolymer contains 20 to 90 mol% of repeating units derived from diesterglycerol in which the hydroxyl groups at both ends are esterified with (meth)acrylic acid, as shown in JP-A-2014-111722, and copolymer. A copolymer composed of 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds, having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH/g. , and a weight average containing a unit derived from a (meth)acrylic acid ester compound and a unit having a (meth)acryloyl group and a di- or tricarboxylic acid residue, as disclosed in JP 2018-141968A. An alkali-soluble resin containing a polymerizable unsaturated group, which is a polymer having a molecular weight (Mw) of 3,000 to 50,000 and an acid value of 30 to 200 mg/KOH, can be used as a reference.

Examples of the unsaturated group-containing alkali-soluble resin which is the polysiloxane (iii) above include polysiloxane compounds having a (meth)acryloyl group and a carboxyl group. Examples of the above-mentioned compounds include siloxane-modified acrylic resins obtained by reacting epoxy acrylate, siloxane diamine, and aromatic dianhydride (Japanese Unexamined Patent Publication No. 2002-226549, etc.), siloxane diamine and ethylenic unsaturated bonds, etc. A siloxane-containing polyamide resin obtained by reacting an aromatic diamine with an aromatic tetracarboxylic dianhydride (International Publication No. 2009/075217, etc.), a diamine containing a siloxane diamine and an aromatic tetracarboxylic dianhydride, A siloxane-containing polyamic acid resin obtained by reacting a siloxane-containing polyamic acid resin (Japanese Patent Application Laid-open No. 2008-070477, International Publication No. 2006/109514, Japanese Patent Application Publication No. 2010-204590, etc.), an epoxy silicone compound having an isocyanuric ring skeleton, and a polymerizable diamic acid resin. An isocyanuric ring skeleton is a group containing a polymerizable double bond and a carboxyl group obtained by reacting a dicarboxylic acid or its acid monoanhydride with a polyhydric alcohol compound obtained by reacting a polyhydric alcohol compound with a carboxylic acid containing a double bond. Included are alkali-soluble resins having a substituent bonded to (Japanese Patent Application Laid-open No. 2011-141518, etc.).

For these resins, for example, by reducing the number of aromatic rings, the energy difference between the HOMO energy and the LUMO energy can be increased. Specifically, at least a portion of aromatic dicarboxylic acids, aromatic tricarboxylic acids, aromatic tetracarboxylic acids, or their anhydrides used in the synthesis of conventional alkali-soluble resins are replaced with non-aromatic carboxylic acids or By using the anhydride, the energy difference between the HOMO energy and the LUMO energy can be increased to the above range.

From the viewpoint of suppressing thermal decomposition of the cured resin film and increasing the glass transition point to suppress thermal deformation, component (A) preferably has a plurality of aromatic rings, and further improves adhesiveness and solvent resistance. From the viewpoint of further improving properties, component (A) preferably has a repeating unit containing a fluorene structure, and even more preferably a repeating unit containing a bisarylfluorene skeleton. For example, component (A) is preferably a resin represented by the following general formula (1).

In formula (1), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar are an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. It may be substituted with an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. l is independently a number from 0 to 3. G is independently a (meth)acryloyl 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 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.

In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkylarylene group having 2 or more carbon atoms and 10 or less carbon atoms, and R ₄ is a carbon number 2 or more It is a saturated or unsaturated hydrocarbon group of 20 or less, p is a number from 0 to 10, and * 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 binding 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, which may have several alkylene oxide modifying groups in one molecule (hereinafter simply "epoxy Compound (a-1)"), (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (6), and (meth)acrylic acid derivative represented by the following general formula (7). At least one kind of acrylic acid derivative is reacted to obtain a diol compound which is an epoxy (meth)acrylate. Note that the bisarylfluorene skeleton is preferably a bisnaphtholfluorene skeleton or a bisphenolfluorene skeleton.

In formula (5), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar are alkyl groups having 1 to 10 carbon atoms, May be substituted with an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. . R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. l is independently a number from 0 to 3.

In formulas (6) and (7), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkylarylene group having 2 or more carbon atoms and 10 or less carbon atoms, and R ₄ is a carbon number 2 or more It is a saturated or unsaturated hydrocarbon group of 20 or less, and p is a number of 0 or more and 10 or less.

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, JP-A-4-355450 discloses that by using about 2 moles of (meth)acrylic acid for 1 mole of an epoxy compound having two epoxy groups, a diol compound containing a polymerizable unsaturated group can be produced. It is stated that this can be obtained. In this embodiment, the compound obtained by the above reaction is a diol (d) containing a polymerizable unsaturated group represented by the following general formula (8) (hereinafter also simply referred to as "diol (d)"). be.

In formula (8), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar are alkyl groups having 1 to 10 carbon atoms, May be substituted with an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. . G is each independently a (meth)acryloyl group, a substituent represented by general formula (2) or general formula (3), and R ₁ is independently an alkylene group having 2 to 4 carbon atoms. It is. l is independently a number from 0 to 3.

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

Next, the diol (d) obtained above, dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), and tetracarboxylic acid or its acid dianhydride (c) are reacted to form the general formula (1). ) An unsaturated group-containing curable resin having a carboxy group and a polymerizable unsaturated group in one molecule can be obtained.

The acid component is a polyvalent acid component that can react with the hydroxyl group in the diol (d) molecule. In order to obtain the resin represented by general formula (1), dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) and tetracarboxylic acid or its acid dianhydride (c) are used in combination. It is necessary. The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, these carboxylic acid residues may contain a bond containing a hetero element such as -O-, -S-, or carbonyl group.

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. Acids and their acid monoanhydrides are included.

