CN116789912A - Curable resin composition, resin cured film, semiconductor package, and display device - Google Patents

Abstract

The invention provides a curable resin composition, a resin cured film, a semiconductor package and a display device, wherein the curable resin composition can obtain the resin cured film, the semiconductor package and the display device which are not easy to generate time yellowing caused by electromagnetic waves with the wavelength of 340-480 nm. A curable resin composition comprising (A) an alkali-soluble resin having 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. The component (A) is a resin having an energy difference between the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) calculated by quantum chemical computation of 3.7eV or more.

Description

Curable resin composition, resin cured film, semiconductor package, and display device

Technical Field

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

Background

A protective film for sealing and protecting each element to a substrate is used in a semiconductor device, an image display device, or the like. As the protective film for which transparency or heat resistance is required, a cured film obtained by applying a curable resin composition containing an alkali-soluble resin having an unsaturated group and a fluorene skeleton, patterning and curing the composition can be used (for example, patent document 1).

[ Prior Art literature ]

[ patent literature ]

[ patent document 1] Japanese patent laid-open publication No. 2003-089716

Disclosure of Invention

[ problem to be solved by the invention ]

It is known that a cured film made of an alkali-soluble resin having a fluorene skeleton as described in patent document 1 is excellent in transparency and heat resistance. However, according to the findings of the present inventors, if the cured film absorbs electromagnetic waves having a wavelength of about 340nm to 480nm, which are emitted from an ultraviolet light emitting diode (UV-LED) or a Blue light emitting diode (Blue-LED), the cured film may be degraded slowly and may undergo yellowing with time.

The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a curable resin composition that can provide a cured film that is less likely to cause yellowing with time due to electromagnetic waves having a wavelength of 340nm to 480nm, a resin cured film formed from the curable resin composition, and a semiconductor package and a display device having the resin cured film.

[ means of solving the problems ]

One embodiment of the present invention for solving the above problems relates to the curable resin compositions of the following [1] to [4 ].

[1] A curable resin composition comprising:

(A) An alkali-soluble resin containing an unsaturated group,

(B) A polymerizable compound having two or more unsaturated bonds,

(C) Epoxy compound having two or more epoxy groups

(D) The solvent is used for the preparation of the aqueous solution,

the component (A) is a resin having an energy difference between the highest occupied molecular orbital (Highest Occupied Molecular Orbital, HOMO) and the lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital, LUMO) calculated by quantum chemical computation of 3.7eV or more.

[2] The curable resin composition according to [1], wherein the component (A) is a resin represented by the following general formula (1).

[ chemical 1]

(in the formula (1), ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, a part of hydrogen atoms constituting Ar may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms and a halogen group, R ₁ Independently an alkylene group having 2 to 4 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 of Z is a substituent represented by the following general formula (4); n is a number having an average value of 1 to 20 inclusive

[ chemical 2]

[ chemical 3]

(in the formula (2) and the formula (3), R ₂ Is a hydrogen atom or methyl group, R ₃ An alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R ₄ Saturated or unsaturated hydrocarbon groups having 2 to 20 carbon atoms, p is a number of 0 to 10 carbon atoms, and is a bond site

[ chemical 4]

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

[3] The curable resin composition according to [1] or [2], wherein the component (A) is a resin having a weight average molecular weight of 1000 or more and 40000 or less and an acid value of 50mgKOH/g or more and 200mgKOH/g or less.

[4] The curable resin composition according to any one of [1] to [3], which comprises at least one of (E) a polymerization initiator and (F) a sensitizer.

Another embodiment of the present invention relates to the resin cured film of the following [5 ].

[5] A resin cured film obtained by curing the curable resin composition according to any one of [1] to [4 ].

Still another embodiment of the present invention relates to a semiconductor package of the following [6 ].

[6] A semiconductor package obtained by using the resin cured film according to [5] as at least one protective film.

A further aspect of the present invention relates to the display device of the following [7 ].

[7] A display device using the resin cured film according to [5] as at least one protective film.

[ Effect of the invention ]

The present invention provides a curable resin composition which can provide a cured film less likely to cause yellowing with time due to electromagnetic waves having a wavelength of 340 to 480nm, a resin cured film formed from the curable resin composition, and a semiconductor package and a display device having the resin cured film.

Detailed Description

1. Curable resin composition

Hereinafter, the curable resin composition according to an embodiment of the present invention comprises (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 ]

(A) The component (a) is an alkali-soluble resin containing an unsaturated group. (A) The component (A) is soluble in an alkali developer and imparts patterning properties to the curable resin composition.

(A) The 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. (A) The component is not particularly limited as long as it is the resin, and may be various kinds of resins. (A) The component (c) has a polymerizable unsaturated group, and therefore imparts excellent photo-hardenability to the curable resin composition, and when cured, the component (c) has a large molecular weight and functions as a binder. In addition, since the component (a) has an acidic group, developability, patterning characteristics (pattern line width, pattern linearity) and the like are improved.

In the present embodiment, the component (a) is a resin having an energy difference between the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) calculated by quantum chemical calculation of 3.7eV or more. The energy difference between the HOMO and LUMO is larger than the energy of electromagnetic wave with the wavelength of 340-480 nm. Therefore, the component (A) is less likely to absorb electromagnetic waves having a wavelength of 340nm to 480nm, and is less likely to cause deterioration in the time-lapse property due to absorption of the electromagnetic waves.

The energy difference is an energy difference between the energy of HOMO and the energy of LUMO, which is obtained by a density functional method (Density Functional Theory, DFT) in the most stable structure among the structures of the structural units, based on the structural units of the component (a). The most stable structure can be obtained from the molecular structure of component (A) by a known structure optimization method. In the present specification, the energy of HOMO and LUMO of the component (a) is set to be the energy of Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) in the most stable structure of the molecular structure calculated using "Gaussian 16, revision b.01 (Gaussian 16, revision b.01)" package (Gaussian inc.), with charge 0 and multiple 1, by Density Functional (DFT), using B3LYP as a functional function and using 6-31G (d) as a basis function, with (Gaussian) input line "#b3lyp/6-31G (d) OPT"), for the molecular structure of the component (a). Among them, other calculation science software having the same function can be used in the calculation of DFT and Time-dependent density functional theory (Time-Dependent Density Functional Theory, TDDFT). In the quantum scientific calculation, the energy of HOMO and LUMO may be obtained for each of the partial structures of the unconjugated component (a), and the minimum value of the energy difference between HOMO and LUMO obtained from these partial structures may be the energy difference.

The energy difference is preferably 3.7eV or more and 6.0eV or less. When the energy difference is 3.7eV or more, electromagnetic waves having a wavelength of about 340nm to 480nm are not easily absorbed, and thus the deterioration of the component (a) with time and the yellowing of the cured film with time can be suppressed. The upper limit of the energy difference is not particularly limited, but may be 6.0eV or less.

(A) The component (b) may be any alkali-soluble resin as long as it satisfies the above-mentioned energy difference requirement. Examples of the component (a) include: an unsaturated group-containing alkali-soluble resin obtained by reacting (i) 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 an acid anhydride thereof, (ii) an unsaturated group-containing alkali-soluble resin as an acrylic (co) polymer, (iii) an unsaturated group-containing alkali-soluble resin as a polysiloxane containing a plurality of siloxane bonds, and the like.

Examples of the unsaturated group-containing monocarboxylic acid used for the synthesis of the component (a) include (meth) acrylic acid, and compounds obtained by reacting (meth) acrylic acid with dicarboxylic acids such as succinic acid, maleic acid, phthalic acid, or acid monoanhydrides thereof.

The term "(meth) acrylic acid" refers to the sum of acrylic acid and methacrylic acid, the term "(meth) acryl" refers to the sum of acryl and methacryl, and the term "(meth) acrylate" refers to the sum of acrylate and methacrylate, and means one or both of these.

