Unsaturated group-containing polymerizable resin, curable resin composition, cured resin film, semiconductor package and display device

Abstract

To provide an unsaturated group-containing polymerizable resin that exhibits low absorption of light within the 340-480 nm wavelength range, while demonstrating high adhesion and developability.SOLUTION: The present invention provides an unsaturated group-containing polymerizable resin that is prepared by the reaction of compound (a-1) of formula (1), compound (a-2) of formula (2), and tetrabasic acid (a-3), with a molar ratio [(a-2) / (a-1)] of 0.5 or more and 5.0 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an unsaturated group-containing polymerizable resin, a curable resin composition, a cured resin film, a semiconductor package, and a display device. [Background technology]

[0002] In μ-LED displays, semiconductor packages, and the like, a planarizing sealing film is provided to eliminate steps between stacked layers. The planarizing sealing film is required to have properties such as adhesion to the substrate, and the material for the planarizing sealing film is required to have high developability, etc. Patent Document 1 discloses a radiation-sensitive resin composition containing an alkali-soluble unsaturated resin having a bisphenol fluorene structure as a material for the planarizing sealing film that can satisfy these requirements. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP2003-089716A Summary of the Invention [Problem to be solved by the invention]

[0004] A cured product of a resin composition containing the alkali-soluble unsaturated resin having a bisphenol fluorene structure described in Patent Document 1 is useful as a planarizing sealing film because it has excellent adhesion to a substrate and solvent resistance.

[0005] However, according to new findings by the present inventors, it was found that the flattening sealing film arranged in the μ-LED display is prone to deterioration at the portion arranged directly above the UV-LED or Blue-LED. In order to suppress this deterioration, it is considered to use a resin with low absorbance at short wavelengths of 340 to 480 nm, which are the emission wavelengths of these LEDs, for the flattening sealing film. As candidates for resins that meet the above-mentioned absorbance requirements, siloxane resins and acrylic resins are considered, but these resins do not have very high adhesion to the substrate or developability.

[0006] The present invention has been made in view of the above-mentioned points, and an object of the present invention is to provide an unsaturated group-containing polymerizable resin capable of obtaining a curable resin composition that has low absorption of light with a wavelength of 340 to 480 nm and is therefore unlikely to deteriorate due to light with this wavelength, and that has high adhesion to substrates and high developability; a curable resin composition containing the unsaturated group-containing polymerizable resin; a cured resin film obtained from the curable resin composition; and a semiconductor package and a display device having the cured resin film. [Means for solving the problem]

[0007] One aspect of the present invention for solving the above problems relates to an unsaturated-group-containing polymerizable resin as described in the following items [1] to [4]. [1] An unsaturated group-containing polymerizable resin obtained by reacting a diol compound (a-1) represented by the following general formula (1), a diol compound (a-2) represented by the following general formula (2), and a tetrabasic acid or a dianhydride thereof (a-3), wherein the molar ratio of (a-1) to (a-2), [(a-2) / (a-1)], is 0.5 or more and 5.0 or less.

[0008] [ka]

[0009] [ka]

[0010] In the general formula (1), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R1 is independently an alkylene group having 2 to 10 carbon atoms. l and m are independently numbers of 0 to 3. G is independently a (meth)acryloyl group, a functional group represented by the following general formula (3), or a functional group represented by the following general formula (4). X is independently -CO-, -SO2-, -C(CH3)2-, -C(CF3)2-, -Si(CH3)2-, -O-, -CH2-, a single bond, or a group represented by the following general formula (5). In general formula (2), R2 is a divalent saturated hydrocarbon group having 2 to 20 carbon atoms.

[0011] [ka]

[0012] [ka]

[0013] [ka]

[0014] In general formulas (3) and (4), R3 is independently a hydrogen atom or a methyl group, R4 is independently an alkylene group or an alkylarylene group having from 2 to 10 carbon atoms, R5 is independently a saturated or unsaturated hydrocarbon group having from 2 to 20 carbon atoms, and p is a number from 0 to 10. * indicates a bonding site to the structure represented by general formula (1). [2] The diol compound (a-2) is a compound in which R2 is a saturated hydrocarbon group having an alicyclic structure. The unsaturated group-containing polymerizable resin according to [1]. [3] The tetrabasic acid or its dianhydride (a-3) is a tetrabasic acid or its dianhydride containing an aromatic ring; The unsaturated group-containing polymerizable resin according to [1] or [2]. [4] The weight average molecular weight is 1000 or more and 40000 or less, and the acid value is 20 mgKOH / g or more and 200 mgKOH / g or less. The unsaturated group-containing polymerizable resin according to any one of [1] to [3].

[0015] Another aspect of the present invention for solving the above problems relates to a curable resin composition as described below in [5]. [5] (A) The unsaturated group-containing polymerizable resin according to any one of [1] to [4]. (B) a polymerizable compound having at least two unsaturated bonds; (C) an epoxy compound having at least two epoxy groups, and (D) a solvent, A curable resin composition comprising:

[0016] Another aspect of the present invention for solving the above problems relates to a cured resin film as described below in [6]. [6] A cured resin film obtained by curing the curable resin composition according to [5].

[0017] Yet another aspect of the present invention for solving the above problem relates to a semiconductor package as described below in [7]. [7] A semiconductor package having the cured resin film according to [6].

[0018] Yet another aspect of the present invention for solving the above problems relates to a display device as described below in [8]. [8] A display device comprising the cured resin film according to [6]. Effect of the Invention

[0019] According to the present invention, there are provided an unsaturated group-containing polymerizable resin capable of obtaining a curable resin composition which has low absorption of light with a wavelength of 340 to 480 nm and is therefore resistant to deterioration due to light with this wavelength, and which has high adhesion to substrates and high developability; a curable resin composition containing the unsaturated group-containing polymerizable resin; a cured resin film obtained from the curable resin composition; and a semiconductor package and a display device having the cured resin film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In this specification, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted. In addition, the compounds, functional groups, or structures exemplified below may be used alone or in combination with one another, unless otherwise specified.

[0021] In this specification, "(meth)acrylic" is a general term for acrylic and methacrylic, and "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group, and means one or both of them.

[0022] 1.Polymerizable resin containing unsaturated groups One embodiment of the present invention relates to an unsaturated group-containing polymerizable resin.

[0023] The unsaturated group-containing polymerizable resin is obtained by reacting a diol compound (a-1) represented by the following general formula (1), a diol compound (a-2) represented by the following general formula (2), and a tetrabasic acid or a dianhydride thereof.

[0024] The unsaturated group-containing polymerizable resin has a molar ratio [(a-2) / (a-1)] of the (a-1) to the (a-2) of 0.5 or more and 5.0 or less. By setting the molar ratio within this range, it is believed that it is possible to achieve both high adhesion to a substrate and high developability due to the diol compound (a-1) and high resistance to wavelengths of 340 to 480 nm due to the diol compound (a-2).