Examples of the chain hydrocarbon dicarboxylic or tricarboxylic acids mentioned above 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, and diglycolic acid, as well as dicarboxylic acids or tricarboxylic acids thereof into which arbitrary substituents have been introduced.

Examples of the above alicyclic hydrocarbon dicarboxylic or tricarboxylic acids include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, hexahydrophthalic acid, Hydrotrimellitic acid, norbornanedicarboxylic acid, and these dicarboxylic acids or tricarboxylic acids into which arbitrary substituents have been introduced are included.

Examples of the above aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and trimellitic acid, and optional substituents are introduced. These include dicarboxylic or tricarboxylic acids.

Among these dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferable, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferable. preferable.

It is preferable to use the acid monoanhydride of the dicarboxylic acid or tricarboxylic acid.

Note that from the viewpoint of enabling finer pattern formation, these dicarboxylic acids or tricarboxylic acids preferably have a cyclic structure. More specifically, it is preferable to use an alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, an aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or an acid monoanhydride thereof. When a dicarboxylic acid or tricarboxylic acid with a cyclic structure is used, a cyclic structure is introduced at the end and the fluidity of the resin is reduced, which suppresses peeling of the coating film during pattern formation, resulting in the formation of a fine pattern. considered to be a thing.

Examples of the above-mentioned tetracarboxylic acid or its dianhydride (c) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, and acid dianhydrides thereof. etc. are included. Among these, chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, and acid dianhydrides thereof are preferred.

Examples of the chain hydrocarbon tetracarboxylic acids mentioned above include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups have been introduced. These chain hydrocarbon tetracarboxylic acids and the like are included.

Examples of the alicyclic hydrocarbon tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid, as well as chain hydrocarbon groups. and these alicyclic tetracarboxylic acids into which substituents such as unsaturated hydrocarbon groups have been introduced.

Examples of the aromatic hydrocarbon tetracarboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and naphthalene-1,4,5,8-tetracarboxylic acid. and naphthalene-2,3,6,7-tetracarboxylic acid. From the viewpoint of increasing LUMO and further increasing the energy difference between HOMO and LUMO, these aromatic hydrocarbon tetracarboxylic acids can be used by introducing electron-donating atoms such as oxygen into the aromatic ring of the acid anhydride moiety. It is preferable to use one in which the acid anhydride skeleton is dispersed in a plurality of non-conjugated aromatic rings. For example, the tetracarboxylic acid is preferably diphenyl ether tetracarboxylic acid.

As for the above-mentioned tetracarboxylic acid, it is preferable to use its acid dianhydride.

Further, instead of the above-mentioned tetracarboxylic acid or its acid dianhydride (c), bis-trimellitic anhydride aryl esters can also be used. Bistrimellitic anhydride aryl esters are compounds produced, for example, by the method described in International Publication No. 2010/074065, and are structurally composed of aromatic diols (naphthalene diol, biphenol, terphenyl diol, etc.). ) is an acid dianhydride in which the two hydroxyl groups of trimellitic anhydride react with the carboxy groups of two molecules of trimellitic anhydride to form an ester bond.

The method for reacting the diol (d) with the acid components (b) and (c) is not particularly limited, and any known method can be employed. For example, JP-A-9-325494 describes a method in which epoxy (meth)acrylate and tetracarboxylic dianhydride are reacted at a reaction temperature of 90 to 140°C.

At this time, epoxy (meth)acrylate (diol (d)), dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b), and tetracarboxylic dianhydride ( It is preferable to carry out the reaction so that the molar ratio of c) is (d):(b):(c)=1.0:0.01 to 1.0:0.2 to 1.0.

For example, when using acid monoanhydride (b) and acid dianhydride (c), the molar ratio of the amount of acid component [(b)/2+(c)] to diol (d) [[(b) /2+(c)]/(d)] is preferably greater than 0.5 and less than 1.0. If the above molar ratio is 1.0 or less, the terminal of the unsaturated group-containing curable resin represented by general formula (1) will not become an acid anhydride, so the content of unreacted acid dianhydride will increase. can be suppressed to improve the stability of the curable composition over time. In addition, when the above molar ratio is larger than 0.5, the increase in the remaining amount of unreacted components of the diol (d) containing a polymerizable unsaturated group is suppressed, thereby stabilizing the curable composition over time. You can increase your sexuality. In addition, for the purpose of adjusting the acid value and molecular weight of the unsaturated group-containing curable resin represented by general formula (1), the molar ratio of each component (b), (c), and (d) was adjusted as described above. It can be changed arbitrarily within the range.

Note that the synthesis of 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 such solvents include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high boiling ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate. , and ketone solvents such as cyclohexanone and diisobutyl ketone. Although there are no particular restrictions on the reaction conditions such as the solvent and catalyst to be used, 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.

Further, the reaction between the epoxy group and the carboxy group or hydroxyl group is preferably carried out using a catalyst. As the above-mentioned catalyst, JP-A-9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, phosphines such as triphenylphosphine, and tris(2,6-dimethoxyphenyl)phosphine, and the like. ing.

When using the resin represented by the above general formula (1) as component (A), from the viewpoint of suppressing thermal decomposition of the cured resin film and increasing the glass transition point to suppress thermal deformation, ( The energy of the LUMO of component A) is preferably −2.0 eV or higher. When the LUMO energy is -2.0 eV or more, the aromatic ring in the resin (specifically dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b), or tetracarboxylic acid or its acid dianhydride (c) By appropriately increasing the number of aromatic rings derived from ), the heat resistance of the cured resin film can be improved.