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

Examples of the epoxy compound having two or more epoxy groups include: bisphenol a type epoxy compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, diphenylfluorene type epoxy compound, phenol novolac type epoxy compound, o-cresol novolac type epoxy compound, m-cresol novolac type epoxy compound, p-cresol novolac type epoxy compound, phenol aralkyl type epoxy compound, biphenyl type epoxy compound (for example, jER YX4000: the "jER" is a registered trademark of the company, manufactured by mitsubishi chemical Co., ltd.), a phenol novolac compound containing a naphthalene skeleton (for example, NC-7000L: manufactured by Japanese chemical Co., ltd.), a naphthol aralkyl type epoxy compound, a triphenol methane type epoxy compound (for example, EPPN-501H: manufactured by Japanese chemical Co., ltd.), an epoxy compound having an aromatic structure such as a tetraphenolethane type epoxy compound, a glycidyl ether of a polyhydric alcohol, a glycidyl ester of a polycarboxylic acid, a copolymer of a monomer having a (meth) acryloyl group containing a glycidyl ester of (meth) acrylic acid as a unit represented by a copolymer of methacrylic acid and a glycidyl ester of methacrylic acid, a hydrogenated bisphenol A diglycidyl ether (for example, rikaresin) HBE-100: manufactured by New Japanese chemical Co., ltd., "Rikaresin (Rikaresin) is a registered trademark of the company), an epoxy compound having a glycidyl group such as 1, 4-cyclohexanedimethanol-bis 3, 4-epoxycyclohexane carboxylate, 2- (3, 4-epoxy) cyclohexyl-5, 1-spiro (3, 4-epoxy) cyclohexyl-m-dioxane (e.g., ala Lu Date (Araldite) CY175: hensmal (Huntsman) corporation, "ara Lu Date (Araldite)" is a registered trademark of the company), bis (3, 4-epoxycyclohexylmethyl) adipate (e.g., hilar (CYRACURE) UVR-6128: manufactured by Dow Chemical corporation), 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexane carboxylate (e.g., 60 (Celloxide) 2021P: daicel) manufactured by the company, "ara Luo Xide (Celloxide)" is a registered trademark of the company), butane tetracarboxylic acid tetrakis (3, 4-epoxycyclohexylmethyl) modified epsilon-caprolactone (e.g., ai Bo li (epolate) GT401: daicel (manufactured by the company), epoxy compound having epoxycyclohexyl (e.g., 60: hirem-1P: daicel) manufactured by the company, registered trademark of the company), industry di (e.g., 7200) having epoxycyclohexyl functional group, such as well as a polydiene (HP) manufactured by the company, industry di-end group, such as the product of the industry di-7200, alicyclic epoxy compounds such as 1, 2-epoxy-4- (2-oxetanyl) cyclohexane adducts of 2, 2-bis (hydroxymethyl) -1-butanol (for example, EHPE3150: manufactured by Daicel Co., ltd.), epoxidized polybutadiene (for example, nirope (NISSO) -PB.JP-100: manufactured by Nisoida Co., ltd., "Nirope (NISSO) -PB" is a registered trademark of the same company), epoxy compounds having a silicone skeleton, and the like.

Examples of the unsaturated group-containing alkali-soluble resin (ii) as the acrylic (co) polymer include resins having a (meth) acryloyl group and a carboxyl group as copolymers of (meth) acrylic acid, (meth) acrylic acid ester and the like. Examples of the resin include an alkali-soluble resin containing a polymerizable unsaturated group obtained by: the copolymer is obtained by copolymerizing (meth) acrylic esters containing glycidyl (meth) acrylate in a solvent, reacting the obtained copolymer with (meth) acrylic acid, and finally reacting with an anhydride of a dicarboxylic acid or a tricarboxylic acid. The copolymers can be referred to: a copolymer represented in Japanese patent application laid-open No. 2014-111722, which comprises 20 to 90 mol% of a repeating unit derived from a diester glycerol obtained by esterifying hydroxyl groups at both ends with (meth) acrylic acid, 10 to 80 mol% of a repeating unit derived from one or more polymerizable unsaturated compounds copolymerizable therewith, and has a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH/g; and an alkali-soluble resin containing a polymerizable unsaturated group, which is a polymer having a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30mgKOH/g to 200mgKOH/g, and containing a unit derived from a (meth) acrylate compound and a unit having a (meth) acryloyl group and a dicarboxylic acid residue or a tricarboxylic acid residue, as shown in JP-A2018-141968.

The unsaturated group-containing alkali-soluble resin (iii) as the polysiloxane includes, for example, a polysiloxane compound having a (meth) acryloyl group and a carboxyl group. Examples of the compounds include: a silicone-modified acrylic resin obtained by reacting an epoxy acrylate, a silicone diamine, and an aromatic acid dianhydride (Japanese patent application laid-open No. 2002-226549, etc.); a silicone-containing polyamide resin obtained by reacting a silicone diamine, an aromatic diamine having an ethylenic unsaturated bond, and an aromatic tetracarboxylic dianhydride (international publication No. 2009/075217, etc.); a silicone-containing polyamic acid resin obtained by reacting a diamine including a siloxane diamine with an aromatic tetracarboxylic dianhydride (japanese patent application laid-open No. 2008-070477, international publication No. 2006/109514, japanese patent application laid-open No. 2010-204590, etc.); an alkali-soluble resin having a substituent having a group containing a polymerizable double bond and a carboxyl group bonded to an isocyanurate ring skeleton, which is obtained by: and reacting an epoxy silicone compound having an isocyanurate ring skeleton with a carboxylic acid having a polymerizable double bond to obtain a polyol compound, and reacting the obtained polyol compound with a dicarboxylic acid or an acid monoanhydride thereof (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 energy of HOMO and the energy of LUMO can be increased. Specifically, the energy difference between the energy of HOMO and the energy of LUMO can be increased to the above range by setting at least a part of the aromatic dicarboxylic acid, the aromatic tricarboxylic acid, the aromatic tetracarboxylic acid, the acid anhydride thereof, or the like used in the synthesis of the conventional alkali-soluble resin to a non-aromatic carboxylic acid or acid anhydride thereof.

The component (a) preferably has a plurality of aromatic rings, and further preferably has a repeating unit including a fluorene structure, and further preferably has a repeating unit including a bisaryl fluorene skeleton, from the viewpoint of suppressing decomposition of the resin cured film due to heat and increasing the glass transition temperature to suppress deformation due to heat. For example, the component (A) is preferably a resin represented by the following general formula (1).

[ chemical 5]

In the formula (1), ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy or halogen group having 1 to 5 carbon atoms. R is R ₁ Independently an alkylene group having 2 to 4 carbon atoms. l is independently a number of 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 of Z is a substituent represented by the following general formula (4). n is a number having an average value of 1 to 20.

[ chemical 6]

[ chemical 7]

In the formula (2) and the formula (3), R ₂ Is a hydrogen atom or methyl group, R ₃ An alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R ₄ Saturated or unsaturated hydrocarbon groups having 2 to 20 carbon atoms, p is a number of 0 to 10 carbon atoms, and p is a bond site.

[ chemical 8]

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

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

First, an epoxy compound (a-1) (hereinafter, also simply referred to as "epoxy compound (a-1)") having a bisaryl fluorene skeleton, which may have several alkylene oxide-modified groups in one molecule, represented by the following general formula (5) is reacted with at least one of (meth) acrylic acid, a (meth) acrylic acid derivative represented by the following general formula (6), and a (meth) acrylic acid derivative represented by the following general formula (7), to obtain a diol compound as an epoxy (meth) acrylate. Further, the bisaryl fluorene skeleton is preferably a binaphthol fluorene skeleton or a biphenol fluorene skeleton.