[0025] [ka]

[0026] [ka]

[0027] In the general formula (1), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R1 is independently an alkylene group having 2 to 10 carbon atoms. l and m are independently numbers of 0 to 3. G is independently a (meth)acryloyl group, a functional group represented by the following general formula (3), or a functional group represented by the following general formula (4). X is independently -CO-, -SO2-, -C(CH3)2-, -C(CF3)2-, -Si(CH3)2-, -O-, -CH2-, a single bond, or a group represented by the following general formula (5).

[0028] In general formula (2), R2 is a divalent saturated hydrocarbon group having 2 to 20 carbon atoms.

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] In general formulas (3) and (4), R3 is independently a hydrogen atom or a methyl group, R4 is independently an alkylene group or an alkylarylene group having from 2 to 10 carbon atoms, R5 is independently a saturated or unsaturated hydrocarbon group having from 2 to 20 carbon atoms, and p is a number from 0 to 10. * indicates a bonding site to the structure represented by general formula (1).

[0033] The diol compound (a-1) represented by the general formula (1) can be synthesized by the following method.

[0034] First, an epoxy compound (a-0) (hereinafter simply referred to as "epoxy compound (a-0)") having a bisarylfluorene skeleton, which may have several alkylene oxide modified groups in one molecule, is prepared, as represented by the following general formula (6).

[0035] [ka]

[0036] In general formula (6), Ar are independently aromatic hydrocarbon groups having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Ar is preferably a phenylene group, which is an aryl group having 6 carbon atoms, or a naphthylene group, which is an aryl group having 10 carbon atoms.

[0037] R1 is independently an alkylene group having 2 to 10 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms.

[0038] l is independently a number between 0 and 3.

[0039] X is independently -CO-, -SO2-, -C(CH3)2-, -C(CF3)2-, -Si(CH3)2-, -O-, -CH2-, a single bond, or a group represented by the following general formula (5). Among these, from the viewpoint of improving the solvent resistance and adhesion to a substrate of the cured resin film, the group represented by the following general formula (5) is preferred. Furthermore, from the viewpoint of improving the resistance of the cured resin film to wavelengths of 340 to 480 nm, -C(CH3)2- and -CH2- are preferred, and -C(CH3)2- is more preferred.

[0040] [ka]

[0041] Then, the epoxy compound (a-0) is reacted with at least one of (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (7), and a (meth)acrylic acid derivative represented by the following general formula (8) to obtain the diol compound (a-1) represented by the general formula (1), which is an epoxy (meth)acrylate.

[0042] [ka]

[0043] [ka]

[0044] In general formulas (7) and (8), R3 is a hydrogen atom or a methyl group, R4 is an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R5 is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10.

[0045] The reaction of the diol compound (a-1) with (meth)acrylic acid or its derivatives can be carried out by a known method. For example, JP-A-4-355450 describes that a diol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth)acrylic acid per mole of an epoxy compound having two epoxy groups. The epoxy compound (a-0) used as a raw material and represented by general formula (6) may be partially oligomerized, and therefore a diol compound (a-1) having m of 1 to 3 may be produced. In this specification, m of the diol compound (a-1) is the average value of these values.

[0046] The unsaturated group-containing polymerizable resin according to this embodiment can be obtained by reacting the diol compound (a-1) with the diol compound (a-2) represented by general formula (2) and a tetrabasic acid or its dianhydride (a-3).

[0047] [ka]

[0048] In the general formula (2), R2 is a divalent saturated hydrocarbon group having 2 to 20 carbon atoms. From the viewpoint of achieving both the resistance of the resin cured film to light having a wavelength of 340 to 480 nm and the developability, the number of carbon atoms in R2 is preferably 4 to 15, more preferably 6 to 10. R2 may be a linear or branched hydrocarbon group, or a hydrocarbon group having an alicyclic structure. From the viewpoint of increasing the adhesion to the substrate and suppressing the decrease in the transmittance after development due to the penetration of the developer, a hydrocarbon group having an alicyclic structure is preferred.

[0049] Examples of the diol compound (a-2) in which R2 is a linear or branched hydrocarbon group include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, and 2,4-diethyl-1,5-pentanediol.

[0050] Examples of the diol compound (a-2) in which R2 is a hydrocarbon group having an alicyclic structure include 2,2-bis(4-hydroxycyclohexyl)propane, tricyclo[5.2.1.0]decanedimethanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cyclodecanediol, 1,5-cyclodecanediol, 1,2-decalindiol, 1,5-decalindiol, 4,4'-bicyclohexanediol, 4,4'-bicyclohexanedimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F. Among these, diols having multiple cyclic structures are preferred from the viewpoint of increasing the adhesion strength to the substrate and suppressing the decrease in transmittance after development due to the penetration of the developer. Diols having a cyclic structure without a crosslinking site are more preferred from the viewpoint of suppressing the yellowing of the resin cured film during curing (post-baking).

[0051] The unsaturated group-containing polymerizable resin is obtained by reacting a diol compound (a-1) with a diol compound (a-2) such that the molar ratio [(a-2) / (a-1)] is 0.5 or more and 5.0 or less. By making the molar ratio 0.5 or more, the resistance of the cured resin film to wavelengths of 340 to 480 nm can be increased. By making the molar ratio 5.0 or less, the adhesion of the cured resin film to the substrate and the developability of the curable resin composition can be increased. From the above viewpoints, [(a-2) / (a-1)] is preferably 1.0 or more and 4.0 or less, more preferably 1.5 or more and 3.0 or less.

[0052] Examples of the tetrabasic acid as the tetrabasic acid or its dianhydride (a-3) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, and acid dianhydrides thereof. Among these, aromatic hydrocarbon tetracarboxylic acid is preferred from the viewpoint of increasing adhesion to the substrate and suppressing a decrease in transmittance due to development. On the other hand, chain hydrocarbon tetracarboxylic acid is preferred from the viewpoint of increasing the resistance of the resin cured film to wavelengths of 340 to 480 nm. It is also preferred to use dianhydrides of these tetrabasic acids.

[0053] Examples of the above-mentioned chain hydrocarbon tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and these chain hydrocarbon tetracarboxylic acids having substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups introduced therein.

[0054] Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid, as well as these alicyclic tetracarboxylic acids having substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups introduced therein.

[0055] 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, 4'-(hexafluoroisopropylidene)diphthalic anhydride, etc. Among these, 4'-(hexafluoroisopropylidene)diphthalic anhydride is preferred from the viewpoint of increasing the resistance of the resin cured film to wavelengths of 340 to 480 nm.

[0056] In addition, bis(trimellitic anhydride) aryl esters can also be used as the tetrabasic acid or its dianhydride (a-3). Bis(trimellitic anhydride) aryl esters are compounds produced, for example, by the method described in International Publication No. 2010 / 074065, and structurally are dianhydrides in the form of ester bonds formed by reaction of two hydroxyl groups of an aromatic diol (such as naphthalenediol, biphenol, and terphenyldiol) with the carboxyl groups of two molecules of trimellitic anhydride.

