Polymerizable resin containing unsaturated group, curable resin composition, resin cured film, semiconductor package and display device

Abstract

The present invention relates to an unsaturated group-containing polymerizable resin which has low absorption of light having a wavelength of 340 to 480 nm and has high adhesion and developability. The present invention is an unsaturated group-containing polymerizable resin obtained by reacting a compound (a-1) represented by formula (1), a compound (a-2) represented by formula (2), and a tetrabasic acid (a-3), and the molar ratio [(a-2) / (a-1)] is 0.5-5.0 (inclusive). # imgabs0 #

Description

Technical Field

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

[0002] A planarization sealing film is provided in μ-LED displays or semiconductor packages to eliminate the height difference between the stacked layers. The planarization sealing film is required to have properties such as adhesion to the substrate, and the material of the planarization sealing film is required to have high developability, etc. As a material for the planarization sealing film that can meet these requirements, Patent Document 1 discloses a radiation-sensitive resin composition comprising an alkali-soluble unsaturated resin having a bisphenol fluorene structure.

[0003] [Prior art literature]

[0004] [Patent Document]

[0005] Patent Document 1: Japanese Patent Application Publication No. 2003-089716. Summary of the invention

[0006] [Problems to be solved by the invention]

[0007] The cured product of the resin composition containing an alkali-soluble unsaturated resin having a bisphenol fluorene structure described in Patent Document 1 is excellent in adhesion to a substrate and solvent resistance, and is therefore useful as a planarizing sealing film.

[0008] In addition, according to the novel discovery of the inventors, it is known that the flattening sealing film disposed on the μ-LED display is prone to degradation at the portion directly above the UV-LED or Blue-LED. In order to suppress this degradation, it is considered to use a resin with low absorbance at short wavelengths of 340 to 480 nm, which is the emission wavelength of these LEDs, for the flattening sealing film. As for the candidate resins that meet the above absorbance requirements, silicone resins or acrylic resins can be considered, but the adhesion or developability of these resins to the substrate is not very high.

[0009] The present invention has been studied in view of this point, and its purpose is to provide a polymerizable resin containing an unsaturated group, a curable resin composition containing the polymerizable resin containing an unsaturated group, a resin cured film obtained from the curable resin composition, and a semiconductor package and a display device having the resin cured film. The polymerizable resin containing an unsaturated group can obtain a curable resin composition that has low absorption for light with a wavelength of 340 to 480 nm, is not easily degraded by light of these wavelengths, and has high adhesion and developability to a substrate.

[0010] [Methods to solve the problem]

[0011] One aspect of the present invention for solving the above-mentioned problems is the unsaturated group-containing polymerizable resin described in the following [1] to [4].

[0012] [1] A polymerizable resin containing an unsaturated group, which is a 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 its dianhydride (a-3), wherein the molar ratio of the aforementioned (a-1) to the aforementioned (a-2) [(a-2) / (a-1)] is greater than 0.5 and less than 5.0.

[0013]

[0014] In the general formula (1), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms constituting Ar may be substituted by 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 a number from 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).

[0015] In the general formula (2), R2 is a divalent saturated hydrocarbon group having 2 to 20 carbon atoms.

[0016]

[0017]

[0018] In the general formulae (3) and (4), R3 is independently a hydrogen atom or a methyl group, R4 is independently an alkylene group or an alkylarylene group having a carbon number of 2 to 10, R5 is independently a saturated or unsaturated hydrocarbon group having a carbon number of 2 to 20, and p is a number of 0 to 10. * indicates a site bonded to the structure represented by the general formula (1).

[0019] [2] The unsaturated group-containing polymerizable resin according to [1], wherein the diol compound (a-2) is a compound in which R2 is a saturated hydrocarbon group having an alicyclic structure.

[0020] [3] The unsaturated group-containing polymerizable resin according to [1] or [2], wherein the tetrabasic acid or its dianhydride (a-3) is an aromatic ring-containing tetrabasic acid or its dianhydride.

[0021] [4] The unsaturated group-containing polymerizable resin according to any one of [1] to [3], which has a weight average molecular weight of 1,000 to 40,000 and an acid value of 20 mgKOH / g to 200 mgKOH / g.

[0022] Another aspect of the present invention for solving the above-mentioned problems relates to the curable resin composition of the following [5].

[0023] [5] A curable resin composition comprising:

[0024] (A) the unsaturated group-containing polymerizable resin according to any one of [1] to [4];

[0025] (B) a polymerizable compound having at least two unsaturated bonds;

[0026] (C) an epoxy compound having at least two epoxy groups; and

[0027] (D) Solvent.

[0028] Another aspect of the present invention for solving the above-mentioned problems relates to the following cured resin film [6].

[0029] [6] A cured resin film obtained by curing the curable resin composition described in [5].

[0030] Still another aspect of the present invention for solving the above-mentioned problems relates to the semiconductor package described below [7].

[0031] [7] A semiconductor package comprising the cured resin film described in [6].

[0032] Still another aspect of the present invention for solving the above-mentioned problems relates to the following display device [8].

[0033] [8] A display device comprising the cured resin film described in [6].