[ chemical 9]

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

[ chemical 10]

[ chemical 11]

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

The reaction of the epoxy compound (a-1) with (meth) acrylic acid or a derivative thereof can be carried out using a known method. For example, japanese patent application laid-open No. 4-355450 describes: by using about 2 moles of (meth) acrylic acid with respect to 1 mole of the epoxy compound having two epoxy groups, a diol compound having a polymerizable unsaturated group can be obtained. In the present embodiment, the compound obtained by the reaction is a polymerizable unsaturated group-containing diol (d) (hereinafter, also simply referred to as "diol (d)") represented by the following general formula (8).

[ chemical 12]

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

[ chemical 13]

[ chemical 14]

In the formula (2) and the formula (3), R ₂ Is a hydrogen atom or methyl group, R ₃ An alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R ₄ Saturated or unsaturated hydrocarbon groups having 2 to 20 carbon atoms, p is a number of 0 to 10 carbon atoms, and p is a bond site.

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

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

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

Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include: succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid (malonic acid), glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, and these dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include: cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, chlormycolic acid, hexahydrotrimellitic acid, norbornanedicarboxylic acid, and the like, and these dicarboxylic acids or tricarboxylic acids having any substituents introduced therein.

Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include: phthalic acid, isophthalic acid, 1, 8-naphthalene dicarboxylic acid, 2, 3-naphthalene dicarboxylic acid, trimellitic acid, and the like, and these dicarboxylic acids or tricarboxylic acids having any substituents introduced therein.

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

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

Further, these dicarboxylic acids or tricarboxylic acids preferably have a cyclic structure in view of being able to form finer patterns. More specifically, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or acid monoanhydrides thereof are preferably used. If dicarboxylic acid or tricarboxylic acid having a cyclic structure is used, the resin fluidity is lowered by introducing the cyclic structure at the end, and thus peeling of the coating film at the time of pattern formation can be suppressed, and thus it is considered that a fine pattern can be formed.

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

Examples of the chain hydrocarbon tetracarboxylic acid include: butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids having substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups introduced therein.

Examples of the alicyclic hydrocarbon tetracarboxylic acid include: cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid, and these alicyclic tetracarboxylic acids having a substituent such as a chain hydrocarbon group and an unsaturated hydrocarbon group introduced therein.

Examples of the aromatic hydrocarbon tetracarboxylic acid include: pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid, naphthalene-2, 3,6, 7-tetracarboxylic acid, and the like. In view of further increasing the energy difference between HOMO and LUMO by increasing LUMO, these aromatic hydrocarbon tetracarboxylic acids are preferably aromatic hydrocarbon tetracarboxylic acids in which an electron donating atom such as oxygen is introduced into an aromatic ring of an acid anhydride moiety or dispersed in a plurality of aromatic rings of which the acid anhydride skeleton is not conjugated. For example, the tetracarboxylic acid is preferably diphenyl ether tetracarboxylic acid.

The tetracarboxylic acid is preferably an acid dianhydride thereof.

Alternatively, instead of the tetracarboxylic acid or its acid dianhydride (c), a trimellitic anhydride aryl ester may be used. The aryltrimellitic anhydride ester is a compound produced by the method described in, for example, international publication No. 2010/074065, and is an acid dianhydride in which two hydroxyl groups of an aromatic diol (naphthalene diol, biphenol, terphenyl diol, etc.) react with carboxyl groups of a two-molecule trimellitic anhydride, respectively, and are bonded by an ester linkage.

The method for reacting the diol (d) with the acid component (b) and the acid component (c) is not particularly limited, and a known method can be used. For example, JP-A-9-325494 discloses a method in which an epoxy (meth) acrylate is reacted with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ℃.

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

For example, when the acid monoanhydride (b) and the acid dianhydride (c) are used, the reaction is preferably carried out such that the molar ratio of the acid component [ (b)/2+ (c) ] to the diol (d) [ [ b)/2+ (c) ]/(d) ] is greater than 0.5 and 1.0 or less. When the molar ratio is 1.0 or less, the terminal of the unsaturated group-containing curable resin represented by the general formula (1) does not become an acid anhydride, and therefore an increase in the content of unreacted acid dianhydride can be suppressed, and the stability over time of the curable composition can be improved. If the molar ratio is more than 0.5, the remaining amount of unreacted components in the polymerizable unsaturated group-containing diol (d) can be suppressed from increasing, and the stability of the curable composition with time can be improved. The molar ratio of the components (b), (c) and (d) may be arbitrarily changed within the above-mentioned range for the purpose of adjusting the acid value and molecular weight of the unsaturated group-containing curable resin represented by the general formula (1).

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

Examples of the solvent include: cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, solvents such as diethylene glycol dimethyl ether, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone solvents such as cyclohexanone and diisobutyl ketone. The reaction conditions of the solvent, catalyst, and the like used are not particularly limited, and, for example, a solvent having no hydroxyl group and a boiling point higher than the reaction temperature is preferably used as the reaction solvent.

The reaction of the epoxy group with the carboxyl group or the hydroxyl group is preferably performed using a catalyst. As the catalyst, JP-A-9-325494 discloses ammonium salts such as tetraethylammonium bromide and triethylbenzyl ammonium chloride, phosphines such as triphenylphosphine and tris (2, 6-dimethoxyphenyl) phosphine, and the like.

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

(A) The component (a) is preferably a compound having a weight average molecular weight (Mw) of 1000 to 40000, more preferably a compound having a weight average molecular weight (Mw) of 2000 to 20000. (A) The higher the Mw of the component is, the more the adhesiveness and flexibility of the resin cured film are improved, and the easier the crosslinking density is to be adjusted. On the other hand, the lower the Mw of the component (A), the more the solubility of the component (A) in the solvent increases, and the more the compatibility with the component (B) improves, and the white turbidity suppressing property, flatness and patterning property of the resin cured film are improved. In view of further improving the compatibility with component (B), the Mw of component (a) is preferably 1000 or more and 30000 or less, more preferably 1500 or more and 25000 or less. In the case of using the resin represented by the general formula (1) as the component (a), the Mw of the 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 equivalent amount of acrylic groups and a large molecular weight is used as the component (B). For example, when the molecular weight (Mw) of the component (B) is 3000 or more, the compatibility of the component (a) can be sufficiently improved by setting the Mw of the component (a) to 6000 or less.

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

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of each component may be calculated as styrene-converted values by gel permeation chromatography (gel permeation chromatograph, GPC) (for example, "HLC-8220GPC" (manufactured by Tosoh) corporation). The acid value may be obtained by using a potential difference titration apparatus (for example, "COM-1600" (manufactured by the company limited of the biogas industry Co.). Among them, for a compound such as a monomer whose molecular weight can be calculated from the structure, a value calculated from the structure can be set as the molecular weight of the compound.

The content of the component (a) is preferably 10 mass% or more and 90 mass% or less, more preferably 20 mass% or more and 80 mass% or less, and even more preferably 40 mass% or more and 80 mass% or less, with respect to the total mass of the solid component, when the patterning characteristics are important. When the content of the component (a) is 10 mass% or more, a high-resolution pattern can be formed.

The component (A) may be used alone or in combination of two or more.

[ (B) component ]

(B) The component (a) is a polymerizable compound having two or more unsaturated bonds. Examples of the component (B) include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 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 hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene (phosphazene) alkylene oxide modified hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like. Only one of these polymerizable compounds may be used alone, or two or more of them may be used in combination. (B) The component (a) may be any component as long as it can crosslink molecules of the component (a), and it is preferable to use a component having three or more unsaturated bonds in view of further sufficiently exerting the above-mentioned functions. The equivalent weight of the acrylic group of the polymerizable compound divided by the number of (meth) acryloyl groups in one molecule is preferably 50 to 300, more preferably 80 to 200. In addition, component (B) does not have a free carboxyl group.