The component (A) preferably has a weight average molecular weight (Mw) of 1,000 or more and 40,000 or less, more preferably 2,000 or more and 20,000 or less. The higher the Mw of component (A), the higher the adhesion and flexibility of the cured resin film, and the easier it is to adjust the crosslink density. On the other hand, the lower the Mw of component (A), the higher the solubility of component (A) in the solvent, and the higher the compatibility with component (B), which improves the cloudiness prevention property and flatness of the cured resin film. And patternability can be improved. From the viewpoint of further increasing the compatibility with component (B), the Mw of component (A) is preferably 1,000 or more and 30,000 or less, more preferably 1,500 or more and 25,000 or less. Further, when using the resin represented by the above general formula (1) as component (A), the Mw of component (A) is preferably 1000 or more and 6000 or less, more preferably 2000 or more and 4000 or less. . In this embodiment, a compound having a relatively large acrylic 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, by setting the Mw of component (A) to 6,000 or less, their compatibility can be sufficiently increased.

From the same viewpoint, component (A) preferably has an acid value of 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 were determined by gel permeation chromatography (GPC) (for example, "HLC-8220GPC" (manufactured by Tosoh Corporation)). It can be a styrene equivalent value. Further, the acid value can be a value determined using a potentiometric titration device (for example, "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.)). However, for compounds such as monomers whose molecular weight can be calculated from the structure, the value calculated from the structure may be used as the molecular weight of the compound.

The content of component (A) is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less based on the total mass of the solid content, with emphasis on patterning properties. In this case, it is more preferably 40% by mass or more and 80% by mass or less. When the content of component (A) is 10% by mass or more, it becomes possible to form a pattern with high resolution.

In addition, (A) component may use only one type independently and may use two or more types together.

[(B) Component]
Component (B) is a polymerizable compound having two or more unsaturated bonds. Examples of component (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and tetramethylene glycol di(meth)acrylate. , glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene (Meth)acrylic acid esters such as alkylene oxide-modified hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate are included. One type of these polymerizable compounds may be used alone, or two or more types may be used in combination. Component (B) only needs to be able to play the role of crosslinking the molecules of component (A), and from the viewpoint of achieving this function more fully, it is preferable to use a component that has three or more unsaturated bonds. . Further, the acrylic equivalent obtained by dividing the molecular weight of the polymerizable compound by the number of (meth)acryloyl groups in one molecule is preferably 50 to 300, and more preferably 80 to 200. Note that component (B) does not have a free carboxyl group.

Component (B) may also include dendritic polymers having (meth)acryloyl groups. Examples of dendritic polymers having (meth)acryloyl groups include those obtained by adding a polyvalent mercapto compound to some of the carbon-carbon double bonds in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Examples include dendritic polymers. Specifically, a dendritic compound obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by the following general formula (9) with a polyvalent mercapto compound represented by the following general formula (10) Includes polymers, etc.

(In formula (9), R ₅ is a hydrogen atom or a methyl group, and R ₆ is the remainder after donating q hydroxy groups out of _k hydroxy groups of R ₇ (OH) to the ester bond in the formula. Preferably R ₇ (OH) _k is a polyhydric alcohol having a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a polyhydric alcohol having multiple molecules of the polyhydric alcohol. It is a polyhydric alcohol ether formed by dehydration condensation of alcohols linked through an ether bond, or an ester of these polyhydric alcohols or polyhydric alcohol ethers and a hydroxy acid. k and q are independently 2 to 2. It represents an integer of 20, but k≧q.)

(In formula (10), R ₈ is a single bond or a divalent to hexavalent hydrocarbon group having 1 to 6 carbon atoms, r is 2 when R ₈ is a single bond, and R ₈ is 2 to When it is a hexavalent group, the number is the same as the valence of _R8 .)

Examples of polyfunctional (meth)acrylates represented by general formula (9) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ethylene oxide-modified trimethylolpropane. Tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone modified pentaerythritol tri(meth)acrylate (meth)acrylic acid esters such as These compounds may be used alone or in combination of two or more.

Examples of the polyvalent mercapto compound represented by the general formula (10) include trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercaptopropionate), pentaerythritol tetra(mercaptoacetate), and pentaerythritol tri(mercaptoacetate). mercaptoacetate), pentaerythritol tetra(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), and the like. These compounds may be used alone or in combination of two or more.

Here, the Michael addition of the polyvalent mercapto compound represented by the general formula (10) to the polyfunctional (meth)acrylate represented by the general formula (9) is such that the resulting dendritic polymer remains carbon-carbon In order to be able to perform radiation polymerization based on double bonds, when the total amount of carbon-carbon double bonds in the compound represented by general formula (9) is 100 mol%, the carbon-carbon double bonds are 0. It is preferable to carry out so that it remains in the range of 1 to 50 mol%.

For example, a mercapto group of a polyvalent mercapto compound represented by general formula (10) and a carbon-carbon double bond of a polyfunctional (meth)acrylate represented by general formula (9) (in general formula (9), CH ₂ =C(R ₅ )-, and is referred to as a double bond when calculating the molar ratio. It is preferably 1/3, more preferably 1/50 to 1/5, and particularly preferably 1/20 to 1/8.

It is also preferred that the dendritic polymer has a sufficient amount of functional groups for radiation polymerization. Therefore, the acrylic equivalent of the dendritic polymer is preferably in the range of 100 to 10,000. In addition, since the dendritic polymer with (meth)acryloyl groups has a large molecular weight, it suppresses the penetration of the developer into the exposed areas of the coating film during pattern formation, and the cured resin film turns yellow during main curing (post-bake). change can be suppressed. For example, the dendritic polymer having a (meth)acryloyl group preferably has a weight average molecular weight (Mw) in the range of 1,000 to 20,000, more preferably 7,000 to 20,000, and more preferably 8,000 to 15,000. More preferably, it is within the range of .