[0034] [Effects of the invention]

[0035] According to the present invention, there can be provided a polymerizable resin containing an unsaturated group, a curable resin composition containing the polymerizable resin containing an unsaturated group, a resin cured film obtained from the curable resin composition, and a semiconductor package and a display device having the resin cured film, wherein the polymerizable resin containing an unsaturated group can obtain low absorption of light with a wavelength of 340 to 480 nm, is not easily degraded by light of these wavelengths, and has high adhesion and developability to a substrate. DETAILED DESCRIPTION

[0036] The following describes the embodiments of the present invention, but the present invention is not limited to the following embodiments. In addition, in this specification, the content of each component is omitted when the first decimal place is 0. In addition, if there is no special description of the compound, functional group or structure illustrated below, only one of the illustrated ones can be used, or multiple ones can be used in combination.

[0037] In the present specification, “(meth)acrylic acid” is a general term for acrylic acid and methacrylic acid, and “(meth)acryloyl” is a general term for acryloyl and methacryloyl, and means one or both of them.

[0038] 1. Polymer resin containing unsaturated groups

[0039] One embodiment of the present invention relates to a polymerizable resin containing an unsaturated group.

[0040] 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.

[0041] In the above-mentioned polymerizable resin containing an unsaturated group, the molar ratio of the above-mentioned (a-1) to the above-mentioned (a-2) [(a-2) / (a-1)] is 0.5 to 5.0. It is believed that by making the above-mentioned molar ratio within this range, it is possible to have both high adhesion to the substrate and high developability derived from the diol compound (a-1) and high resistance to light with a wavelength of 340 to 480 nm derived from the diol compound (a-2).

[0042]

[0043]

[0044] In the general formula (1), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms constituting Ar may be substituted by 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 a number from 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).

[0045] In the general formula (2), R2 is a divalent saturated hydrocarbon group having 2 to 20 carbon atoms.

[0046]

[0047] In the general formulae (3) and (4), R3 is independently a hydrogen atom or a methyl group, R4 is independently an alkylene group or an alkylarylene group having a carbon number of 2 to 10, R5 is independently a saturated or unsaturated hydrocarbon group having a carbon number of 2 to 20, and p is a number of 0 to 10. * indicates a site bonded to the structure represented by the general formula (1).

[0048] The diol compound (a-1) represented by the general formula (1) can be synthesized by the following method.

[0049] First, an epoxy compound (a-0) having a bisarylfluorene skeleton and optionally having a plurality of alkylene oxide-modified groups in one molecule represented by the following general formula (6) (hereinafter referred to as “epoxy compound (a-0)”) is prepared.

[0050]

[0051] In the general formula (6), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms constituting Ar may be substituted by 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. 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.

[0052] R1 is independently an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and still more preferably an alkylene group having 2 to 3 carbon atoms.

[0053] l is independently a number from 0 to 3.

[0054] 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). Among these, from the viewpoint of improving the solvent resistance of the cured resin film and the adhesion to the substrate, the group represented by the following general formula (5) is more preferred. In addition, from the viewpoint of improving the resistance of the cured resin film to light with a wavelength of 340 to 480 nm, -C(CH 3 ) 2 - and - CH 2 -, more preferably -C(CH 3 ) 2 -.

[0055]

[0056] Next, 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 a diol compound (a-1) represented by the general formula (1) which is an epoxy (meth)acrylate.

[0057]

[0058] In the general formulae (7) and (8), R3 is a hydrogen atom or a methyl group, R4 is an alkylene group or an alkylarylene group having a carbon number of 2 to 10, R5 is a saturated or unsaturated hydrocarbon group having a carbon number of 2 to 20, and p is a number of 0 to 10.

[0059] The reaction of the diol compound (a-1) with (meth) acrylic acid or its derivative can be carried out using a well-known method. For example, Japanese Patent Publication No. 4-355450 states that about 2 moles of (meth) acrylic acid are used for 1 mole of an epoxy compound having two epoxy groups, thereby obtaining a diol compound containing a polymerizable unsaturated group. In addition, the epoxy compound (a-0) represented by the general formula (6) used as a raw material may also partially oligomerize, so a diol compound (a-1) with m of 1 to 3 is also generated. In this specification, m of the diol compound (a-1) is an average value of these.

[0060] The unsaturated group-containing polymerizable resin of the present embodiment can be obtained by reacting the diol compound (a-1) with the diol compound (a-2) represented by the general formula (2) and a tetrabasic acid or a dianhydride thereof (a-3).

[0061]

[0062] In the general formula (2), R2 is a divalent saturated hydrocarbon group having a carbon number of 2 or more and 20 or less. From the viewpoint of achieving both the resistance and developability of the cured resin film to light of a wavelength of 340 to 480 nm, the carbon number of R2 is preferably 4 or more and 15 or less, and more preferably 6 or more and 10 or less. R2 may be a straight-chain or branched hydrocarbon group, or a hydrocarbon group having an alicyclic structure. From the viewpoint of improving the adhesion to the substrate and suppressing the decrease in the transmittance after development caused by the penetration of the developer, a hydrocarbon group having an alicyclic structure is more preferred.