The component (B) may be a dendrimer having (meth) acryloyl groups. Examples of the dendritic polymer having a (meth) acryloyl group include: dendritic polymers obtained by adding a polyvalent mercapto compound to a part of carbon-carbon double bonds in (meth) acryl groups of polyfunctional (meth) acrylates. Specifically, the method comprises the following steps: a dendritic polymer 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).

[ 15]

(in the formula (9), R ₅ Is a hydrogen atom or methyl group, R ₆ To R is ₇ (OH) _k Q hydroxyl groups among k hydroxyl groups of (a) are supplied to the residue after the ester bond in the formula; preferred R ₇ (OH) _k A polyol having a hydrocarbon skeleton which is not an aromatic straight chain or branched chain having 2 to 8 carbon atoms, a polyol ether in which a plurality of molecules of the polyol are linked via an ether bond by dehydration condensation of an alcohol, or an ester of the polyol or the polyol ether with a hydroxy acid; k and q independently represent an integer of 2 to 20, but k+.q)

[ 16]

(in the formula (10), R ₈ Is a single bond or a divalent to hexavalent hydrocarbon group having 1 to 6 carbon atoms, and is represented by R ₈ When the bond is single, R is 2, and R is ₈ When the radical is bivalent-hexavalent, R is the same as R ₈ The same number of valence as the number of (c)

Examples of the polyfunctional (meth) acrylate represented by the general formula (9) include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, and the like. 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 tris (mercaptoacetate), trimethylolpropane tris (mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tris (mercaptoacetate), pentaerythritol tetrakis (mercaptopropionate), dipentaerythritol hexa (mercaptoacetate), dipentaerythritol hexa (mercaptopropionate), and the like. These compounds may be used alone or in combination of two or more.

Here, 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 preferably performed so that the carbon-carbon double bond remains in the range of 0.1 mol% to 50 mol% when the total amount of the carbon-carbon double bonds of the compound represented by the general formula (9) is 100 mol%, so that the obtained dendritic polymer can be further subjected to radiation polymerization based on the carbon-carbon double bond thereafter.

For example, the mercapto group of the polyvalent mercapto compound represented by the general formula (10) and the carbon-carbon double bond (in the general formula (9), CH ₂ ＝C(R ₅ ) The double bond represented, referred to as double bond in the case of calculated molar ratio), the molar ratio of mercapto groups/double bond is preferably 1/100 to 1/3, more preferably 1/50 to 1/5, particularly preferably 1/20 to 1/8.

In addition, the dendritic polymer preferably has a functional group in an amount sufficient for radiation polymerization. Therefore, the acrylic group equivalent of the dendritic polymer is preferably in the range of 100 to 10000. Further, since the molecular weight of the dendritic polymer having a (meth) acryloyl group is large, the penetration of the developer into the exposed portion of the coating film can be suppressed during pattern formation, and yellowing of the resin cured film can be suppressed during main curing (post baking). For example, the weight average molecular weight (Mw) of the dendritic polymer having a (meth) acryloyl group is preferably in the range of 1000 to 20000, more preferably in the range of 7000 to 20000, and still more preferably in the range of 8000 to 15000.

(A) The blending ratio of the component (A) to the component (B) is preferably 30/70 to 90/10, more preferably 60/40 to 80/20, in terms of the mass ratio (A)/(B). When the blending ratio of the component (A) is 30/70 or more, the cured product after photo-curing is less likely to become brittle, and the acid value of the coating film in the unexposed portion is less likely to become low, so that the decrease in solubility in an alkali developer can be suppressed. Therefore, defects such as burrs or unclear edges of the pattern are less likely to occur. In addition, if the blending ratio of the component (A) is 90/10 or less, the proportion of the photoreactive functional group in the resin is sufficient, and thus the formation of a desired crosslinked structure can be performed. Further, since the acid value of the resin component is not excessively high, the solubility of the exposed portion in the alkali developer is not easily increased, and thus the formed pattern can be suppressed from becoming finer than the target line width or from being lost.

[ (C) component ]

(C) The component (a) is an epoxy compound having two or more epoxy groups. (C) The composition can improve the chemical resistance of the resin cured film and the moisture-resistant adhesion of the resin cured film. The reason for this is considered that the hygroscopicity of the component (a) due to the carboxyl group can be reduced by protecting the carboxyl group of the component (a) by reacting with the epoxy group of the component (C) at the time of main curing (post baking).

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

Among these, bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, biphenyl type epoxy compounds are preferable, and biphenyl type epoxy compounds are more preferable. The biphenyl type epoxy compound can give a cured product having satisfactory properties in terms of mechanical strength and chemical resistance.

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

The epoxy equivalent of component (C) can be determined by titration with a 1/10N-perchloric acid solution using a potential difference titration apparatus "COM-1600" (manufactured by Ping Zhu Shi industry Co., ltd.).

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

[ (D) component ]

(D) The component is solvent.

Examples of the component (D) include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as alpha-terpineol and beta-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as 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, and 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 like acetates. (D) Only one of the components may be used alone, or two or more of the components may be used in combination.

(D) The content of the component (a) varies depending on the target viscosity, and is preferably 30 mass% or more and 90 mass% or less with respect to the total mass of the curable resin composition. If the content of the component (D) is 30 mass% or more, the viscosity of the curable resin composition can be set to be easily applied to the substrate, and if it is 90 mass% or less, the time required for drying after the curable resin composition is applied to the substrate can be shortened.

[ (E) component, (F) component ]

(E) The component (F) is a sensitizer.

(E) The component (c) is not particularly limited as long as it is a compound capable of initiating polymerization of a compound having a polymerizable unsaturated bond and capable of addition polymerization. Examples of the component (E) include: photopolymerization initiators such as acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and acyloxime compounds. In this specification, a photopolymerization initiator is used in the sense of containing a sensitizer.

Examples of acetophenone compounds include: acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzildimethylketal, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butan-1-one, 2-hydroxy-2-methyl-1- [ 4- (1-methylvinyl) phenyl ] propan-1-one, and the like.

Examples of the triazine compound include: 2,4, 6-three (three methyl) -1,3,5 three triazine, 2-methyl-4, 6-double (three methyl chloride) -1,3,5 three triazine, 2-phenyl-4, 6-double (three methyl chloride) -1,3,5 three triazine, 2- (4-chlorophenyl) -4, 6-double (three methyl chloride) -1,3,5 three triazine, 2- (4-methoxy phenyl) -4, 6-double (three methyl chloride) -1,3,5 three triazine, 2- (4-methoxy naphthyl) -4, 6-double (three methyl chloride) -1,3,5 three triazine, 2- (4-methoxy styryl) -4, 6-double (three methyl chloride) -1,3,5 three methyl styryl) -4, 6-double (three methyl chloride) -1,3,5 three triazine, 2- (4-methyl sulfide styryl) -4, 6-double (three methyl chloride) -1,3,5 three triazine, 2- (3, 6-three methyl three vinyl) -1,3,5 three triazine.

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

Examples of the benzophenone compound include: benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, 3',4 '-tetra (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, 4' -bis (N, N-diethylamino) benzophenone, and the like.