[0057] In this case, a dibasic acid or a tribasic acid or an acid monoanhydride thereof (b) may be used in combination. Examples of the dibasic acid or tribasic acid include chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, etc. It is preferable to use an acid monoanhydride of these dibasic acids or tribasic acids.

[0058] Examples of the above-mentioned 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, and diglycolic acid, as well as these dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0059] Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyl tetrahydrophthalic acid, methyl end methylene tetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid, and norbornane dicarboxylic acid, as well as these dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0060] Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and trimellitic acid, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0061] Of these, the dicarboxylic acid or tricarboxylic acid is preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, or trimellitic acid, and more preferably succinic acid, itaconic acid, or tetrahydrophthalic acid.

[0062] When a dibasic acid or a tribasic acid is used in combination, it is preferable to react the diol compound (a-1), the diol compound (a-2), the dibasic acid or tribasic acid or its monoanhydride (b), and the tetrabasic acid or its dianhydride (a-3) in such a molar ratio that ((a-1)+(a-2)):(b):(a-3)=1.0:0.01-1.0:0.2-1.0 so that the terminals of the compounds become carboxy groups.

[0063] For example, when a dibasic acid or tribasic acid or its monoanhydride (b) is used with a tetrabasic acid or its dianhydride (a-3), it is preferable to react them so that the molar ratio [(b) / 2+(a-3)] / [(a-1)+(a-2)] of the amount of acid component to the total of diol compounds (a-1) and (a-2) is greater than 0.5 and less than 1.0. If the molar ratio is less than 1.0, the terminal of the unsaturated group-containing polymerizable resin represented by general formula (1) does not become an acid anhydride, so that the content of unreacted acid dianhydride is suppressed from increasing, and the stability of the curable resin composition over time can be improved. In addition, if the molar ratio is greater than 0.5, the amount of unreacted components remaining in the diol compound (a-1) is suppressed from increasing, and the stability of the curable resin composition over time can be improved. For the purpose of adjusting the acid value and molecular weight of the unsaturated group-containing polymerizable resin represented by general formula (1), the molar ratio of each component can be changed as desired within the above-mentioned ranges.

[0064] The reaction method of the diol compound (a-1), the diol compound (a-2) and the tetrabasic acid (and dibasic acid or tribasic acid) or its anhydride is not particularly limited, and a known method can be adopted. For example, JP-A-9-325494 describes a method of reacting an epoxy (meth)acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140° C. Under these conditions, the diol compound (a-2) can also be reacted at the same time.

[0065] By reacting the diol compound (a-1), the diol compound (a-2) and the tetrabasic acid in this manner, the unsaturated group-containing polymerizable resin according to this embodiment is obtained.

[0066] The weight average molecular weight (Mw) of the unsaturated group-containing polymerizable resin in terms of polystyrene, as measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation), is preferably 1000 to 40000, more preferably 1500 to 30000, and even more preferably 2000 to 15000. When the weight average molecular weight (Mw) is 1000 or more, the adhesion between the adhesive layer and the adherend can be improved. In addition, when the weight average molecular weight (Mw) is 40000 or less, the solution viscosity of the curable resin composition can be easily adjusted to a range suitable for application, and application to the surface of the support substrate is easy.

[0067] The acid value of the unsaturated group-containing polymerizable resin is preferably 20 mgKOH / g or more and 200 mgKOH / g or less, more preferably 25 mgKOH / g or more and 200 mgKOH / g or less. When the acid value is 20 mgKOH / g or more, residues are less likely to remain during alkaline development. When the acid value is 200 mgKOH / g or less, the penetration of the alkaline developer is not too fast, so peeling development is less likely to occur. When the acid value is 20 mgKOH / g or more, the strength of the adhesive layer is improved through a crosslinking reaction with the (C) component, and residues when irradiated with light can be reduced. The acid value can be determined by titration with a 1 / 10N-KOH aqueous solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0068] 2. Curable resin composition Another embodiment of the present invention relates to a curable resin composition comprising the unsaturated group-containing polymerizable resin described above.

[0069] The curable resin composition is (A) unsaturated group-containing polymerizable resin; (B) a polymerizable compound having at least two unsaturated bonds; (C) an epoxy compound having at least two epoxy groups, and (D) Solvent Includes.

[0070] Each component will be described in detail below.

[0071] [Component (A)] The component (A) is the unsaturated group-containing polymerizable resin described in the above embodiment. By using this unsaturated group-containing polymerizable resin, it is possible to obtain a curable resin composition that has low absorption of light at a wavelength of 340 to 480 nm after curing, and has high adhesion to a substrate and developability after curing.

[0072] The content of component (A) is preferably 5% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less, and even more preferably 10% by mass or more and 65% by mass or less, based on the total mass of the solid content. When the content of component (A) is 5% by mass or more, it is possible to increase adhesion and developability while reducing the absorption of light with a wavelength of 340 to 480 nm after curing. When the content is 70% by mass or less, it is possible to blend a sufficient amount of other components (particularly component (B)).

[0073] [(B) Component] The component (B) is a polymerizable compound having at least two unsaturated bonds.

[0074] The (B) component can increase the sensitivity and developability of the curable resin composition, and can increase the adhesion of the cured resin film obtained by curing the curable resin composition. The (B) component may have at least two or more polymerizable unsaturated groups that can react (polymerize) with the polymerizable unsaturated group of the (A) component. The polymerizable unsaturated group is preferably the same functional group as the polymerizable unsaturated group of the (A) component. Specifically, the polymerizable unsaturated group is preferably a (meth)acryloyl group. The (B) component may be a monomer, an oligomer, or a polymer, but is preferably a monomer or an oligomer.

[0075] Examples of component (B) include: (Meth)acrylic acid esters of 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 (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, sorbitol hexa(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, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate; urethane acrylate monomers such as pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene isocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer; Epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol fluorene type epoxy (meth)acrylate, diphenyl fluorene type epoxy (meth)acrylate, phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, and phenol aralkyl type epoxy (meth)acrylate; and and dendritic polymers having a plurality of polymerizable unsaturated groups (preferably (meth)acryloyl groups).

[0076] As the component (B), these photopolymerizable compounds may be used alone or in combination of two or more.

[0077] The (B) component preferably has two or more polymerizable unsaturated groups, and more preferably has three or more polymerizable unsaturated groups. When the (B) component has two or more polymerizable unsaturated groups, the solvent resistance and adhesion of the cured film are improved. In addition, the (B) component preferably has an acrylic equivalent, calculated by dividing the molecular weight by the number of (meth)acrylic groups in one molecule, of 50 to 300, and more preferably 80 to 200. The (B) component does not have a free carboxy group.