[0063] Examples of the diol compound (a-2) in which R2 is a linear or branched hydrocarbon group include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, 1,12-dodecanediol, 2-methyl-1,3-propylene glycol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propylene glycol, 2-butyl-2-ethyl-1,3-propylene glycol, 2-ethyl-1,3-hexanediol and 2,4-diethyl-1,5-pentanediol.

[0064] 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 a plurality of cyclic structures are more preferred from the viewpoint of improving the adhesion strength to the substrate and suppressing the decrease in the post-development transmittance due to the penetration of the developer. From the viewpoint of suppressing the yellowing of the cured resin film during curing (post-bak), diols having a cyclic structure without a crosslinking site are more preferred.

[0065] The polymerizable resin containing an unsaturated group is obtained by reacting a diol compound (a-1) and a diol compound (a-2) in a molar ratio [(a-2) / (a-1)] of 0.5 to 5.0. By making the molar ratio greater than 0.5, the resistance of the cured resin film to light of a wavelength of 340 to 480 nm can be improved. By making the molar ratio less than 5.0, the adhesion between the cured resin film and the substrate and the developability of the curable resin composition can be improved. From the above viewpoints, [(a-2) / (a-1)] is preferably greater than 1.0 and less than 4.0, and more preferably greater than 1.5 and less than 3.0.

[0066] Examples of tetracarboxylic acids as tetracarboxylic acids or their dianhydrides (a-3) include: chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, and their dianhydrides. Among these, aromatic hydrocarbon tetracarboxylic acids are more preferred from the viewpoint of improving the adhesion to the substrate and suppressing the reduction in transmittance caused by development. On the other hand, chain hydrocarbon tetracarboxylic acids are more preferred from the viewpoint of improving the resistance of the resin cured film to light of a wavelength of 340 to 480 nm. In addition, these tetracarboxylic acids are more preferably dianhydrides.

[0067] Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and these chain hydrocarbon tetracarboxylic acids into which a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group is introduced.

[0068] Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and nor Alkanedetaracarboxylic acids, and alicyclic tetracarboxylic acids into which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups are introduced.

[0069] Examples of the aromatic hydrocarbon tetracarboxylic acid include pyromelitic acid, diphenyl ketone 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 more preferred from the viewpoint of improving the resistance of the cured resin film to light of a wavelength of 340 to 480 nm.

[0070] In addition, the tetrabasic acid or its dianhydride (a-3) can be used as bis-trimellitic anhydride aryl esters. Bis-trimellitic anhydride aryl esters are compounds produced by the method described in International Publication No. 2010 / 074065, and are dianhydrides in which two hydroxyl groups of an aromatic diol (naphthalene diol, biphenol, and terphenyl glycol, etc.) react with two carboxyl groups of two molecules of trimellitic anhydride to form an ester bond.

[0071] At this time, a dibasic acid or a tribasic acid or an acid monoanhydride (b) thereof may be used in combination. The dibasic acid or the tribasic acid may include, for example, a chain hydrocarbon dicarboxylic acid or a tricarboxylic acid, an alicyclic hydrocarbon dicarboxylic acid or a tricarboxylic acid, an aromatic hydrocarbon dicarboxylic acid or a tricarboxylic acid, etc. It is more preferred to use an acid monoanhydride for these dibasic acids or tribasic acids.

[0072] Examples of the above-mentioned chain hydrocarbon dicarboxylic acids or tricarboxylic acids 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 introduced with arbitrary substituents.

[0073] Examples of the alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorotrimethic acid, hexahydrotrimellitic acid, and cyclohexanedicarboxylic acid. Alkanedicarboxylic acids, etc., and these dicarboxylic acids or tricarboxylic acids, etc., into which any substituent is introduced.

[0074] Examples of the aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids 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 into which any substituent is introduced.

[0075] Among the above-mentioned dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid are more preferred, and succinic acid, itaconic acid and tetrahydrophthalic acid are more preferred.

[0076] When a dibasic acid or a tribasic acid is used in combination, it is more preferred that the ends of the compounds become carboxyl groups so that the molar ratio of the diol compound (a-1), the diol compound (a-2), the dibasic acid or the tribasic acid or their monoanhydrides (b) and the tetrabasic acid or their dianhydrides (a-3) becomes ((a-1) + (a-2)): (b): (a-3) = 1.0:0.01 to 1.0:0.2 to 1.0.

[0077] For example, when a dibasic acid or tribasic acid or an acid monoanhydride thereof (b) and a tetrabasic acid or an acid dianhydride thereof (a-3) are used, it is more preferred to react such that the molar ratio of the amount of the acid component [(b) / 2+(a-3)] to the total of the diol compounds (a-1) and (a-2) [[(b) / 2+(a-3)] / [(a-1)+(a-2)]] is greater than 0.5 and less than 1.0. When the molar ratio is less than 1.0, the terminal of the polymerizable resin containing an unsaturated group represented by the general formula (1) will not become an acid anhydride, so that the increase in the content of the unreacted acid dianhydride can be suppressed, and the temporal stability of the curable resin composition can be improved. In addition, when the molar ratio is greater than 0.5, the increase in the residual amount of the unreacted component in the diol compound (a-1) can be suppressed, and the temporal stability of the curable resin composition can be improved. Furthermore, the molar ratio of each component may be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the unsaturated group-containing polymerizable resin represented by the general formula (1).