Examples of the thioxanthone compound include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

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

Examples of the acyloxime 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-carbazol-3-yl ] -adamantylmethane-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -tetrahydrofuranylmethan-1-one oxime-O-benzoate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -tetrahydrofuranylmethan-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -thiophenyl methane-1-one oxime-O-benzoate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -thiophenyl-methane-1-one oxime-O-acetic acid ester, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -morpholinomethane-1-one oxime-O-benzoic acid ester, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -morpholinomethane-1-one oxime-O-acetic acid ester, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-one oxime-O-bicycloheptane carboxylic acid ester, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-one oxime-O-tricyclodecane carboxylic acid ester, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-one oxime-O-c-oic acid ester, 1- [4- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-one oxime-O-c-oic acid ester, 1- [ phenyl ] octane-2-one oxime-O-carboxylic acid ester, 1- [ phenyl ] octane-2-yl ] -phenyl-oxime-O-2-carbonyl ] -2-one oxime-carboxylic acid ester, 1- [ 9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl ] ethanone-O-acetyl oxime, (2-methylphenyl) (7-nitro-9, 9-dipropyl-9H-fluoren-2-yl) -acetyl oxime, ethanone, 1- [7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] -1- (O-acetyl oxime), ethanone, 1- (9, 9-dibutyl-7-nitro-9H-fluoren-2-yl) -1-O-acetyl oxime, ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyl oxime), 1, 2-octadiene, 1- [4- (phenylthio) -,2- (O-benzoyl oxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyl oxime), 1- (4-phenylthio) -1, 4-phenylbutan-3-yl ] -2-dioxime, 1-diphenyloxime 1- (4-methylmercaptophenyl) butane-1, 2-dione-2-oxime-O-acetate, 1- (4-methylmercaptophenyl) butane-1-ketoxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazolo-3-yl-O-acetyl oxime, 5- (4-isopropylthiophenyl) -1, 2-indandione, 2- (O-acetyl oxime) and the like. The photopolymerization initiator may be used alone or in combination of two or more.

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

[ chemical 17]

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

[ chemical 18]

(in the formula (12), R ₁₂ R is R ₁₃ Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group, cycloalkylalkyl group or alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms; r is R ₁₄ Each independently is a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, wherein-CH in the alkyl or alkenyl group ₂ Part of the radicals may be substituted by-O-radicals; further, these R' s ₁₂ ～R ₁₄ Part of the hydrogen atoms in the radicals of (2) may also be substituted by halogen atoms)

The molar absorptivity of component (E) at 365nm is preferably 10000L/mol cm or more. Since such a photopolymerization initiator has high sensitivity, even in a curable resin composition containing a component (B) having a relatively large equivalent amount of acrylic groups, sufficient photosensitivity can be ensured, and the developability (resolution) of the curable resin composition can be sufficiently improved. Examples of such photopolymerization initiators include: ohmic nilrad (Omnirad) 1312 (manufactured by IGM resin (IGM Resins) b.v. company, "ohmic nilrad (Omnirad)" is a registered trademark of the company), ai Dike acaruz (ADEKA ARKLS) NCI-831 (manufactured by ADEKA corporation, ai Dike (ADEKA), and "Ai Dike acaruz (ADEKA ARKLS)" is a registered trademark of the company), and the like.

In the present specification, the molar absorptivity of the photopolymerization initiator can be set to a value obtained by measuring the absorbance of an acetonitrile solution having a concentration of 0.001 wt% in a quartz cell having an optical path length of 1cm using an ultraviolet-visible infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science) corporation).

In addition, as the component (E), a thermal polymerization initiator may be used. As examples of the thermal polymerization initiator, organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-t-butyl hexahydroterephthalate peroxide, t-butyl peroxy-2-ethylhexanoate, 1-t-butylperoxy-3, 5-trimethylcyclohexane and the like can be used; azo compounds such as azobisisobutyronitrile, azobis-4-methoxy-2, 4-dimethylvaleronitrile, azobicyclohexanone-1-carbonitrile, azobisbenzoyl, 1 '-azobis (1-acetoxy-1-phenylethane), and 2,2' -azobis (methyl isobutyrate); any of compounds that can be used in general radical polymerization, such as a water-soluble catalyst such as potassium persulfate or ammonium persulfate, and a redox catalyst obtained by combining a peroxide or persulfate with a reducing agent. The thermal polymerization initiator may 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.

In addition, as the component (E), a reactive radical generator or an acid generator may be used.

Examples of the active radical generator include: 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2 '-bis (o-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9, 10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, and the like.

Examples of the acid generator include: 4-hydroxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzyl sulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, onium salts such as diphenyliodonium hexafluoroantimonate, nitrobenzyl toluene sulfonate, benzoin toluene sulfonate, and the like.

Examples of the sensitizer (F) include: acetophenones such as triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, benzophenone, 4' -bis-dimethylaminobenzophenone (milbetone), 4-phenylbenzophenone, 4' -dichlorobenzophenone, hydroxybenzophenone, 4' -diethylaminobenzophenone, acetophenone, 2-diethoxyacetophenone, p-dimethylacetacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-t-butylacetophenone; benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone systems such as 2-dimethylaminoethyl benzoate, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (N-butoxy) ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 4-benzoyl-4 '-methyl-diphenyl sulfide, acrylated benzophenone, 3',4 '-tetra (t-butylperoxycarbonyl) benzophenone and 3,3' -dimethyl-4-methoxybenzophenone; thioxanthone systems such as 2-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2, 4-dichlorothioxanthone; aminobenzophenone systems such as 4,4' -bis (dimethylamino) benzophenone, 4' -bis (diethylaminobenzophenone, and 4,4' -bis (ethylmethylamino) benzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9, 10-phenanthrenequinone, camphorquinone, and the like.

The content of the component (E) is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total of the component (a) and the component (B). In the case of using an acyloxime photopolymerization initiator as the component (D), the content of the component (E) is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total of the component (a) and the component (B). When the content of the component (E) is not less than the above-mentioned lower limit, the photopolymerization rate is moderate, and thus sufficient sensitivity can be ensured. If the content of the component (E) is equal to or less than the upper limit value, the line width faithful to the mask can be reproduced, and the pattern edge can be made clear.

When the total mass of the component (E) is 100 parts by mass, the content of the component (F) is preferably 0.5 parts by mass or more and 400 parts by mass or less, more preferably 1 part by mass or more and 300 parts by mass or less. When the content of the photo sensitizer is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be improved and the photopolymerization rate can be increased. Further, when the content of the photosensitizer is 400 parts by mass or less, excessive improvement in sensitivity can be suppressed, and scorching, peeling residues, and the like are less likely to occur when light is irradiated.

[ other Components ]

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, an ultraviolet absorber, a surfactant, a coupling agent, a viscosity regulator, and other additives may be optionally blended into the curable resin composition.

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

Examples of the hardening agent include: amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamide, lewis acid complex compounds, and the like, which contribute to the hardening of epoxy resins.

Examples of the hardening accelerator include: tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borates, lewis acids, organometallic compounds, imidazoles, and the like which contribute to the acceleration of the hardening of the epoxy resin.

Examples of the thermal polymerization inhibitor and the antioxidant include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, hindered phenol compounds, and the like.

Examples of plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the filler include: glass fibers, silica, mica, alumina, and the like.

Examples of leveling agents or defoamers include: silicone-based, fluorine-based, and acrylic-based compounds.

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

Examples of the surfactant include: anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether triethanolamine sulfate; cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride; amphoteric surfactants such as lauryl dimethylamine oxide and lauryl carboxymethyl hydroxyethyl imidazolium betaine; nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate and the like; silicone-based surfactants having a main skeleton such as polydimethylsiloxane; and a fluorine-based surfactant.

As the coupling agent, a silane coupling agent can be exemplified. The silane coupling agent is preferably a silane coupling agent having an amino group, an isocyanate group, a urea group, an epoxy group, a vinyl group, a (meth) acryl group, a mercapto group or the like as a reactive group, and more preferably a silane coupling agent having an epoxy group, an isocyanate group, a (meth) acryl group as a reactive group. Specific examples of the coupling agent include: 3- (glycidoxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

[ method of production ]

The curable resin composition can be obtained by mixing the above-mentioned components.