[0078] Examples of dendritic polymers having a (meth)acryloyl group that can be used as component (B) include dendritic polymers obtained by adding a polyvalent mercapto compound to a part of the carbon-carbon double bonds in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Specifically, they include dendritic polymers 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).

[0079] [ka]

[0080] (In the general formula (9), R6 is a hydrogen atom or a methyl group, and R7 is R8(OH) r The remaining portion is the portion where q of the r hydroxyl groups are donated to the ester bond in the formula. R8(OH) r is preferably a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, a polyhydric alcohol ether formed by linking a plurality of molecules of the polyhydric alcohol via ether bonds by dehydration condensation of the alcohol, or an ester of such a polyhydric alcohol or polyhydric alcohol ether with a hydroxy acid. r and q independently represent integers of 2 to 20, with r≧q.

[0081] [ka]

[0082] (In the general formula (10), R9 is a single bond or a divalent to hexavalent hydrocarbon group having 1 to 6 carbon atoms, and s is 2 when R9 is a single bond, and is the same as the valence of R9 when R9 is a divalent to hexavalent group.)

[0083] Examples of the polyfunctional (meth)acrylate represented by the general formula (9) include (meth)acrylic acid esters such as 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, and caprolactone modified pentaerythritol tri(meth)acrylate. These polyfunctional (meth)acrylates may be used alone or in combination of two or more.

[0084] Examples of polyvalent mercapto compounds represented by general formula (10) include trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercaptopropionate), pentaerythritol tetra(mercaptoacetate), pentaerythritol tri(mercaptoacetate), pentaerythritol tetra(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), etc. These polyvalent mercapto compounds may be used alone or in combination of two or more.

[0085] The dendritic polymer can increase the adhesive strength of the cured resin film to the substrate, and can suppress a decrease in transmittance after development and a decrease in adhesion after development caused by penetration of the developer.

[0086] The blending ratio of the (A) component to the (B) component is preferably 30 / 70 to 90 / 10, more preferably 50 / 50 to 80 / 20, in terms of the weight ratio (A) / (B). When the blending ratio of the (A) component is 30 / 70 or more, the cured product after photocuring is less likely to become brittle, and the acid value of the coating film is less likely to become low in the unexposed areas, so that the decrease in solubility in an alkaline developer can be suppressed. Therefore, problems such as jagged pattern edges and lack of sharpness are less likely to occur. In addition, when the blending ratio of the (A) component is 90 / 10 or less, the ratio of photoreactive functional groups in the resin is sufficient, so that the desired crosslinked structure can be formed. In addition, since the acid value of the resin component is not too high, the solubility in an alkaline developer in the exposed areas is less likely to increase, so that the formed pattern is less likely to be narrower than the target line width, and pattern loss can be suppressed.

[0087] [(C) component] Component (C) is an epoxy compound having at least two epoxy groups.

[0088] Examples of the component (C) include 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 (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jERYX4000: manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds, tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers of monomers having (meth)acrylic groups containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (e.g., celloxide 2021P: manufactured by Daicel Corporation), butane tetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone (for example, Epolead GT401: manufactured by Daicel Corporation), epoxy compounds having epoxycyclohexyl groups such as HiREM-1 manufactured by Shikoku Kasei Kogyo Co., Ltd., polyfunctional epoxy compounds having a dicyclopentadiene skeleton (for example, HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (for example, EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (for example, NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd.), epoxy compounds having a silicone skeleton, etc. are included. In addition, these compounds may be used alone or in combination of two or more types.

[0089] 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, and biphenyl type epoxy compounds are preferred, and bisphenol A type epoxy compounds and biphenyl type epoxy compounds are more preferred. By using bisphenol A type epoxy compounds, the flexibility of the adhesive layer can be increased, and the adhesion to the substrate can be improved. In addition, by using biphenyl type epoxy compounds, the patterning property of the curable resin composition during photocuring can be increased, and the degree of freedom in designing the curable resin composition can be increased.

[0090] The epoxy equivalent of the (C) component is preferably 100 g / eq or more and 300 g / eq or less, more preferably 100 g / eq or more and 250 g / eq or less. The number average molecular weight (Mn) of the (C) component is preferably 100 or more and 5000 or less. When the epoxy equivalent is 100 g / eq or more and 300 g / eq or less, and the number average molecular weight (Mn) of the epoxy compound is 100 to 5000, a cured film having good solvent resistance can be obtained. When the epoxy equivalent is 300 g / eq or less, sufficient alkali resistance can be maintained even when an alkaline chemical solution is used in a post-process.

[0091] The content of component (C) is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less, based on the total mass of the solid contents. When the content of component (C) is 5% by mass or more, based on the total mass of the solid contents, the chemical resistance of the cured resin film can be improved. When the content is 60% by mass or less, the adhesion during development can be improved.

[0092] The curable resin composition may be used in combination with a curing agent and a curing accelerator as necessary. Examples of the curing agent include amine compounds, polyvalent carboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc., which contribute to the curing of epoxy resins. Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc., which contribute to the curing of epoxy resins.

[0093] [(D) component] Component (D) is a solvent.

[0094] The component (D) dissolves or disperses each component contained in the curable resin composition, and improves the applicability of the curable resin composition to a supporting substrate.

[0095] Examples of 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 α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monobutyl ... glycol ethers such as 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; and esters such as 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, and propylene glycol monoethyl ether acetate. By dissolving and mixing using these, the curable resin composition can be made into a uniform solution.

[0096] The content of the (D) component varies depending on the target viscosity of the curable resin composition, but is preferably from 40% by mass to 90% by mass based on the total mass of the curable resin composition.

[0097] [Other ingredients] The curable resin composition may contain, as necessary, a photopolymerization initiator, a photosensitizer, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, a coupling agent, and the like.

[0098] Examples of the photopolymerization initiator include acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and acyloxime ester compounds.

[0099] Examples of the acetophenone compound include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

[0100] Examples of triazine compounds include 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and the like.

[0101] Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin tert-butyl ether, and the like.

[0102] Examples of the benzophenone compound include benzophenone, o-benzoylmethylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(N,N-diethylamino)benzophenone, and the like.

[0103] Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxane, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

[0104] Examples of the imidazole compound include 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(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.

[0105] Examples of oxime ester 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]-adamantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol -3-yl]-tetrahydrofuranylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one Oxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-adamantane carboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione = 2-o-benzoyl oxime, 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-acetyloxime), ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-o-acetyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2-octanedien, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)- 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyloxime, etc.

[0106] As the oxime ester-based initiator, an O-oxime ester-based photopolymerization initiator represented by general formula (11) or general formula (12) may be used.

[0107] [ka]

[0108] In the general formula (11), R10 and R11 each independently represent an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms, and R12 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 portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. The alkyl group may be any of linear, branched, and cyclic alkyl groups.

[0109] [ka]

[0110] In general formula (12), R13 and R14 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group, or an 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. R15 are each independently a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and some of the -CH2- groups in the alkyl group or alkenyl group may be substituted with -O- groups. Furthermore, some of the hydrogen atoms in these groups R13 to R15 may be substituted with halogen atoms.