The mixing ratio of component (A) and component (B) is preferably 30/70 to 90/10, and preferably 60/40 to 80/20 in terms of mass ratio (A)/(B). More preferred. When 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 is less likely to decrease in unexposed areas, so that the solubility in alkaline developers is reduced. can suppress the decline in Therefore, problems such as pattern edges becoming jagged or not being sharp are less likely to occur. Furthermore, when the blending ratio of component (A) is 90/10 or less, the proportion of photoreactive functional groups in the resin is sufficient, so that a desired crosslinked structure can be formed. In addition, since the acid value of the resin component is not too high, the solubility in the alkaline developer in the exposed area is unlikely to increase, so the formed pattern may be thinner than the target line width or the pattern may be missing. Can be suppressed.

[(C) Component]
Component (C) is an epoxy compound having two or more epoxy groups. Component (C) can improve the chemical resistance of the cured resin film and the moisture-resistant adhesion of the cured resin film. This protects the carboxy group of component (A) by reacting with the epoxy group of component (C) during main curing (post-bake), thereby reducing the hygroscopicity of component (A) caused by the carboxy group. This is thought to be because it is possible to

Examples of component (C) include epoxy compounds having two or more epoxy groups as described for component (A). Note that these compounds may be used alone or in combination of two or more.

Among these, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, and biphenyl type epoxy compounds are preferred, and biphenyl type epoxy compounds are preferable. Epoxy compounds are more preferred. Biphenyl-type epoxy compounds can provide both mechanical strength and chemical resistance of cured products that meet the required properties.

The epoxy equivalent of component (C) is preferably 100 g/eq or more and 300 g/eq or less, more preferably 100 g/eq or more and 250 g/eq or less. Further, the number average molecular weight (Mn) of component (C) is preferably 100 or more and 5000 or less. When the epoxy equivalent of component (C) is 100 g/eq or more, the solvent resistance of the cured film increases. When 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 a subsequent process. Further, when the Mn of the component (C) is 5000 or less, sufficient alkali resistance can be maintained even when an alkaline chemical solution is used in a subsequent process.

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

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

Examples of component (D) include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol. alcohols such as, terpenes such as α- or β-terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, methyl Cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl Ether, glycol ethers such as 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 , 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 acetic acid esters. Component (D) may be used alone or in combination of two or more.

The content of component (D) varies depending on the target viscosity, but is preferably 30% by mass or more and 90% by mass or less based on the total mass of the curable resin composition. When the content of component (D) is 30% by mass or more, the curable resin composition can be easily coated on the substrate, and when the content is 90% by mass or less, the curable resin composition can be coated on the substrate. The time required for drying after coating can be shortened.

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

Component (E) is not particularly limited as long as it is a compound that has a polymerizable unsaturated bond and can initiate the polymerization of an addition polymerizable compound. Examples of component (E) include photopolymerization initiators such as acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and acyloxime compounds. Note that in this specification, the term "photopolymerization initiator" is used to include a sensitizer.

Examples of acetophenone compounds include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2- hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)butan-1-one, oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, and the like.

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-(pipronyl)-4,6-bis(trichloro Examples include methyl)-1,3,5-triazine.

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'-tetra(tert-butylperoxycarbonyl ) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(N,N-diethylamino)benzophenone, and the like.

Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- Contains propoxythioxanthone.

Examples of imidazole compounds include 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, -(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, etc. is included.

Examples of acyl oxime compounds include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9-ethyl -6-(2-Methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-adamantylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane-1-one oxime- O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6 -(2-Methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime -O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime-O-acetate, 1-[9-ethyl -6-(2-Methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H- carbazol-3-yl]-ethane-1-one oxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1- oxime-O-adamantanecarboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione=2-o-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole -3-yl]ethanone-o-acetyloxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyloxime, ethanone, 1-[7-(2 -methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(O-acetyloxime), ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2 -yl)-1-o-acetyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), 1, 2-octanediene, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl ]-,1-(O-acetyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1 , 2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H -carbazolo-3-yl-O-acetyloxime, 5-(4-isopropylphenylthio)-1,2-indanedione, 2-(O-acetyloxime), and the like. The above photopolymerization initiators may be used alone or in combination of two or more.

Other examples of acyloxime photopolymerization initiators include O-acyloxime photopolymerization initiators represented by general formula (11) or general formula (12).

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 arylalkyl group having 4 to 12 carbon atoms. It represents a heterocyclic group, and 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 aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen; It may contain a saturated bond, an ether bond, a thioether bond, or an ester bond. Further, the alkyl group may be any linear, branched, or cyclic alkyl group.

(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 or cycloalkylalkyl group having 4 to 10 carbon atoms. or an alkylcycloalkyl group, or a phenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms.R ₁₄ each independently represents a linear or branched group having 2 to 10 carbon atoms. It is an alkyl group or an alkenyl group, and a part of the -CH ₂ - group in the alkyl group or alkenyl group may be substituted with an -O- group.Furthermore, hydrogen in these R ₁₂ to R ₁₄ groups Some of the atoms may be substituted with halogen atoms.)

Further, it is preferable that the component (E) has a molar extinction coefficient of 10000 L/mol·cm or more at 365 nm. Since such a photopolymerization initiator has high sensitivity, it is possible to ensure sufficient photosensitivity even in a curable resin composition containing component (B) with a relatively large acrylic equivalent. Developability (resolution) can be sufficiently improved. Examples of such photopolymerization initiators include Omnirad 1312 (manufactured by IGM Resins B.V., "Omnirad" is a registered trademark of that company), and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation, "Adeka Arcles"). ” is a registered trademark of the company).