2. Use of the same

The curable resin composition can be used as a protective layer in various display devices such as a liquid crystal display, an organic Electroluminescence (EL) display device, a micro light emitting diode (micron light emitting diode, μled) display device, and a display device using quantum dots, by forming a resin cured film by irradiation with radiation; an insulating film for a printed wiring board and a semiconductor package, for example, a solder resist layer, a plating resist layer, a resist layer such as an etching resist layer, an interlayer insulating layer such as a multilayer printed wiring board, and a film for gas barrier; a sealing material for semiconductor light emitting elements such as lenses and Light Emitting Diodes (LEDs); top coats of paints or inks; a hard coating of plastics type; metal rust-preventive films, and the like. In the present specification, the term "semiconductor package" refers to not only a flip chip package, a wafer level package, or the like, but also a package including a package formed to include a semiconductor chip and capable of being mounted on a printed board, such as a package in which a flip chip package is stacked on an Interposer (Interposer). In particular, the present invention is useful for an optical semiconductor package combined with a light emitting element (preferably, an LED such as a UV-LED or a Blue-LED). The thermosetting resin composition itself may be molded and applied to the production of films, substrates, plastic parts, optical lenses, and the like.

In particular, since the resin cured film is less likely to cause yellowing with time due to electromagnetic waves having a wavelength of 340nm to 480nm, it is possible to suppress drawbacks due to yellowing with time when used in various devices having a light source (for example, UV-LED or Blue-LED) that emits the electromagnetic waves. In view of the above, the resin cured film is preferably disposed closer to the light source, and particularly when the resin cured film is used as a protective film (sealing material) for sealing the light source by being arranged on a mounting board, the effect of suppressing the defect caused by the yellowing with time is remarkable as compared with other materials.

The resin cured film can be produced, for example, by applying the curable resin composition to a substrate or the like, and drying the composition and irradiating (exposing) the composition with light (including ultraviolet rays, radiation rays, and the like) to cure the composition. In this case, the portions irradiated with light and the portions not irradiated with light are provided using a photomask or the like, and only the portions irradiated with light are cured, and the other portions are dissolved by an alkali solution, whereby a cured product of a desired pattern can be obtained.

When the curable resin composition is applied to a substrate, a known solution impregnation method can be used; spraying; a method using a roll coater, a disk coater (Land coater machine), a slit coater, or a rotary machine, or the like.

After the curable resin composition is applied to a desired thickness by these methods, the solvent is removed (prebaked), thereby forming a film. The pre-baking is performed by heating using an oven, a hot plate, or the like, vacuum drying, or a combination thereof. The heating temperature and heating time in the prebaking may be appropriately selected depending on the solvent used, and for example, the heating is performed at a temperature of 80 to 120℃for 1 to 10 minutes.

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

The alkali development may be performed using an aqueous solution of, for example, sodium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like as a developer. These developer solutions may be selected according to the characteristics of the resin layer, and surfactants may be added as needed. The development is preferably carried out at a temperature of 20℃to 35 ℃. A fine image can be precisely formed by using a commercially available developing machine, ultrasonic cleaning machine, or the like. Further, after alkali development, water washing is generally performed. Examples of the development treatment method include a spray development method, a dip (dip) development method, a liquid coating (pump) development method, and the like.

After development in this manner, heat treatment (post baking) is performed at a temperature of 180℃to 250℃and under conditions of 20 minutes to 100 minutes. The post baking is performed for the purpose of improving adhesion of the patterned coating film to the substrate, and the like. The post-baking can be performed by heating using an oven, a hot plate, or the like, as in the pre-baking.

Thereafter, polymerization or curing (both may be collectively referred to as curing) is completed by heat, and a cured film such as an insulating film can be obtained. The curing temperature in this case is preferably 160℃to 250 ℃.

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

Examples (example)

Hereinafter, embodiments of the present invention will be described specifically based on examples and comparative examples, but the present invention is not limited to these.

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

In addition, in the case where the same model is used for various measurement devices, the device manufacturer name is omitted from the second place. In the examples, all glass substrates used for producing substrates with a resin cured film for measurement were subjected to the same treatment and used. In addition, when the first decimal place is 0, the contents of the components may be omitted from the description below the decimal point.

[ concentration of solid content ]

According to the method of impregnating a glass filter with 1g of the resin solution obtained in the synthesis example [ weight: w (W) ₀ (g) In and weigh the measured weight [ W ₁ (g) And weight after heating at 160℃for 2 hours [ W ] ₂ (g) And is obtained by the following equation.

Solid content concentration (wt%) =100× (W ₂ -W ₀ )/(W ₁ -W ₀ )

[ acid value ]

The acid value was obtained by dissolving the resin solution in dioxane, using a potential difference titration apparatus "COM-1600" (manufactured by Pingyu industries Co., ltd.) and titrating with a 1/10N-KOH aqueous solution.

[ molecular weight ]

The molecular weight was measured by a gel permeation chromatograph (gel permeation chromatograph, GPC) "HLC-8220GPC" (manufactured by Tosoh Co., ltd., tosoh.) and a solvent tetrahydrofuran, column TSKgelSuper H-2000 (2) +TSKgelSuper H-3000 (1) +TSKgelSuper H-4000 (1) +TSKgelSuper H-5000 (1) (manufactured by Tosoh Co., ltd.), at a temperature of 40℃and a speed of 0.6ml/min, and the weight average molecular weight (Mw) was obtained as a standard polystyrene (manufactured by Tosoh Co., ltd., PS-oligomer set) conversion value.

The abbreviations used in the synthesis examples are as follows.

BPFE: bisphenol fluorene type epoxy resin (in the general formula (5), ar is an epoxy resin having a benzene ring and l is 0, epoxy equivalent weight is 256 g/eq)

TPP: triphenylphosphine (triphenyl phosphine, TPP)

AA: acrylic acid (acrylic acid, AA)

PGMEA: propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate, PGMEA)

HPMDA:1,2,4, 5-cyclohexane tetracarboxylic dianhydride (1, 2,4,5-cyclohexane tetracarboxylic dianhydride)

ODPA:4, 4'-oxydiphthalic dianhydride (4, 4' -oxydiphthalic dianhydride, ODPA)

THPA:1,2,3, 6-tetrahydrophthalic anhydride (1, 2,3,6-tetrahydrophthalic anhydride, THPA)

PA: phthalic anhydride (phthalic anhydride, PA)

SA: succinic anhydride (succinic anhydride, SA)

DCPMA: dicyclopentanyl methacrylate (dicyclopentanyl methacrylate, DCPMA)

GMA: glycidyl methacrylate (glycidyl methacrylate, GMA)

St: styrene (styrene, st)

AIBN: azobisisobutyronitrile (AIBN)

TDMAMP: tri-dimethylaminomethylphenol (tris-dimethyl amino methyl phenol, TDMAMP)

HQ: hydroquinone (HQ)

TEA: triethylamine (TEA)

BPDA:3,3', 4' -biphenyltetracarboxylic dianhydride (3, 3', 4' -biphenyl tetracarboxylic dianhydride, BPDA)

BTDA:3,3', 4' -benzophenone tetracarboxylic dianhydride (3, 3', 4' -benzophenone tetracarboxylic dianhydride, BTDA)

PMDA: benzene 1,2,4,5-tetracarboxylic dianhydride (Benzene 1,2,4,5-tetracarboxylic dianhydride, PMDA)

DPHA: dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate, DPHA)

PTMA: pentaerythritol tetrakis (mercaptoacetate) (pentaerythritol tetra (mercaptoacetate), PTMA)

BzDMA: benzyl dimethylamine (benzyl dimethyl amine, bzDMA)

(unsaturated group-containing alkali-soluble resin)

Synthesis example 1

Into a 250mL four-necked flask equipped 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 charged, and the mixture was stirred at 100℃to 105℃for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was charged and the solid content was adjusted to 50 mass%.

Subsequently, HPDA (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℃for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A) -1. The solid content concentration of the obtained resin solution was 56.0 mass%, the acid value (in terms of solid content) was 105mgKOH/g, and the Mw based on GPC analysis was 4000.