[0111] The content of the photopolymerization initiator is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 0.3 parts by mass or more and 20 parts by mass or less, when the total mass of the (A) component and the (B) component is taken as 100 parts by mass. When the content of the photopolymerization initiator is 0.1 parts by mass or more, photopolymerization can be promoted and the rate of photopolymerization can be increased. When the content of the photopolymerization initiator is 30 parts by mass or less, the concentration of radicals generated during exposure can be controlled, and the polymerization reaction of the unexposed part can be suppressed to improve the resolution. In addition, when a pattern is formed by photolithography, it is preferable that the curable resin composition contains a photopolymerization initiator, but when a pattern is not formed or a pattern is formed by a method other than photolithography, the photopolymerization initiator may not be contained.

[0112] Examples of photosensitizers include acetophenones such as triethanolamine, triisopropanolamine, benzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, and (n-butoxy)ethyl 4-dimethylaminobenzoate. benzophenones such as benzoyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone; thioxanthones such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenones such as 4,4'-bisdiethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone.

[0113] The content of the photosensitizer is preferably 0.5 parts by mass or more and 400 parts by mass or less, and more preferably 1 part by mass or more and 300 parts by mass or less, when the total mass of the photopolymerization initiator is 100 parts by mass. When the content of the photosensitizer is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be improved, and the photopolymerization speed can be increased. In addition, when the content of the photosensitizer is 400 parts by mass or less, the coloring of the cured film can be suppressed, and the transmittance of the cured film can be increased.

[0114] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina. Examples of defoamers and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of surfactants include fluorine-based surfactants and silicone-based surfactants. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0115] [Preparation method] The curable resin composition can be prepared by mixing the above-mentioned components.

[0116] 3.Resin cured film The above-mentioned curable resin composition forms a resin cured film by irradiation with radiation, and can be used as a protective layer in various display devices such as liquid crystal displays, organic EL display devices, μLED display devices, and display devices to which quantum dots are applied, an insulating film for printed wiring boards and semiconductor packages, resist layers such as solder resist layers, plating resist layers, and etching resist layers, interlayer insulating layers for multilayer printed wiring boards, gas barrier films, sealing materials for lenses and semiconductor light-emitting elements such as light-emitting diodes (LEDs), top coats for paints and inks, hard coats for plastics, and rust-proof films for metals. In this specification, the term "semiconductor package" refers to a flip chip package, a wafer level package, and the like, as well as a package that includes a semiconductor chip and is configured to be mounted on a printed board, such as a flip chip package stacked on an interposer. In particular, the present invention is useful for optical semiconductor packages that are combined with light-emitting elements (preferably LEDs such as UV-LEDs and Blue-LEDs). The thermosetting composition itself can also be molded and used to produce films, substrates, plastic parts, optical lenses, and the like.

[0117] In particular, the cured resin film is less likely to yellow over time due to electromagnetic waves with wavelengths of about 340 to 480 nm, and therefore, when used in various devices having a light source (such as a UV-LED or a Blue-LED) that emits the electromagnetic waves, the adverse effects of yellowing over time can be suppressed. From this viewpoint, the cured resin film is preferably disposed closer to the light source, and, in particular, when used as a protective film (sealant) for arranging and sealing the light source on a mounting board, the effect of suppressing the adverse effects of yellowing over time is remarkable compared to other materials.

[0118] The cured resin film can be produced, for example, by applying the curable resin composition to a substrate or the like, drying it, and irradiating (exposing) it to light (including ultraviolet light, radiation, etc.) to cure it. At this time, a photomask or the like is used to provide areas that are exposed to light and areas that are not exposed to light, and only the areas that are exposed to light are cured, while the other areas are dissolved in an alkaline solution, to obtain a cured product having a desired pattern.

[0119] When applying the curable resin composition to a substrate, any of the known methods such as a solution immersion method, a spray method, or a method using a roller coater, a land coater, a slit coater or a spinner can be used.

[0120] By these methods, the curable resin composition is applied to a desired thickness, and then the solvent is removed (prebaked) to form a coating. Prebaking is performed by heating in an oven or a hot plate, vacuum drying, or a combination of these. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, and are performed, for example, at a temperature of 80 to 120°C for 1 to 10 minutes.

[0121] Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays, with radiation having a wavelength in the range of 250 to 450 nm being preferred.

[0122] Alkaline development can be carried out using, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like as a developer. These developers are selected according to the characteristics of the resin layer, and a surfactant may be added as necessary. Development is preferably carried out at a temperature of 20 to 35°C. Fine images can be precisely formed by using a commercially available developer or ultrasonic cleaner. After alkaline development, the substrate is usually washed with water. Examples of development methods include shower development, spray development, dip (immersion) development, and puddle (liquid puddle) development.

[0123] After development in this manner, a heat treatment (post-baking) is performed at a temperature of 180 to 250° C. for 20 to 100 minutes. This post-baking is performed for the purpose of increasing the adhesion between the patterned coating film and the substrate. Like the pre-baking, the post-baking is performed by heating in an oven, a hot plate, or the like.

[0124] Thereafter, polymerization or curing (both may be collectively referred to as curing) is completed by heat to obtain a cured film such as an insulating film, etc. The curing temperature at this time is preferably in the range of 160 to 250°C.

[0125] In addition, when preparing a resin cured film by thermal curing using a thermal polymerization initiator, the above-mentioned curable resin composition may be applied to a substrate, etc., dried, and heat-treated. The conditions for application, drying (pre-bake), and heat treatment (post-bake) at this time may be the same as those described for the above-mentioned method including exposure and alkali development.

[0126] The above-mentioned curable resin composition can be used for various applications, including forming a resin cured film by irradiation with radiation, a protective film, an insulating material, an adhesive, etc. In addition, since the curable resin composition contains an alkali-soluble resin and thus can be developed after exposure or heating, it can also be suitably used for applications in which a fine line pattern is formed.

[0127] Furthermore, the above-mentioned curable resin composition can be used as an adhesive composition, particularly since it has high adhesive strength even after pattern formation, for bonding various members in the production of semiconductor packages such as MEMS packages and LEDs.

[0128] When used for adhesive applications, the entire coating film may be exposed to light without a negative mask. In this case, alkaline development is not necessary. When used as an adhesive for semiconductor elements or different materials without patterning, the coating film may be thermally cured by heating instead of photocuring by exposure. EXAMPLES

[0129] Hereinafter, the embodiments of the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to these.

[0130] First, synthesis examples of the unsaturated group-containing polymerizable resin, component (A), will be described. Unless otherwise specified, the resins in these synthesis examples were evaluated as follows.

[0131] In addition, when the same model of measuring equipment is used, the name of the equipment manufacturer is omitted from the second place. In addition, in the examples, all glass substrates used to prepare the substrates with cured films for measurement are used after the same treatment. In addition, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted.