In this specification, the molar extinction coefficient of a photopolymerization initiator is determined by measuring the absorbance of an acetonitrile solution with a concentration of 0.001% by weight using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.). The value can be determined by measurement in a quartz cell with an optical path length of 1 cm.

Further, as the component (E), a thermal polymerization initiator may be used. Examples of thermal polymerization initiators include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, 1,1-t-butylperoxy -Organic peroxides such as 3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, azodibenzoyl, Azo compounds such as 1,1'-azobis(1-acetoxy-1-phenylethane) and 2,2'-azobis(methyl isobutyrate), water-soluble catalysts such as potassium persulfate and ammonium persulfate, and peroxides or Any catalyst that can be used in normal radical polymerization can be used, such as a redox catalyst using a combination of a sulfate and a reducing agent. The thermal polymerization initiator can be selected in consideration of the storage stability of the thermosetting resin composition of the present invention and the conditions for forming a cured product.

Note that as component (E), an active radical generator or an acid generator may be used.

Examples of active radical generators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like.

Examples of acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl sulfonate, and 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin Contains tosylates, etc.

(F) Examples of sensitizers include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, benzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichloro Benzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, etc. acetophenones; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- (n-butoxy)ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylpara-toluidine, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone benzophenone series such as 2-isopropylthioxanthone, thioxanthone series such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; 4,4'-bis(dimethylamino)benzophenone, 4, Aminobenzophenones such as 4'-bisdiethylaminobenzophenone and 4,4'-bis(ethylmethylamino)benzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, It also includes camphorquinone.

The content of component (E) is preferably 1 part by mass or more and 30 parts by mass or less, and 2 parts by mass or more and 10 parts by mass or less, based on a total of 100 parts by mass of components (A) and (B). It is more preferable that there be. When an acyloxime photopolymerization initiator is used as the component (D), the content of the component (E) is 0.00 parts by mass based on a total of 100 parts by mass of the components (A) and (B). It is preferably 5 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less. When the content of the component (E) is equal to or higher than the above lower limit, the photopolymerization rate is appropriate, so that sufficient sensitivity can be ensured. Moreover, when the content of the component (E) is below the above-mentioned upper limit value, it is possible to reproduce line widths faithful to the mask and to sharpen pattern edges.

The content of component (F) is preferably 0.5 parts by mass or more and 400 parts by mass or less, and 1 part by mass or more and 300 parts by mass or less, when the total mass of component (E) is 100 parts by mass. It is more preferable. When the content of the photosensitizer is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be improved and the speed of photopolymerization can be accelerated. Moreover, when the content of the photosensitizer is 400 parts by mass or less, excessive increase in sensitivity can be suppressed, and scorching, peeling residue, etc. can be made less likely to occur during irradiation with light.

[Other ingredients]
The curable resin composition may contain other resin components, a curing agent, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, and an ultraviolet absorber, as necessary. , surfactants, coupling agents, viscosity modifiers, and other additives may be added.

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

Examples of the curing agent include amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc. that contribute to curing of epoxy resins.

Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc. that contribute to accelerating the curing of epoxy resins. It can be done.

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, and the like.

Examples of leveling agents and antifoaming 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, polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate, lauryl trimethylammonium chloride, lauryl dimethylamine oxide, lauryl Amphoteric surfactants such as carboxymethyl hydroxyethylimidazolinium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate, and silicone-based substances whose main skeleton is polydimethylsiloxane. Includes surfactants, fluorosurfactants, etc.

Examples of the coupling agent include silane coupling agents. The silane coupling agent preferably has a reactive group such as an amino group, an isocyanate group, a ureido group, an epoxy group, a vinyl group, a (meth)acryloyl group, or a mercapto group. It is more preferable to have the following. Specific examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc. .

[Production method]
The curable resin composition can be obtained by mixing the above-mentioned components.

2. Application The above-mentioned curable resin composition can be used as a protective layer in various display devices such as liquid crystal displays, organic EL display devices, μLED display devices, and display devices to which quantum dots are applied by forming a resin cured film by irradiation with radiation. , insulation films for printed wiring boards and semiconductor packages, such as resist layers such as solder resist layers, plating resist layers, and etching resist layers, interlayer insulation layers such as multilayer printed wiring boards, gas barrier films, lenses, and light emitting diodes (LEDs). It can be used for encapsulants for semiconductor light emitting devices such as ), top coats for paints and inks, hard coats for plastics, antirust films for metals, etc. Note that in this specification, a semiconductor package includes a semiconductor chip and is mounted on a printed circuit board, such as a flip-chip package stacked on an interposer, in addition to a flip-chip package, a wafer-level package, etc. It means things that are made into a form that can be used. In particular, it is useful for optical semiconductor packages that are combined with light emitting elements (preferably LEDs such as UV-LEDs and Blue-LEDs). Furthermore, the thermosetting composition itself can be molded to produce films, substrates, plastic parts, optical lenses, etc.

In particular, the cured resin film is less likely to yellow over time due to electromagnetic waves with a wavelength of around 340 to 480 nm, so it can be used in various devices that have light sources that emit the electromagnetic waves (such as UV-LEDs and Blue-LEDs). It is possible to suppress the harmful effects of yellowing over time. From this point of view, the cured resin film is preferably placed closer to the light source, and is particularly used as a protective film (sealing material) for arranging and sealing the light source on the mounting board. In some cases, it is more effective than other materials in suppressing the harmful effects of yellowing over time.

The cured resin film can be produced by, for example, applying the curable resin composition to a substrate, drying it, irradiating it with light (including ultraviolet rays, radiation, etc.), and curing it. I can do it. At this time, if you use a photomask etc. to set up areas that are exposed to light and areas that are not, and cure only the areas that are exposed to light and dissolve the other areas with an alkaline solution, you can create a cured product with the desired pattern. is obtained.