[0078] 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 well-known method can be used. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method of reacting epoxy (meth)acrylate with tetracarboxylic dianhydride at a reaction temperature of 90 to 140° C. The diol compound (a-2) can be reacted simultaneously under such conditions.

[0079] 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 of the present embodiment can be obtained.

[0080] The polystyrene-equivalent weight average molecular weight (Mw) of the polymerizable resin containing an unsaturated group measured by colloid permeation chromatography (GPC) (HLC-8220GPC, manufactured by TOSOH Co., Ltd.) is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 15,000. If the weight average molecular weight (Mw) is 1,000 or more, the adhesion between the adhesive layer and the substrate can be improved. If the weight average molecular weight (Mw) is 40,000 or less, it is easy to adjust the solution viscosity of the curable resin composition to a range suitable for coating, and it is easier to apply to the surface of the substrate.

[0081] The acid value of the polymerizable resin containing an unsaturated group is preferably 20 mgKOH / g or more and 200 mgKOH / g or less, and more preferably 25 mgKOH / g or more and 200 mgKOH / g or less. If the acid value is 20 mgKOH / g or more, it is not easy to leave residue during alkali development. If the acid value is 200 mgKOH / g or less, the penetration of the alkali developer will not be too fast, so it is not easy to produce peeling development. If the acid value is 20 mgKOH / g or more, the strength of the adhesive layer can be improved through the cross-linking reaction with the (C) component, and the residue during irradiation can be reduced. In addition, the acid value can be obtained by titrating with a 1 / 10N-KOH aqueous solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Industry Co., Ltd.).

[0082] 2. Curable resin composition

[0083] Another embodiment of the present invention is a curable resin composition containing the above-mentioned unsaturated group-containing polymerizable resin.

[0084] The curable resin composition contains:

[0085] (A) a polymerizable resin containing an unsaturated group;

[0086] (B) a polymerizable compound having at least two unsaturated bonds;

[0087] (C) an epoxy compound having at least two epoxy groups; and

[0088] (D) Solvent.

[0089] Each component is described in detail below.

[0090] [(A) ingredient]

[0091] Component (A) is the polymerizable resin containing an unsaturated group as described in the above embodiment. By using the polymerizable resin containing an unsaturated group, a curable resin composition can be obtained which has low absorption of light with a wavelength of 340 to 480 nm after curing and has high adhesion and developability to the substrate after curing.

[0092] 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 relative to the total mass of the solid content. If the content of component (A) is 5% by mass or more, the absorption of light with a wavelength of 340 to 480 nm after curing is low, and the adhesion and developability can be improved. If the content is 70% by mass or less, a sufficient amount of other components (particularly component (B)) can be blended.

[0093] [(B) ingredient]

[0094] (B) The component is a polymerizable compound having at least two unsaturated bonds.

[0095] The (B) component can improve the sensitivity and developability of the curable resin composition, or improve the adhesion of the resin cured film formed by curing the curable resin composition. The (B) component only needs to have at least two or more polymerizable unsaturated groups that can react (polymerize) with the polymerizable unsaturated groups possessed by the (A) component. The above-mentioned polymerizable unsaturated group is preferably the same functional group as the polymerizable unsaturated group possessed by the (A) component. Specifically, the above-mentioned polymerizable unsaturated group is more preferably a (meth)acryloyl group. In addition, the (B) component can be a monomer, an oligomer, or a polymer, but is more preferably a monomer or an oligomer.

[0096] Examples of (B) ingredients include:

[0097] (Meth)acrylates 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, and dipentaerythritol hexa(meth)acrylate;

[0098] Urethane acrylate monomers such as pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer;

[0099] Epoxy (meth)acrylates such as bisphenol A epoxy (meth)acrylate, bisphenol F epoxy (meth)acrylate, bisphenol fluorene epoxy (meth)acrylate, diphenylfluorene epoxy (meth)acrylate, phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and phenol aralkyl epoxy (meth)acrylate; and

[0100] Dendrimers having a plurality of polymerizable unsaturated groups (preferably (meth)acryloyl groups), and the like.

[0101] (B) The component may be one of these photopolymerizable compounds alone or two or more of them may be used in combination.

[0102] The component (B) preferably has two or more polymerizable unsaturated groups, and more preferably has three or more polymerizable unsaturated groups. If the component (B) has two or more polymerizable unsaturated groups, the solvent resistance and adhesion of the cured film can be improved. In addition, in the component (B), the acrylic acid equivalent of the molecular weight divided by the number of (meth) acrylic acid groups in one molecule is preferably 50 to 300, and more preferably 80 to 200. In addition, the component (B) does not have a free carboxyl group.

[0103] Examples of dendritic polymers having (meth)acryloyl groups that can be used as component (B) include dendritic polymers obtained by adding a polyvalent mercapto compound to a portion of the carbon-carbon double bonds in the (meth)acryloyl groups of polyfunctional (meth)acrylates. Specifically, they include dendritic polymers obtained by reacting the (meth)acryloyl groups of polyfunctional (meth)acrylates represented by the following general formula (9) with the polyvalent mercapto compound represented by the following general formula (10).