Synthesis example 2

Into a 250mL four-necked flask equipped 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 charged, and the mixture was stirred at 100℃to 105℃for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was charged and the solid content was adjusted to 50 mass%.

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

Synthesis example 3

Into a 250mL four-necked flask equipped 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 charged, and the mixture was stirred at 100℃to 105℃for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was charged and the solid content was adjusted to 50 mass%.

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

Synthesis example 4

Into a 250mL four-necked flask equipped 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 charged, and the mixture was stirred at 100℃to 105℃for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was charged and the solid content was adjusted to 50 mass%.

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

Synthesis example 5

Into a 250mL four-necked flask equipped 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 charged, and the mixture was stirred at 100℃to 105℃for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was charged and the solid content was adjusted to 50 mass%.

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

Synthesis example 6

PGMEA (300 g) was placed in a 1L four-necked flask equipped with a reflux condenser, and the flask was purged with nitrogen and then heated to 120 ℃. 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) and St (31.2 g, 0.30 mol)) was added dropwise from an addition funnel over 2 hours, and the mixture was stirred at 120℃for 2 hours to obtain a copolymer solution.

Subsequently, after the flask was replaced 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, and the mixture was stirred at 120℃for 6 hours to obtain a copolymer solution containing a polymerizable unsaturated group. SA (30.0 g, 90% of the molar amount of AA added) and TEA (0.5 g) were added to the obtained polymerizable unsaturated group-containing copolymer solution, and the mixture was reacted at 120℃for 4 hours to obtain a polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (A) -6. The solid content concentration of the resin solution was 46.0% by mass, the acid value (in terms of solid content) was 76mgKOH/g, and the Mw obtained by GPC analysis was 5300.

Synthesis example 7

Into a 250mL four-necked flask equipped 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 charged, and the mixture was stirred at 100℃to 105℃for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was charged and the solid content was adjusted to 50 mass%.

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

Synthesis example 8

Into a 250mL four-necked flask equipped 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 charged, and the mixture was stirred at 100℃to 105℃for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was charged and the solid content was adjusted to 50 mass%.

Then, 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℃for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A)' -8. The solid content concentration of the obtained resin solution was 57.4% by mass, the acid value (in terms of solid content) was 105mgKOH/g, and the Mw obtained by GPC analysis was 3200.

Synthesis example 9

Into a 250mL four-necked flask equipped 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 charged, and the mixture was stirred at 100℃to 105℃for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was charged and the solid content was adjusted to 50 mass%.

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

Synthesis example 10

A1L four-necked flask was charged with 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), and reacted at 60℃for 12 hours to obtain a dendrimer solution (B) -2. The disappearance of thiol groups was confirmed by iodine quantification for the obtained dendrimer. The solid content concentration of the obtained dendrimer solution was 80.0 mass%, and the Mw obtained based on GPC analysis was 10000.

Curable resin compositions of examples 1 to 10 and comparative examples 1 to 3 were prepared in the amounts (in mass%) shown in table 1. The formulation components used in table 1 are as follows.

(unsaturated group-containing alkali-soluble resin)

(A) -1: the resin solution (solid content concentration: 56.0% by mass) obtained in Synthesis example 1

(A) -2: the resin solution (solid content concentration: 55.6% by mass) obtained in Synthesis example 2

(A) -3: the resin solution (solid content concentration: 55.9% by mass) obtained in Synthesis example 3

(A) -4: the resin solution (solid content: 54.8% by mass) obtained in Synthesis example 4

(A) -5: the resin solution (solid content: 57.2% by mass) obtained in Synthesis example 5

(A) -6: the resin solution (solid content concentration 46.0% by mass) obtained in Synthesis example 6

(A) ' -7: the resin solution (solid content: 57.0% by mass) obtained in Synthesis example 7

(A) ' -8: the resin solution (solid content: 57.4% by mass) obtained in Synthesis example 8

(A) ' -9: the resin solution (solid content concentration: 55.9% by mass) obtained in Synthesis example 9

(polymerizable Compound)

(B) -1: dipentaerythritol penta/hexaacrylate mixture (Kayarad (KAYARAD) DPHA, molecular weight 740, manufactured by Japanese chemical Co., ltd., "Kayarad (KAYARAD)" is a registered trademark of the same company)

(B) -2: the dendrimer solution (solid content concentration 80.0% by mass) obtained in Synthesis example 10

(epoxy Compound)

(C) The method comprises the following steps Biphenyl type epoxy resin (jER YX4000, mitsubishi chemical Co., ltd.)

(solvent)

(D) The method comprises the following steps Propylene Glycol Monomethyl Ether Acetate (PGMEA)

(polymerization initiator)

(E) The method comprises the following steps 2- [4- (methylthio) benzoyl ] -2- (4-morpholino) propane ("ohmic Nirad) 907" IGM resin (IGM Resins) manufactured by the company "ohmic Nirad (Omnirad)" is a registered trademark of said company

(sensitizer)

(F) The method comprises the following steps Mitstone

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[ evaluation ]

[ calculation of highest molecular occupied molecular orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) ]

The energies of the highest molecular occupied orbitals (HOMO) and the Lowest Unoccupied Molecular Orbitals (LUMO) of the unsaturated group-containing alkali-soluble resins ((A) -1 to (A) -5 and (A) '-7 to (A)' -9) are calculated by quantum chemistry based on the structural units of these resins represented by the following general formula (13). In quantum chemistry, the "Gaussian 16, revision b.01 (Gaussian 16, revision b.01)" package (Gaussian inc.) is used. Specifically, with respect to the molecular structure (molecular coordinates) of the structural unit (terminal hydrogen substituted) of these resins represented by the general formula (13), the most stable structure of the structural unit calculated by the density functional method (DFT) using B3LYP as a general function and using 6-31G (d) as a basis function is represented by charge 0 and multiple 1, and the energy of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) in this structure (Gaussian) input line "#b3lyp/6-31G (d) OPT").

[ chemical 19]

(in the formula (13), Y is a residue derived from tetracarboxylic dianhydride used in the synthesis of each resin, and Z is a residue derived from dicarboxylic anhydride used in the synthesis of each resin)

The energies of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) of the unsaturated group-containing alkali-soluble resin ((A) -6) are calculated in the same manner as (A) -1 to (A) -5 and (A) '-7 to (A)' -9 based on the structural units of these resins represented by the following general formula (14).

[ chemical 20]

( In the formula (14), a, b and c are molar ratios of the respective structural units, and a is set as a in the calculation: b: c=1: 1:1 )

(production of a resin cured film-equipped substrate for evaluation of transmittance after initial transmittance/light resistance test)

The photosensitive resin compositions shown in Table 1 were applied to a glass substrate "#1737" using a spin coater so that the film thickness after the heat curing treatment became 10.0. Mu.m, in which a wavelength of 254nm was irradiated with a low-pressure mercury lamp and the illuminance was 1000mJ/cm ² On a 125mm×125mm glass substrate "#1737" after cleaning the surface, a pre-bake was performed at 90℃for 3 minutes using a hot plate to prepare a dry film. Subsequently, the substrates with the resin cured films of examples 1 to 10 and comparative examples 1 to 3 were obtained by main curing (post baking) at 230℃for 30 minutes using a hot air dryer.

[ evaluation of initial transmittance ]

The transmittance of the cured film-equipped substrate after the main curing and before the light resistance test at a wavelength of 400nm was measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., ltd.).

[ evaluation of transmittance after light resistance test ]

A blue filter "IEB400" (manufactured by Woodberg Nitro Co., ltd., 50 mm. Times.50 mm. Times.5 mmt, transmittance at a wavelength of 340nm or less/480 nm or more of less than 10%) was placed on the cured substrate, and light irradiation was performed for 500 hours using a Xe test chamber "Q-SUN Xe-1" (manufactured by Q-Lab Corporation). The transmittance at 400nm was measured for the region of the resin cured film-equipped substrate irradiated with light through the blue filter using an ultraviolet-visible infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science co., ltd.).