When applying the curable resin composition to the substrate, any known method such as a solution dipping method, a spray method, a roller coater machine, a land coater machine, a method using a slit coater machine or a spinner machine may be used. I can do it.

By these methods, a film is formed by applying a curable resin composition to a desired thickness and then removing the solvent (prebaking). Prebaking is performed by heating using an oven, hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, and is carried out, for example, at a temperature of 80 to 120° C. for 1 to 10 minutes.

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

Alkaline development can be carried out using, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like as a developer. These developing solutions are selected depending on the characteristics of the resin layer, and a surfactant may be added if necessary. The development is preferably carried out at a temperature of 20 to 35°C. By using a commercially available developing machine, ultrasonic cleaning machine, etc., fine images can be precisely formed. Note that after alkaline development, the film is usually washed with water. Examples of development processing methods include shower development, spray development, dip development, paddle development, and the like.

After developing in this manner, heat treatment (post-bake) is performed at a temperature of 180 to 250° C. for 20 to 100 minutes. This post-baking is performed for the purpose of increasing the adhesion between the patterned coating film and the substrate. Post-baking, like pre-baking, is performed by heating with an oven, hot plate, or the like.

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

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

Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.

First, synthesis examples of unsaturated group-containing alkali-soluble resins as component (A) will be described. Evaluations of the resins in these synthesis examples were performed as follows unless otherwise specified.

Note that when the same model of various measuring instruments is used, the name of the instrument manufacturer is omitted from the second place onward. In addition, in the examples, all glass substrates used for producing substrates with cured resin films for measurement were subjected to the same treatment. Further, regarding the content of each component, when the first decimal place is 0, the notation below the decimal point may be omitted.

[Solid content concentration]
A glass filter [weight: W ₀ (g)] was impregnated with 1 g of the resin solution obtained in the synthesis example and weighed [W ₁ (g)], and the weight after heating at 160°C for 2 hours [W ₂ (g)] using the following formula.
Solid content concentration (wt%) = 100 x (W ₂ - W ₀ )/(W ₁ - W ₀ )

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

[Molecular weight]
The molecular weight is determined by gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 ( 1 bottle) +TSKgelSuper H-5000 (1 bottle) (manufactured by Tosoh Corporation), temperature: 40°C, speed: 0.6 ml/min), converted to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit) The weight average molecular weight (Mw) was determined as a value.

The abbreviations used in the synthesis examples are as follows.
BPFE: Bisphenol fluorene type epoxy resin (epoxy resin in which Ar is a benzene ring and l is 0 in general formula (5), epoxy equivalent 256 g/eq)
TPP: Triphenylphosphine AA: Acrylic acid PGMEA: Propylene glycol monomethyl ether acetate HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride ODPA: 4,4'-oxydiphthalic dianhydride THPA: 1,2 ,3,6-tetrahydrophthalic anhydride PA: Phthalic anhydride SA: Succinic anhydride DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: Styrene AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ : Hydroquinone TEA : Triethylamine BPDA : 3,3',4,4'-biphenyltetracarboxylic dianhydride BTDA : 3,3',4,4'-benzophenonetetracarboxylic dianhydride PMDA : Benzene 1,2, 4,5-Tetracarboxylic dianhydride DPHA: dipentaerythritol hexaacrylate
PTMA: Pentaerythritol tetra (mercaptoacetate)
BzDMA: Benzyldimethylamine

(Unsaturated group-containing alkali-soluble resin)
[Synthesis example 1]
In a 250 mL four-necked flask with a reflux condenser, BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g), and PGMEA (40.00 g) were added. The mixture was charged and stirred at 100 to 105°C for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added to adjust the solid content to 50% by mass.

Next, HPMDA (10.95 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 to 120°C for 6 hours to obtain an unsaturated group-containing alkali-soluble resin. (A)-1 was obtained. The solid content concentration of the obtained resin solution was 56.0% by mass, the acid value (in terms of solid content) was 105 mgKOH/g, and the Mw by GPC analysis was 4000.

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

Next, 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 115-120 The mixture was stirred at ℃ 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% by mass, the acid value (solid content equivalent) was 106 mgKOH/g, and the Mw by GPC analysis was 3300.

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

Next, 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 115-120 The mixture was stirred at ℃ 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% by mass, the acid value (solid content equivalent) was 110 mgKOH/g, and the Mw by GPC analysis was 2500.

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

Next, 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 The mixture was stirred at ℃ 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% by mass, the acid value (solid content equivalent) was 110 mgKOH/g, and the Mw by GPC analysis was 4000.

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

Next, 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 to 120°C for 6 hours to dissolve the unsaturated group-containing alkali-soluble resin. (A)-5 was obtained. The solid content concentration of the obtained resin solution was 57.2% by mass, the acid value (solid content equivalent) was 96 mgKOH/g, and the Mw by GPC analysis was 3500.

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

Next, after purging the inside of the flask with air, AA (24.0 g, 95% of the number of moles of glycidyl groups), TDMAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution. The mixture was added and stirred at 120° C. for 6 hours to obtain a polymerizable unsaturated group-containing copolymer solution. SA (30.0 g, 90% of the number of moles of AA added) and TEA (0.5 g) were added to the obtained copolymer solution containing polymerizable unsaturated groups, and the reaction was carried out at 120°C for 4 hours to remove polymerizable unsaturated groups. An alkali-soluble copolymer resin solution (A)-6 was obtained. The solid content concentration of the resin solution was 46.0% by mass, the acid value (solid content equivalent) was 76 mgKOH/g, and the Mw by GPC analysis was 5300.