[0132] [Solid content concentration] The weight [W1(g)] after 1 g of the resin solution obtained in Synthesis Example was impregnated into a glass filter [weight: W0(g)] and the weight [W2(g)] after heating for 2 hours at 130°C for component (A) and at 160°C for component (B) were calculated from the following formula. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0133] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content.

[0134] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0135] The abbreviations used in the Synthesis Examples are as follows. BPFE: Bisphenol fluorene type epoxy resin (in general formula (6), Ar is a benzene ring, X is a fluorene structure represented by general formula (5), l is an epoxy resin of 0, epoxy equivalent 250g / eq) jER 828: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the company, epoxy equivalent 185g / eq) AA: Acrylic acid TPP: Triphenylphosphine PGMEA: Propylene glycol monomethyl ether acetate 6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride THPA: 1,2,3,6-Tetrahydrophthalic anhydride DPHA: Dipentaerythritol hexaacrylate PTMA: Pentaerythritol tetra(mercaptoacetate) HQ: Hydroquinone BzDMA: benzyldimethylamine

[0136] [Synthesis Example 1] In a 300 mL four-neck flask equipped with a reflux condenser, BPFE (77.28 g, 0.16 mol), AA (22.28 g, 0.32 mol), TPP (0.41 g), and PGMEA (17.60 g) were charged and stirred at 100 to 105 ° C for 12 hours to obtain a reaction product. Then, PGMEA (82.44 g) was charged and adjusted to a solid content of 50 mass%, to obtain a resin solution (a-1)-1 containing a diol compound represented by general formula (1).

[0137] Next, in a 300 mL four-neck flask equipped with a reflux condenser, 2,2'-bis(4-hydroxycyclohexyl)propane (14.42 g, 0.06 mol), 6FDA (39.12 g, 0.09 mol), THPA (13.42 g, 0.09 mol), and PGMEA (40.00 g) were charged into the resin solution (a-1)-1 (150.00 g, 0.12 mol) containing the obtained diol compound, and the mixture was stirred at 115 to 120 ° C for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-1. The solid content concentration of the obtained resin solution was 55.3 mass%, the acid value (solid content equivalent) was 105 mg KOH / g, and the Mw by GPC analysis was 2800.

[0138] [Synthesis Example 2] In a 300 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (120.00 g, 0.09 mol) containing the diol compound described in Synthesis Example 1, 2,2'-bis(4-hydroxycyclohexyl)propane (22.39 g, 0.09 mol), 6FDA (41.38 g, 0.09 mol), THPA (14.17 g, 0.09 mol), and PGMEA (50.00 g) were charged and stirred at 115 to 120 ° C. for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-2. The solid content concentration of the obtained resin solution was 55.6 mass%, the acid value (solid content equivalent) was 114 mg KOH / g, and the Mw by GPC analysis was 2700.

[0139] [Synthesis Example 3] In a 300 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (90.00 g, 0.07 mol) containing the diol compound described in Synthesis Example 1, 2,2'-bis(4-hydroxycyclohexyl)propane (34.10 g, 0.14 mol), 6FDA (47.02 g, 0.11 mol), THPA (16.10 g, 0.11 mol), and PGMEA (70.00 g) were charged and stirred at 115 to 120 ° C. for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-3. The solid content concentration of the obtained resin solution was 55.3 mass%, the acid value (solid content equivalent) was 125 mg KOH / g, and the Mw by GPC analysis was 2400.

[0140] [Synthesis Example 4] In a 300 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (60.00 g, 0.05 mol) containing the diol compound described in Synthesis Example 1, 2,2'-bis(4-hydroxycyclohexyl)propane (44.78 g, 0.19 mol), 6FDA (51.73 g, 0.12 mol), THPA (17.11 g, 0.12 mol), and PGMEA (85.00 g) were charged and stirred at 115 to 120 ° C. for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-4. The solid content concentration of the obtained resin solution was 55.6 mass%, the acid value (solid content equivalent) was 136 mg KOH / g, and the Mw by GPC analysis was 2200.

[0141] [Synthesis Example 5] In a 300 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (95.00 g, 0.07 mol) containing the diol compound described in Synthesis Example 1, tricyclo[5.2.1.0]decane dimethanol (29.39 g, 0.15 mol), 6FDA (49.64 g, 0.11 mol), THPA (17.00 g, 0.11 mol), and PGMEA (70.00 g) were charged and stirred at 115 to 120 ° C. for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-5. The solid content concentration of the obtained resin solution was 55.0 mass%, the acid value (solid content equivalent) was 131 mg KOH / g, and the Mw by GPC analysis was 2300.

[0142] [Synthesis Example 6] In a 300 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g, 0.08 mol) containing the diol compound described in Synthesis Example 1, 1,4-cyclohexanedimethanol (22.73 g, 0.16 mol), 6FDA (52.25 g, 0.12 mol), THPA (17.89 g, 0.12 mol), and PGMEA (65.00 g) were charged and stirred at 115 to 120 ° C. for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-6. The solid content concentration of the obtained resin solution was 55.4 mass%, the acid value (solid content equivalent) was 139 mg KOH / g, and the Mw by GPC analysis was 2100.

[0143] [Synthesis Example 7] In a 300 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (90.00 g, 0.07 mol) containing the diol compound described in Synthesis Example 1, 1,6-hexanediol (16.76 g, 0.14 mol), 6FDA (47.02 g, 0.11 mol), THPA (16.10 g, 0.11 mol), and PGMEA (55.00 g) were charged and stirred at 115 to 120 ° C. for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-7. The solid content concentration of the obtained resin solution was 55.5 mass%, the acid value (solid content equivalent) was 143 mg KOH / g, and the Mw by GPC analysis was 2000.

[0144] [Synthesis Example 8] In a 300 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (100.00 g, 0.08 mol) containing the diol compound described in Synthesis Example 1, 2,2'-bis(4-hydroxycyclohexyl)propane (37.89 g, 0.16 mol), 1,2,3,4-butanetetracarboxylic dianhydride (23.30 g, 0.12 mol), THPA (17.89 g, 0.12 mol), and PGMEA (55.00 g) were charged and stirred at 115 to 120 ° C. for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-8. The solid content concentration of the obtained resin solution was 55.1 mass%, the acid value (solid content equivalent) was 153 mg KOH / g, and the Mw by GPC analysis was 2000.

[0145] [Synthesis Example 9] In a 300 mL four-neck flask equipped with a reflux condenser, jER 828 (71.40 g, 0.19 mol), AA (28.09 g, 0.39 mol), TPP (0.55 g), and PGMEA (17.60 g) were charged and stirred at 100 to 105 ° C for 12 hours to obtain a reaction product. Then, PGMEA (82.40 g) was charged and adjusted so that the solid content was 50 mass%, and a resin solution (a-1)-2 containing a diol compound represented by general formula (1) was obtained.