[0104]

[0105] (In the general formula (9), R6 is a hydrogen atom or a methyl group, R7 is R8 (OH) r The q hydroxyl groups out of the r hydroxyl groups are provided to the remaining part after the ester bond in the formula. R8(OH) r More preferably, it is a polyol based on a non-aromatic straight-chain or branched hydrocarbon skeleton having a carbon number of 2 to 8, or 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 these polyols or polyol ethers with a hydroxy acid. r and q independently represent an integer of 2 to 20, but r ≥ q)

[0106]

[0107] (In the general formula (10), R9 is a single bond or a hydrocarbon group with a valency of 2 or more and 6 or less and a carbon number of 1 or more and 6 or less, and s is 2 when R9 is a single bond, and has the same valency as R9 when R9 is a group with a valency of 2 or more and 6 or less)

[0108] Examples of the polyfunctional (meth)acrylate represented by the general formula (9) include (meth)acrylates 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.

[0109] Examples of the polyvalent mercapto compounds represented by the general formula (10) include trimethylolpropane tris(thioglycolate), trimethylolpropane tris(thiopropionate), pentaerythritol tetra(thioglycolate), pentaerythritol tris(thioglycolate), pentaerythritol tetra(thiopropionate), dipentaerythritol hexa(thioglycolate), dipentaerythritol hexa(thiopropionate), etc. These polyvalent mercapto compounds may be used alone or in combination of two or more.

[0110] The dendritic polymer can improve the adhesion strength of the cured resin film to the substrate, and can suppress a decrease in transmittance after development or a decrease in adhesion after development caused by penetration of a developer.

[0111] The blending ratio of component (A) to component (B) is preferably 30 / 70 to 90 / 10, and more preferably 50 / 50 to 80 / 20, in terms of weight ratio (A) / (B). If the blending ratio of component (A) is 30 / 70 or more, the hardened material after photocuring is not easy to become brittle. In addition, the acid value of the coating in the unexposed portion is not easy to become low, so the solubility in the alkaline developer can be suppressed. Therefore, the edge of the pattern is not easy to produce jagged or unclear defects. In addition, if the blending ratio of component (A) is 90 / 10 or less, the proportion of photoreactive functional groups in the resin is sufficient, so the desired cross-linked structure can be formed. In addition, the acid value in the resin component will not be too high, so the solubility in the alkaline developer in the exposed portion is not easy to increase, so the formed pattern can be suppressed from becoming thinner than the target line width or the pattern is missing.

[0112] [(C) ingredient]

[0113] (C) Component is an epoxy compound having at least two epoxy groups.

[0114] 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., jER YX4000: manufactured by Mitsubishi Chemical Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds, tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyols, glycidyl esters of polycarboxylic acids, copolymers of monomers having (meth)acrylic acid groups containing glycidyl (meth)acrylate as units, represented by copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., celloxide 2021P: manufactured by Daicel Co., Ltd.), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (e.g., EPL GT401: manufactured by Daicel Co., Ltd.), epoxy compounds having an epoxycyclohexyl group represented by HiREM-1 manufactured by Shikoku Chemical Industry Co., Ltd., multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g. HP7200 series: manufactured by DIC Co., Ltd.), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g. EHPE3150: manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (e.g. NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd.), epoxy compounds having a polysiloxane skeleton, etc. In addition, these compounds may be used alone or in combination of two or more.

[0115] 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 more 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 improved, 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 light curing can be improved, and the degree of freedom in designing the curable resin composition can be expanded.

[0116] The epoxy equivalent of component (C) is preferably 100 g / eq to 300 g / eq, and more preferably 100 g / eq to 250 g / eq. In addition, the number average molecular weight (Mn) of component (C) is preferably 100 to 5000. If the epoxy equivalent is 100 g / eq to 300 g / eq, and the number average molecular weight (Mn) of the epoxy compound is 100 to 5000, a cured film with good solvent resistance can be obtained. In addition, if the epoxy weight is 300 g / eq or less, sufficient alkali resistance can be maintained even when an alkaline solution is used in a subsequent step.

[0117] The content of component (C) is preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 50% by mass or less, relative to the total mass of the solids. If the content of component (C) is 5% by mass or more relative to the total mass of the solids, the chemical resistance of the cured resin film can be improved. If it is 60% by mass or less, the adhesion during development can be improved.

[0118] The curable resin composition may optionally contain a curing agent and a curing accelerator. Examples of the curing agent include amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamide, Lewis acid complexes, etc., which help to cure the epoxy resin. Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borates, Lewis acids, organometallic compounds, imidazoles, etc., which help to cure the epoxy resin.

[0119] [(D) ingredient]

[0120] The component (D) is a solvent.

[0121] The component (D) dissolves or disperses the components contained in the curable resin composition and improves the coating properties of the curable resin composition on the holding substrate.

[0122] 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 α- or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; pyrrolidone) and other ketones; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; glycol ethers such as cellosol, methyl cellosol, ethyl cellosol, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol dimethyl ether, 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; esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosol acetate, ethyl cellosol acetate, butyl cellosol acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. By dissolving and mixing these, the curable composition can be made into a uniform solution.