(preparation of resin cured film powder for evaluation of thermal decomposition resistance)

The photosensitive resin compositions shown in table 1 were applied to a glass substrate "#1737" using a spin coater so that the film thickness after the heat hardening treatment became 10.0 μm, and pre-baked at 90℃for 3 minutes using a hot plate to prepare a dry film. Thereafter, the substrates with the resin cured films of examples 1 to 10 and comparative examples 1 to 3 were obtained by final curing (post baking) at 230℃for 30 minutes using a hot air dryer. The obtained hardened film was cut into powder and used in Thermogravimetry/differential thermal analysis (TG/DTA) measurement.

[ evaluation of thermal decomposition resistance ]

(evaluation method)

The obtained powder of the resin cured film was heated from 30℃to 400℃in air at a heating rate of 5℃per minute by using a TG-DTA apparatus "TG/DTA6200" (manufactured by Seiko instruments (Seiko Instruments) Co., ltd.), and the temperature at which the weight of the specimen was reduced by 5% was measured. Further, Δ or more is qualified.

(evaluation criterion)

And (3) the following materials: 5% weight reduction temperature of 320 ℃ or higher

O: a weight reduction temperature of 5% of 300 ℃ or higher and less than 320 DEG C

Delta: a weight reduction temperature of 5% of 280 ℃ or higher and less than 300 DEG C

X: 5% weight reduction temperature less than 280 DEG C

(production of a resin cured film for evaluation of glass transition temperature)

The photosensitive resin compositions shown in table 1 were applied to a release aluminum foil "sapanium" (manufactured by eastern aluminum co., ltd.) using a spin coater so that the film thickness after the heat-hardening treatment became 30.0 μm, and pre-baked at 90 ℃ for 3 minutes using a hot plate to prepare a dry film. Thereafter, the cured product was cured (post-baked) at 230℃for 30 minutes using a hot air dryer. Finally, the resin cured films were peeled off from the release aluminum foil to obtain the resin cured films of examples 1 to 10 and comparative examples 1 to 3.

[ evaluation of glass transition temperature ]

A hardened film having a width of 5mm was set so that the inter-chuck length became 22mm by using a dynamic viscoelasticity (dynamic thermo-mechanical analysis (Dynamic mechanical analysis, DMA)) measuring device (RSA-G2 manufactured by TA instruments Co., ltd.) and the glass transition temperature was measured at a temperature range of 30℃to 300 ℃. Further, Δ or more is qualified.

(evaluation criterion)

And (3) the following materials: the glass transition temperature is above 180 DEG C

O: the glass transition temperature is 160 ℃ or higher but less than 180 DEG C

Delta: the glass transition temperature is 140 ℃ or higher and less than 160 DEG C

X: the glass transition temperature is less than 140 DEG C

(production of a substrate with a resin cured film for evaluation of development adhesion/Pattern initial transmittance)

The photosensitive resin compositions shown in table 1 were applied to a glass substrate "#1737" using a spin coater so that the film thickness after the heat hardening treatment became 10.0 μm, and pre-baked at 90℃for 3 minutes using a hot plate to prepare a dry film. Then, the illuminance was 30mW/cm by using the i-ray ² Is irradiated with 500mJ/cm by an ultra-high pressure mercury lamp ² The ultraviolet ray of the film is dried to carry out the photo hardening reaction of the dried film.

Then, for the exposed film, 2.38% tetramethylammonium hydroxide (tetramethylammonium hydroxide, TMAH) at 23℃was used at 1kgf/cm ² After the development treatment was performed for 60 seconds under the spray pressure of (3), 5kgf/cm was performed ² The unexposed portions were removed by spray water washing to form a 10 μm dot pattern. Finally, the substrates with the resin cured films of examples 1 to 10 and comparative examples 1 to 3 were obtained by final curing (post baking) at 230℃for 30 minutes using a hot air dryer.

[ development adhesion ]

The obtained dot pattern of the resin cured film of the substrate with the resin cured film was observed with an optical microscope at 10 μm, and whether or not the pattern was peeled was determined. Further, Δ or more is qualified.

(evaluation criterion)

O: no pattern peeling was observed

Delta: minimal part of the pattern peeling was observed

X: most of the pattern is stripped

[ evaluation of initial transmittance of Pattern ]

The transmittance of the cured film-equipped substrate after development/main curing was measured at a wavelength of 400nm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., ltd.).

The evaluation results are shown in table 2.

As shown in table 2, it can be seen that: the resin cured films of examples 1 to 10 obtained from the photosensitive resin composition of the present invention have small changes in transmittance of the coating film and can suppress yellowing of the coating film when light having a wavelength of 340nm to 480nm is irradiated. The reason for this is considered that by setting the energy difference between HOMO and LUMO of the component (a) to 3.7eV or more, absorption of light in the above-mentioned wavelength region can be suppressed, and deterioration of the resin cured film can be suppressed.

By using the unsaturated group-containing thermosetting resin represented by the general formula (1) as the component (a), the thermal decomposition resistance can be improved, and further, the glass transition temperature can be improved, and therefore, the dimensional stability at the time of temperature increase can be improved. The reason for this is considered to be that the unsaturated group-containing thermosetting resin represented by the general formula (1) has a plurality of aromatic rings and is excellent in heat stability.

As shown in examples 7 to 9, it is clear that: by using a resin containing a dicarboxylic acid, a tricarboxylic acid, or an acid monoanhydride thereof having a cyclic structure as the component (a), peeling at the time of pattern formation can be suppressed, and a fine pattern of a resin cured film can be formed.

As shown in examples 7 to 10, it is clear that: by using the dendritic polymer as the component (B), penetration of the developer into the photo-cured portion can be suppressed, and yellowing of the resin cured film at the time of main curing (post baking) can be suppressed.

[ Industrial applicability ]

The present invention can provide a photosensitive resin composition which can be used in the production of various products. In particular, a resin cured film suitable for the purpose of fixing and sealing an optical semiconductor to a mounting board can be provided.

Claims (7)

1. A curable resin composition comprising:

(A) An alkali-soluble resin containing an unsaturated group,

(B) A polymerizable compound having two or more unsaturated bonds,

(C) Epoxy compound having two or more epoxy groups

(D) The solvent is used for the preparation of the aqueous solution,

the component (A) is a resin having an energy difference between the highest occupied molecular orbital and the lowest unoccupied molecular orbital calculated by quantum chemical calculation of 3.7eV or more.

2. The curable resin composition according to claim 1, wherein the component (A) is a resin represented by the following general formula (1);

in the formula (1), ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of hydrogen atoms constituting Ar may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group; r is R ₁ Independently an alkylene group having 2 to 4 carbon atoms; l is independently 0 or moreAnd 3 or less; 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 of Z is a substituent represented by the following general formula (4); n is a number having an average value of 1 to 20,

In the formula (2) and the formula (3), R ₂ Is a hydrogen atom or methyl group, R ₃ An alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R ₄ A saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, p is a number of 0 to 10 carbon atoms, and is a bond site,

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

3. The curable resin composition according to claim 1 or 2, wherein the component (A) is a resin having a weight average molecular weight of 1000 or more and 40000 or less and an acid value of 50mgKOH/g or more and 200mgKOH/g or less.

4. The curable resin composition according to claim 1 or 2, comprising at least one of (E) a polymerization initiator and (F) a sensitizer.

5. A resin cured film obtained by curing the curable resin composition according to any one of claims 1 to 4.

6. A semiconductor package using the resin cured film according to claim 5 as at least one protective film.

7. A display device comprising at least one protective film comprising the resin cured film according to claim 5.