[0146] Next, in a 300 mL four-neck flask equipped with a reflux condenser, 2,2'-bis(4-hydroxycyclohexyl)propane (33.23 g, 0.14 mol), 6FDA (45.82 g, 0.10 mol), THPA (15.69 g, 0.10 mol), and PGMEA (70.00 g) were charged into the resin solution (a-1)-2 (70.00 g, 0.07 mol) containing the obtained diol compound, and the mixture was stirred at 115 to 120 ° C for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)-9. The solid content concentration of the obtained resin solution was 55.3 mass%, the acid value (solid content equivalent) was 134 mg KOH / g, and the Mw by GPC analysis was 2900.

[0147] [Synthesis Example 10] In a 300 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (160.00 g, 0.12 mol) containing the diol compound described in Synthesis Example 1, 6FDA (27.59 g, 0.06 mol), THPA (9.45 g, 0.06 mol), and PGMEA (15.00 g) were charged and stirred at 115 to 120 ° C. for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)'-10. The solid content concentration of the obtained resin solution was 55.2 mass%, the acid value (solid content equivalent) was 89 mg KOH / g, and the Mw by GPC analysis was 3000.

[0148] [Synthesis Example 11] In a 300 mL four-neck flask equipped with a reflux condenser, 2,2'-bis(4-hydroxycyclohexyl)propane (55.00 g, 0.23 mol), 6FDA (50.82 g, 0.11 mol), THPA (17.40 g, 0.11 mol), and PGMEA (100.00 g) were charged and stirred at 115 to 120 ° C for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)'-11. The solid content concentration of the obtained resin solution was 55.2 mass%, the acid value (solid content equivalent) was 156 mg KOH / g, and the Mw by GPC analysis was 1900.

[0149] [Synthesis Example 12] In a 300 mL four-neck flask equipped with a reflux condenser, the resin solution (a-1)-1 (43.00 g, 0.03 mol) containing the diol compound described in Synthesis Example 1, 2,2'-bis(4-hydroxycyclohexyl)propane (45.47 g, 0.19 mol), 6FDA (49.43 g, 0.11 mol), THPA (16.93 g, 0.11 mol), and PGMEA (85.00 g) were charged and stirred at 115 to 120 ° C. for 8 hours to obtain an unsaturated group-containing polymerizable resin (A)'-12. The solid content concentration of the obtained resin solution was 55.6 mass%, the acid value (solid content equivalent) was 140 mg KOH / g, and the Mw by GPC analysis was 2100.

[0150] [Synthesis Example 13] 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) were added to a 1 L four-neck flask and reacted at 60 ° C for 12 hours to obtain dendritic polymer solution (B)-2. The disappearance of mercapto groups in the obtained dendritic polymer was confirmed by iodometry. The solid content concentration of the obtained dendritic polymer solution was 80.0 mass %, and Mw by GPC analysis was 10,000.

[0151] Curable resin compositions of Examples 1 to 13 and Comparative Examples 1 to 3 were prepared in the amounts (unit: mass %) shown in Tables 1 and 2. The components used in Tables 1 and 2 are as follows.

[0152] (Unsaturated group-containing curable resin) (A)-1: Resin solution obtained in Synthesis Example 1 (solid content concentration: 55.3% by mass) (A)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration: 55.6% by mass) (A)-3: Resin solution obtained in Synthesis Example 3 (solid content concentration: 55.3% by mass) (A)-4: Resin solution obtained in Synthesis Example 4 (solid content concentration: 55.6% by mass) (A)-5: Resin solution obtained in Synthesis Example 5 (solid content concentration: 55.0% by mass) (A)-6: Resin solution obtained in Synthesis Example 6 (solid content concentration: 55.4% by mass) (A)-7: Resin solution obtained in Synthesis Example 7 (solid content concentration: 55.5% by mass) (A)-8: Resin solution obtained in Synthesis Example 8 (solid content concentration: 55.1% by mass) (A)-9: Resin solution obtained in Synthesis Example 9 (solid content concentration: 55.3% by mass) (A)'-10: Resin solution obtained in Synthesis Example 10 (solid content concentration: 55.2% by mass) (A)'-11: Resin solution obtained in Synthesis Example 11 (solid content concentration: 55.2% by mass) (A)'-12: Resin solution obtained in Synthesis Example 12 (solid content concentration: 55.6% by mass)

[0153] (polymerizable compound) (B)-1: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) (B)-2: Dendritic polymer solution obtained in Synthesis Example 13 (solid content concentration: 80.0% by mass)

[0154] (C): Biphenyl-type epoxy resin (jER YX4000, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190 g / eq)

[0155] (Photopolymerization initiator) (D): 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) (manufactured by BASF, "IrgacureOXE-01" and "Irgacure" are registered trademarks of the company)

[0156] (solvent) (E): Propylene glycol monomethyl ether acetate (PGMEA)

[0157] [Table 1]

[0158] [Table 2]

[0159] [evaluation] The compositions shown in Tables 1 and 2 were evaluated as follows.

[0160] (Initial transmittance, transmittance after light resistance test, preparation of substrate with cured resin film for evaluation of adhesion strength with glass substrate) The curable resin compositions shown in Tables 1 and 2 were each preliminarily irradiated with a low-pressure mercury lamp at a wavelength of 254 nm and an illuminance of 1000 mJ / cm 2 The resin was applied to a 125 mm x 125 mm glass substrate "#1737" whose surface had been cleaned by irradiating it with ultraviolet light of 10.0 μm using a spin coater so that the film thickness after heat curing would be 10.0 μm, and the substrate was prebaked at 90° C. for 3 minutes using a hot plate to prepare a dry film. The substrate was then main cured (post-baked) at 230° C. for 30 minutes using a hot air dryer to obtain substrates with resin cured films according to Examples 1 to 13 and Comparative Examples 1 to 3.

[0161] [Initial transmittance evaluation] Using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation), the transmittance at a wavelength of 400 nm of the substrate with the cured resin film after main curing and before a light resistance test was measured.

[0162] [Evaluation of changes in transmittance through light resistance testing] A blue filter "IEB400" (manufactured by Isuzu Precision Glass Co., Ltd., 50mm x 50mm x 5mmt, transmittance of wavelengths of 340nm or less to 480nm or more is less than 10%) was placed on the substrate with the cured resin film after the main curing, and light was irradiated for 1000 hours in a Xe test chamber "Q-SUN Xe-1" (manufactured by Q-Lab Corporation). The transmittance at a wavelength of 400nm was measured for the region of the substrate with the cured resin film irradiated with light through the blue filter using a UV-Visible-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.). The change in transmittance due to the light resistance test was evaluated based on the change in transmittance before and after light irradiation (change in transmittance / transmittance before light irradiation) relative to the transmittance before light irradiation, according to the following criteria. Note that △ or higher was considered to be pass.