[0123] The content of the component (D) may be changed depending on the target viscosity of the curable resin composition, but is preferably 40% by mass or more and 90% by mass or less based on the total mass of the curable resin composition.

[0124] [Other ingredients]

[0125] The curable resin composition may optionally be blended with a photopolymerization initiator, a photosensitizer, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, a defoaming agent, a surfactant, a coupling agent, and the like.

[0126] Examples of photopolymerization initiators include acetophenone compounds, Compounds, benzoin compounds, diphenyl ketone compounds, thioxanthone compounds, imidazole compounds, acyl oxime ester compounds and other photopolymerization initiators.

[0127] Examples of acetophenone compounds include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-〔4-(2-hydroxyethoxy)phenyl〕propane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, oligomers of 2-hydroxy-2-methyl-1-〔4-(1-methylvinyl)phenyl〕propane-1-one, and the like.

[0128] three Examples of compounds include: 2,4,6-tris(trichloromethyl)-1,3,5-tri , 2-methyl-4,6-bis(trichloromethyl)-1,3,5-tri , 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-tri , 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-tri , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tri , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-tri , 2-(4-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-tri , 2-(3,4,5-trimethoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-trimethoxyphenylvinyl , 2-(4-methylthiophenylphenyl)-4,6-bis(trichloromethyl)-1,3,5-tri wait.

[0129] 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.

[0130] Examples of the phenyl ketone compound include phenyl ketone, methyl o-benzoylbenzoate, 4-phenyl phenyl ketone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylpercarbonyl)phenyl ketone, 2,4,6-trimethylphenyl ketone, 4,4'-bis(N,N-diethylamino)phenyl ketone, and the like.

[0131] 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, and the like.

[0132] 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.

[0133] Examples of the 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]-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]-tetrahydrofuranylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-benzoate, Hydrofuranylmethane-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]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morpholinylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morpholinylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-adamantanecarboxylate, 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-o-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]ethanone-o-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethyl ketone, 1-[7-(2-methylbenzoyl)- 9,9-dipropyl-9H-fluoren-2-yl]-1-(O-acetyl oxime), ethyl ketone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-o-acetyl oxime, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), 1,2-octanediene, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiophenyl)butane-1,2-diketo-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butane-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazo-3-yl-O-acetyl oxime, etc.

[0134] As the oxime ester initiator, an O-oxime ester photopolymerization initiator represented by the general formula (11) or (12) can be used.

[0135]

[0136] 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 by 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.

[0137]

[0138] In the general formula (12), R13 and R14 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl group or an alkylcycloalkyl group, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. R15 is each independently a linear or branched alkyl group or an alkenyl group having 2 to 10 carbon atoms, wherein -CH 2 A part of the - group may be substituted with an -O- group. In addition, a part of the hydrogen atoms in the groups of R13 to R15 may be substituted with a halogen atom.

[0139] As for the content of the photopolymerization initiator, when the total mass of the components (A) and (B) is set to 100 parts by mass, it is more 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. If the above content of the photopolymerization initiator is 0.1 parts by mass or more, photopolymerization can be promoted and the speed of photopolymerization can be accelerated. In addition, if the above content of the photopolymerization initiator is 30 parts by mass or less, the concentration of free radicals generated during exposure can be controlled, the polymerization reaction of the unexposed part can be suppressed, and the resolution can be improved. In addition, the curable resin composition preferably contains a photopolymerization initiator when forming a pattern by photolithography, and may not contain a photopolymerization initiator when no pattern is formed or when a pattern is formed by a method other than photolithography.

[0140] Examples of photosensitizers include: acetophenones such as triethanolamine, triisopropanolamine, diphenyl ketone, 4,4'-bisdimethylaminodiphenyl ketone (Michelle's ketone), 4-phenyldiphenyl ketone, 4,4'-dichlorodiphenyl ketone, hydroxydiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, 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, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butyloxy) ... diphenyl ketone series such as isopentyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated phenyl ketone, 3,3',4,4'-tetrakis(tert-butylcarbonylperoxy)phenyl ketone and 3,3'-dimethyl-4-methoxyphenyl ketone, thioxanthone series such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; aminophenyl ketone series such as 4,4'-bisdiethylaminophenyl ketone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone and camphorquinone.

[0141] When the total mass of the photopolymerization initiator is 100 parts by mass, 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. If the content of the photosensitizer is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be increased and the speed of photopolymerization can be accelerated. In addition, if the content of the photosensitizer is 400 parts by mass or less, the coloring of the cured film can be suppressed and the penetration rate of the cured film can be increased.

[0142] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenanthridine, 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, fluorine, and acrylic compounds. Examples of surfactants include fluorine-based surfactants and silicone-based surfactants. Examples of coupling agents include 3-(epoxypropyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0143] [Preparation method]

[0144] The curable resin composition can be prepared by mixing the above-mentioned components.