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

Next, 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 to 120°C for 6 hours to dissolve the unsaturated group-containing alkali-soluble resin. (A)′-7 was obtained. The solid content concentration of the obtained resin solution was 57.0% by mass, the acid value (in terms of solid content) was 96 mgKOH/g, and the Mw by GPC analysis was 3600.

[Synthesis example 8]
In a 250 mL four-necked flask with a reflux condenser, BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g), and PGMEA (40.00 g) were added. The mixture was charged and stirred at 100 to 105°C for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added to adjust the solid content 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 to 120°C for 6 hours to dissolve the unsaturated group-containing alkali-soluble resin. (A)'-8 was obtained. The solid content concentration of the obtained resin solution was 57.4% by mass, the acid value (solid content equivalent) was 105 mgKOH/g, and the Mw by GPC analysis was 3200.

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

Next, 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 to 120°C for 6 hours to dissolve the unsaturated group-containing alkali-soluble resin. (A)′-9 was obtained. The solid content concentration of the obtained resin solution was 55.9% by mass, the acid value (solid content equivalent) was 105 mgKOH/g, and the Mw by GPC analysis was 3600.

[Synthesis example 10]
In a 1 L four-neck flask, PTMA (20.00 g, mercapto group 0.19 mol), DPHA (212.00 g, acrylic group 2.12 mol), PGMEA (58.00 g), HQ (0.1 g), and BzDMA (0.01 g) was added and reacted at 60° C. for 12 hours to obtain dendritic polymer solution (B)-2. The disappearance of mercapto groups in the obtained dendritic polymer was confirmed by iodometry. The solid content concentration of the obtained dendritic polymer solution was 80.0% by mass, and the Mw by GPC analysis was 10,000.

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

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

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

(epoxy compound)
(C): Biphenyl type epoxy resin (jER YX4000, manufactured by Mitsubishi Chemical Corporation)

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

(Polymerization initiator)
(E): 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane ("Omnirad907" manufactured by IGM Resins B.V., "Omnirad" is a registered trademark of the company)

(sensitizer)
(F): Michler ketone

[evaluation]
[Calculation of highest occupied orbit (HOMO) and lowest unoccupied orbit (LUMO)]
Highest occupied orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of unsaturated group-containing alkali-soluble resins ((A)-1 to (A)-5, and (A)'-7 to (A)'-9) The energy was determined by quantum chemical calculation based on the constituent units of these resins represented by the following general formula (13). The "Gaussian 16, Revision B.01" software package (Gaussian Inc.) was used for quantum chemical calculations. Specifically, the density functional theory ( DFT), using B3LYP as the functional and 6-31G(d) as the basis function, calculate the most stable structure of the constituent unit and the energy of the highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO) in that structure. (Gaussian input line "#B3LYP/6-31G(d)OPT").

（式（１３）中、Ｙはそれぞれの樹脂の合成に用いたテトラカルボン酸二無水物に由来する残基であり、Ｚはそれぞれの樹脂の合成に用いたジカルボン酸無水物に由来する残基である。）

(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 acid anhydride used in the synthesis of each resin. )

The energies of the highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO) of the unsaturated group-containing alkali-soluble resin ((A)-6) are expressed by the constituent units of these resins expressed by the following general formula (14). Based on this, calculations were made in the same manner as (A)-1 to (A)-5 and (A)'-7 to (A)'-9.

（式（１４）中、ａ、ｂおよびｃは各構成単位のモル比であり、算出時にはａ：ｂ：ｃ＝１：１：１とした。）

(In formula (14), a, b, and c are the molar ratios of each structural unit, and at the time of calculation, a:b:c=1:1:1.)

(Preparation of substrate with cured resin film for transmittance evaluation after initial transmittance/light resistance test)
The photosensitive resin composition shown in Table 1 was heated and cured on a 125 mm x 125 mm glass substrate "#1737" whose surface had been cleaned by irradiating ultraviolet rays with a wavelength of 254 nm and an illuminance of 1000 mJ/ ^cm2 using a low-pressure mercury lamp. The coating was applied using a spin coater so that the film thickness after treatment was 10.0 μm, and a dry film was prepared by prebaking at 90° C. for 3 minutes using a hot plate. Next, main curing (post-baking) was performed at 230° C. for 30 minutes using a hot air dryer to obtain substrates with cured resin films according to Examples 1 to 10 and Comparative Examples 1 to 3.

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

[Transmittance evaluation after light resistance test]
After main curing, a blue filter "IEB400" (manufactured by Isuzu Seiko Glass Co., Ltd., 50 mm x 50 mm x 5 mm thick, transmittance of wavelengths below 340 nm and above 480 nm is less than 10%) was placed on the substrate with the cured film, and the Xe Light irradiation was performed for 500 hours in a test chamber "Q-SUN Xe-1" (manufactured by Q-Lab Corporation). The transmittance at a wavelength of 400 nm was measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.) in the area on the substrate with the resin cured film that was irradiated with light through a blue filter. did.

(Preparation of cured resin film powder for evaluation of thermal decomposition resistance)
The photosensitive resin composition shown in Table 1 was coated on a glass substrate "#1737" using a spin coater so that the film thickness after heat curing was 10.0 μm, and then coated with a hot plate for 90 μm. A dry film was prepared by prebaking at ℃ for 3 minutes. Thereafter, main curing (post-baking) was performed at 230° C. for 30 minutes using a hot air dryer to obtain substrates with cured resin films according to Examples 1 to 10 and Comparative Examples 1 to 3. The obtained cured film was shaved into powder and used for TG-DTA measurement.

[Heat decomposition resistance evaluation]
(Evaluation method)
The resulting cured resin film powder was heated in air from 30°C to 400°C at a heating rate of 5°C/min using a TG-DTA device "TG/DTA6200" (manufactured by Seiko Instruments Inc.). , the temperature at which the weight of the specimen decreased by 5% was measured. Note that a score of △ or higher was considered to be a pass.