[0163] ⊚: The change in transmittance before and after the light resistance test is less than 10%. ○: The change in transmittance before and after the light resistance test is 10% or more and less than 15%. △: The change in transmittance before and after the light resistance test is 15% or more and less than 20%. ×: The change in transmittance before and after the light resistance test is 20% or more.

[0164] [Adhesion strength evaluation with glass substrate] A 2.7 mmΦ stud pin with epoxy adhesive was placed on the resin cured film of the above-mentioned resin cured film-coated substrate cut to 15 mm x 20 mm, and dried in an oven at 80°C for 30 minutes. After that, a heat curing treatment was carried out using a hot air dryer at 150°C for 60 minutes to adhere the stud pin to the resin cured film, thereby preparing an adhesion test specimen.

[0165] Next, the adhesive strength between the glass substrate and the cured resin film was measured using a stud-pull peel strength tester (Romulus, manufactured by Quad Group).

[0166] (Evaluation Criteria) ◎: Adhesion strength is 160kgf / cm 2 Super ○: Adhesion strength is 150kgf / cm 2 Super 160kgf / cm 2 Is less than or equal to △: Adhesion strength is 140kgf / cm 2 Super 150kgf / cm 2 Is less than or equal to ×: Adhesion strength is 140kgf / cm 2 Is less than or equal to

[0167] (Preparation of substrates with cured resin film for evaluation of initial pattern transmittance and development adhesion) The curable resin compositions shown in Tables 1 and 2 were applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing treatment would be 10.0 μm, and the substrate was prebaked at 90° C. for 3 minutes using a hot plate to prepare a dry film. Next, an i-line illuminance of 30 mW / cm was applied to the dry film. 2 100mJ / cm2 ultra-high pressure mercury lamp 2 The dried film was exposed to ultraviolet light of 1000 ohms to cause a photocuring reaction.

[0168] Next, the exposed film was developed at 1 kgf / cm using a 2.38% TMAH (tetramethylammonium hydroxide) developer at 23°C. 2 After developing for 60 seconds with a shower pressure of 5kgf / cm 2 The unexposed areas were removed by spray washing with water to form dot patterns with diameters of 5 to 40 μm. Finally, the substrate was post-cured (post-baked) at 230° C. for 30 minutes using a hot air dryer to obtain substrates with cured resin films according to Examples 1 to 13 and Comparative Examples 1 to 3.

[0169] [Evaluation of initial pattern transmittance] The transmittance of the substrate with the cured resin film after development and main curing at a wavelength of 400 nm was measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

[0170] [Development adhesion] The dot pattern of the cured resin film on the obtained substrate with the cured resin film was observed using an optical microscope to judge whether the pattern peeled off or not.

[0171] (Evaluation Criteria) ⊚: The minimum dot pattern size that can be formed without peeling is less than 10 μm. ◯: The minimum dot pattern size that can be formed without peeling is 10 μm or more and less than 20 μm. Δ: The minimum size of the dot pattern that can be formed without peeling is 20 μm or more and less than 40 μm. ×: 40 μm dot pattern peeled off.

[0172] The evaluation results are shown in Tables 3 and 4.

[0173] [Table 3]

[0174] [Table 4]

[0175] As can be seen from the comparison between Examples 1 to 13 and Comparative Examples 1 to 3, by using a curable resin composition containing an unsaturated group-containing polymerizable resin (A) in which the molar ratio of diol compound (a-1) to diol compound (a-2) [(a-2) / (a-1)] is 0.5 or more and 5.0 or less, it is possible to suppress yellowing of the cured resin film caused by light of 340 nm to 480 nm, and to achieve both adhesion to a glass substrate and adhesion when developed.

[0176] As can be seen from the comparison of Examples 3, 5 to 7, it was found that the (a-2) component having at least one alicyclic structure can suppress the penetration of the developer into the photocured portion during development, and can suppress peeling of fine patterns and yellowing of the cured resin film after main curing. It was also found that the use of a polymerizable compound having a high molecular weight as the (B) component can similarly suppress the penetration of the developer, and can further suppress yellowing of the cured resin film.

[0177] As can be seen from a comparison between Examples 3 and 8, by using an acid dianhydride having at least one aromatic ring structure as the component (a-3), the toughness of the cured resin film could be improved, and the adhesion to a substrate such as glass could be improved. [Industrial Applicability]

[0178] The present invention can provide an unsaturated group-containing polymerizable resin and a curable resin composition capable of producing a resin cured film having low absorption of light having a wavelength of 340 to 480 nm. The present invention can be suitably used in various fields in which low absorption of light having the above wavelengths is required, and in various fields in which it is desired to suppress deterioration caused by light having the above wavelengths.

Claims

1. The unsaturated group-containing polymerizable resin is obtained by reacting a diol compound (a-1) represented by the following general formula (1), a diol compound (a-2) represented by the following general formula (2), and a tetrabasic acid or a dianhydride thereof (a-3), wherein the molar ratio of (a-1) to (a-2), [(a-2) / (a-1)], is 0.5 or more and 5.0 or less. 【Chemistry 1】 【Chemistry 2】 In general formula (1), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and some of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R1 is independently an alkylene group having 2 to 10 carbon atoms. l and m are independently numbers of 0 to 3. G is independently a (meth)acryloyl group, a functional group represented by the following general formula (3), or a functional group represented by the following general formula (4). X is independently -CO-, -SO ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -Si(CH ３ ) ２ --, --O-, --CH ２ -, a single bond, or a group represented by the following general formula (5). In general formula (2), R2 is a divalent saturated hydrocarbon group having 2 to 20 carbon atoms. 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 In general formulas (3) and (4), R3 is independently a hydrogen atom or a methyl group, R4 is independently an alkylene group or an alkylarylene group having from 2 to 10 carbon atoms, R5 is independently a saturated or unsaturated hydrocarbon group having from 2 to 20 carbon atoms, and p is a number from 0 to 10. * indicates a bonding site to the structure represented by general formula (1).

2. The diol compound (a-2) is a compound in which R2 is a saturated hydrocarbon group having an alicyclic structure. The unsaturated group-containing polymerizable resin according to claim 1 .

3. The tetrabasic acid or its dianhydride (a-3) is a tetrabasic acid or its dianhydride containing an aromatic ring. The unsaturated group-containing polymerizable resin according to claim 1 .

4. The weight average molecular weight is 1,000 or more and 40,000 or less, and the acid value is 20 mgKOH / g or more and 200 mgKOH / g or less. The unsaturated group-containing polymerizable resin according to claim 1 .

5. (A) the unsaturated group-containing polymerizable resin according to any one of claims 1 to 4, (B) a polymerizable compound having at least two unsaturated bonds; (C) an epoxy compound having at least two epoxy groups, and (D) a solvent, A curable resin composition comprising:

6. A cured resin film obtained by curing the curable resin composition according to claim 5.

7. A semiconductor package comprising the cured resin film according to claim 6.

8. A display device comprising the cured resin film according to claim 6.

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