[0145] 3. Resin hardening film

[0146] The above-mentioned curable resin composition can form a resin cured film by irradiating radiation, and is used for a protective layer in various display devices such as a liquid crystal display, an organic EL display device, a μLED display device, and a display device using quantum dots, such as an insulating film for printed wiring substrates and semiconductor packaging, such as a solder mask, a plating-resistant layer, an etching-resistant layer, an interlayer insulating layer such as a multilayer printed circuit board, a gas barrier film, a lens, and a semiconductor light-emitting element such as a light-emitting diode (LED) The surface coating (topcoat) of the coating or printing ink, a hard coating of plastics, and a rust-proof film of metals. In addition, in this specification, semiconductor packaging means that in addition to flip chip packaging, wafer-level packaging, etc., it also includes, for example, a flip chip package stacked on an interposer, etc., generally containing a semiconductor chip (chip) and can be installed on a printed substrate. In particular, it is useful for optical semiconductor packaging combined with a light-emitting element (preferably an LED such as UV-LED or Blue-LED). In addition, it can also be applied to molding the thermosetting composition itself and making films, substrates, plastic parts, optical lenses, etc.

[0147] In particular, the resin cured film is not prone to yellowing over time due to electromagnetic waves with a wavelength of about 340 to 480 nm, so when used in various devices having a light source (such as UV-LED or Blue-LED, etc.) that emits the electromagnetic wave, the disadvantages caused by yellowing over time can be suppressed. From this point of view, the resin cured film is preferably arranged at a position closer to the light source, and especially when used as a protective film (sealing material) for arranging the light source on a mounting board and sealing it, the effect of suppressing the disadvantages caused by yellowing over time is more significant than other materials.

[0148] The above-mentioned cured resin film can be produced, for example, by applying the above-mentioned curable resin composition to a substrate, drying it, and irradiating it with light (including ultraviolet rays, radiation, etc.) (exposing it) to cure it. At this time, if a photomask or the like is used to set the irradiated part and the non-irradiated part, and only the irradiated part is cured and the other part is dissolved with an alkaline solution, a cured product with a desired pattern can be obtained.

[0149] When the curable resin composition is applied to the substrate, any method may be adopted, such as a well-known solution dipping method, a spraying method, a method using a roll coater, a land coater, a slit coater, or a spinner.

[0150] After the curable resin composition is applied to a desired thickness by these methods, the solvent is removed (pre-baking) to form a film. Pre-baking can be performed by heating with an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in pre-baking can be appropriately selected according to the solvent used, for example, at a temperature of 80 to 120° C. for 1 to 10 minutes.

[0151] Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays, and radiation having a wavelength in the range of 250 to 450 nm is more preferred.

[0152] Alkali development can be carried out using aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine and tetramethylammonium hydroxide as developer. These developers can be selected according to the characteristics of the resin layer, and a surfactant can be optionally added. Development is preferably carried out at a temperature of 20 to 35°C. Commercially available developers or ultrasonic washing machines can be used to accurately form fine images. In addition, water washing is usually performed after alkali development. Examples of development treatment methods include shower development, spray development, dip development, and puddle development.

[0153] After development as described above, heat treatment (post-baking) is performed at a temperature of 180 to 250° C. for 20 to 100 minutes. The purpose of the post-baking is to improve the adhesion between the patterned coating film and the substrate. The post-baking can be performed by heating in an oven or a hot plate, as in the pre-baking.

[0154] Thereafter, polymerization or curing (both are sometimes collectively referred to as curing) by heat is completed, and a cured film such as an insulating film can be obtained. The curing temperature at this time is more preferably in the range of 160 to 250°C.

[0155] When a resin cured film is produced by thermal curing using a thermal polymerization initiator, the curable resin composition may be applied to a substrate, etc., and then dried and heat treated. The conditions for coating, drying (pre-baking) and heat treatment (post-baking) at this time may be the same as those described in the above method including exposure and alkali development.

[0156] In addition, the curable resin composition can be used for various applications including protective films, insulating materials, and adhesives that form a resin cured film by irradiation with radiation. In addition, the curable resin composition can be developed after exposure or heating by containing an alkali-soluble resin, so it is also suitable for the application of forming a fine line pattern.

[0157] The curable resin composition can be used as an adhesive composition. In particular, since it has high adhesive strength even after patterning, it can be used for bonding various members in the production of semiconductor packages such as MEMS packages and LEDs.

[0158] When used for adhesive purposes, the entire coating can be exposed without using a negative mask. In the above case, alkali development is not required. In addition, when patterning is not performed and the adhesive is used as a semiconductor element or a heterogeneous material, the coating can be cured by heating instead of photocuring by exposure.

[0159] (Example)

[0160] Hereinafter, the embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.

[0161] First, the synthesis examples of the unsaturated group-containing polymerizable resin of the component (A) will be described. However, the evaluation of the resins in these synthesis examples was performed in the following manner unless otherwise specified.

[0162] In addition, when the same machine model is used for various measurement machines, the machine manufacturer name is omitted from the second occurrence. In addition, in the examples, the glass substrates used to make the substrates with cured films for measurement were all subjected to the same treatment and used. In addition, the content of each component is omitted when the first decimal place is 0.