(Evaluation criteria)
◎: 5% weight loss temperature is 320°C or higher ○: 5% weight loss temperature is 300°C or higher and lower than 320°C △: 5% weight loss temperature is 280°C or higher and lower than 300°C ×: 5% weight loss temperature is less than 280°C

(Preparation of cured resin film for glass transition point evaluation)
The photosensitive resin composition shown in Table 1 is coated on a release aluminum foil "Sepanium" (manufactured by Toyo Aluminum Co., Ltd.) using a spin coater so that the film thickness after heat curing is 30.0 μm. Then, a dry film was prepared by prebaking at 90° C. for 3 minutes using a hot plate. Next, main curing (post-baking) was performed at 230° C. for 30 minutes using a hot air dryer. Finally, the cured resin film was peeled off from the release aluminum foil to obtain cured resin films according to Examples 1 to 10 and Comparative Examples 1 to 3.

[Glass transition point evaluation]
Using a dynamic viscoelasticity (DMA) measuring device (RSA-G2 manufactured by TA Instruments Co., Ltd.), a cured film with a width of 5 mm was set so that the length between the chucks was 22 mm, and the temperature was heated from 30 to 300 °C. The glass transition point was measured in the temperature range of . Note that a score of △ or higher was considered to be a pass.

(Evaluation criteria)
◎: The glass transition point is 180°C or higher. ○: The glass transition point is 160°C or higher and lower than 180°C. △: The glass transition point is 140°C or higher and lower than 160°C. ×: The glass transition point is 140°C or higher and lower than 160°C. , less than 140℃

(Preparation of substrate with cured resin film for evaluation of development adhesion and initial pattern transmittance)
The photosensitive resin composition shown in Table 1 was coated on a glass substrate "#1737" using a spin coater so that the film thickness after heat curing was 10.0 μm, and then coated with a hot plate for 90 μm. A dry film was prepared by prebaking at ℃ for 3 minutes. Next, the dried film was irradiated with ultraviolet rays of 500 mJ/cm ² using an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm ² to perform a photocuring reaction of the dried film.

Next, the exposed film was developed with a 2.38% TMAH (tetramethylammonium hydroxide) developer at 23° C. at a shower pressure of 1 kgf/cm ² for 60 seconds, and then developed at a shower pressure of 5 kgf/cm ² . Spray washing was performed to remove unexposed areas to form a 10 μm dot pattern. Finally, main curing (post-baking) was performed at 230° C. for 30 minutes using a hot air dryer to obtain substrates with cured resin films according to Examples 1 to 10 and Comparative Examples 1 to 3.

[Development adhesion]
The 10 μm dot pattern of the resin cured film of the obtained resin cured film coated substrate was observed using an optical microscope to determine whether or not the pattern was peeled off. Note that a score of △ or higher was considered to be a pass.

(Evaluation criteria)
○: No peeling is seen in the pattern △: Peeling is seen in a small part of the pattern ×: Most of the pattern is peeled off

[Pattern initial transmittance evaluation]
Using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.), the transmittance of the cured film-coated substrate after development and main curing was measured at a wavelength of 400 nm.

The evaluation results are shown in Table 2.

As shown in Table 2, the resin cured films of Examples 1 to 10 obtained from the photosensitive resin compositions of the present invention showed small changes in transmittance of the coating films when irradiated with light with a wavelength of 340 nm to 480 nm. It was found that yellowing of the paint film was suppressed. This is thought to be because by setting the energy difference between the HOMO and LUMO of component (A) to 3.7 eV or more, it was possible to suppress the absorption of light in the relevant wavelength range and suppress the deterioration of the cured resin film. .

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

As shown in Examples 7 to 9, by using a resin made of a dicarboxylic acid or tricarboxylic acid having a cyclic structure or an acid monoanhydride thereof as the component (A), peeling during pattern formation is suppressed, and resin curing is suppressed. It has been found that it is possible to form fine patterns in the film.

As shown in Examples 7 to 10, by using a dendritic polymer as the component (B), penetration of the developer into the photocured area is suppressed, and yellowing of the resin cured film during main curing (post-bake) is suppressed. It was found that changes can be suppressed.

INDUSTRIAL APPLICATION This invention can provide the photosensitive resin composition which can be used at the time of manufacture of various products. In particular, a cured resin film suitable for use in fixing and sealing an optical semiconductor on a mounting board can be provided.

Claims (7)

(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;
(D) a solvent;
including;
The component (A) is a curable resin composition in which the energy difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) is 3.7 eV or more, as calculated by quantum chemical calculation. . 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 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar are alkyl groups having 1 to 10 carbon atoms, carbon Substitution selected from the group consisting of an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. may be substituted with a group. R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. 1 is independently a number of 0 or more and 3 or less. G is independently ( meth)acryloyl 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 It is 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. .)

(In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkylarylene group having 2 or more carbon atoms and 10 or less carbon atoms, and R ₄ is a carbon number 2 or less. (It is a saturated or unsaturated hydrocarbon group with a number of 0 to 10, p is a number of 0 to 10, and * 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 binding site.) The curable resin composition according to claim 1, wherein the component (A) is a resin having a weight average molecular weight of 1000 to 40000 and an acid value of 50 mgKOH to 200 mgKOH. The curable resin composition according to claim 1, comprising at least one of (E) a polymerization initiator and (F) a sensitizer. A cured resin film obtained by curing the curable resin composition according to any one of claims 1 to 4. A semiconductor package comprising the cured resin film according to claim 5 as at least one protective film. A display device comprising the cured resin film according to claim 5 as at least one protective film.