[0163] [Solid content]

[0164] 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter (weight: W 0 (g) The weight after 1 (g)], and the weight of component (A) at 130°C and component (B) at 160°C after heating for 2 hours [W 2 (g)〕, the solid content concentration was calculated by the following formula.

[0165] Solid content (wt%) = 100 × (W 2 -W 0 ) / (W 1 -W 0 )

[0166] [Acid value]

[0167] Dissolve the resin solution in The alkane was titrated with a 1 / 10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the acid value.

[0168] [Molecular weight]

[0169] The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by TOSOH Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by TOSOH Co., Ltd.), temperature: 40°C, speed: 0.6 ml / min), and the weight average molecular weight (Mw) was calculated using the converted value of standard polystyrene (manufactured by TOSOH Co., Ltd., PS-Oligomer Kit).

[0170] The abbreviations described in the synthesis examples are as follows.

[0171] BPFE: bisphenol fluorene epoxy resin [in general formula (6), A is a benzene ring, X is a fluorene structure shown in general formula (5), l is 0 epoxy resin, epoxy equivalent 250g / eq]

[0172] jER 828: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., "jER" is a registered trademark of the same company, epoxy equivalent 185 g / eq)

[0173] AA: Acrylic acid

[0174] TPP: triphenylphosphine

[0175] PGMEA: Propylene glycol monomethyl ether acetate

[0176] 6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

[0177] THPA: 1,2,3,6-Tetrahydrophthalic anhydride

[0178] DPHA: Dipentaerythritol hexaacrylate

[0179] PTMA: Pentaerythritol tetrakis(thioglycolate)

[0180] HQ: Hydroquinone

[0181] BzDMA: benzyl dimethylamine

[0182] [Synthesis example 1]

[0183] BPFE (77.28 g, 0.16 mol), AA (22.28 g, 0.32 mol), TPP (0.41 g), and PGMEA (17.60 g) were added to a 300 mL four-necked flask equipped with a reflux cooler, and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. PGMEA (82.44 g) was then added and adjusted to a solid content of 50% by mass to obtain a resin solution (a-1)-1 containing a diol compound represented by the general formula (1).

[0184] Next, 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 added to the obtained resin solution (a-1)-1 (150.00 g, 0.12 mol) containing the diol compound in a 300 mL four-necked flask equipped with a reflux cooler, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)-1 containing an unsaturated group. The obtained resin solution had a solid content concentration of 55.3% by mass, an acid value (solid content conversion) of 105 mgKOH / g, and a Mw of 2800 by GPC analysis.

[0185] [Synthesis example 2]

[0186] In a 300 mL four-necked flask with a reflux cooler, 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 added, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)-2 containing an unsaturated group. The solid content concentration of the obtained resin solution was 55.6% by mass, the acid value (solid content conversion) was 114 mgKOH / g, and the Mw of the GPC analysis was 2700.

[0187] [Synthesis example 3]

[0188] In a 300 mL four-necked flask with a reflux cooler, 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 added, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)-3 containing an unsaturated group. The solid content concentration of the obtained resin solution was 55.3% by mass, the acid value (solid content conversion) was 125 mgKOH / g, and the Mw of the GPC analysis was 2400.

[0189] [Synthesis Example 4]

[0190] In a 300 mL four-necked flask with a reflux cooler, 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 added, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)-4 containing an unsaturated group. The solid content concentration of the obtained resin solution was 55.6% by mass, the acid value (solid content conversion) was 136 mgKOH / g, and the Mw of the GPC analysis was 2200.

[0191] [Synthesis Example 5]

[0192] In a 300 mL four-necked flask equipped with a reflux cooler, 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]decanedimethanol (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 added, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)-5 containing an unsaturated group. The solid content concentration of the obtained resin solution was 55.0% by mass, the acid value (solid content conversion) was 131 mgKOH / g, and the Mw of the GPC analysis was 2300.

[0193] [Synthesis example 6]

[0194] In a 300 mL four-necked flask with a reflux cooler, 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 added, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)-6 containing an unsaturated group. The solid content concentration of the obtained resin solution was 55.4% by mass, the acid value (solid content conversion) was 139 mgKOH / g, and the Mw of the GPC analysis was 2100.

[0195] [Synthesis Example 7]

[0196] In a 300 mL four-necked flask with a reflux cooler, 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 added, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)-7 containing an unsaturated group. The solid content concentration of the obtained resin solution was 55.5% by mass, the acid value (solid content conversion) was 143 mgKOH / g, and the Mw of the GPC analysis was 2000.

[0197] [Synthesis example 8]

[0198] In a 300 mL four-necked flask equipped with a reflux cooler, 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 added, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)-8 containing an unsaturated group. The obtained resin solution had a solid content concentration of 55.1% by mass, an acid value (solid content conversion) of 153 mgKOH / g, and a Mw of 2000 by GPC analysis.

[0199] [Synthesis Example 9]

[0200] In a 300 mL four-necked flask equipped with a reflux cooler, 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 added and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. PGMEA (82.40 g) was then added and adjusted to a solid content of 50% by mass to obtain a resin solution (a-1)-2 containing a diol compound represented by the general formula (1).

[0201] Then, in a 300 mL four-necked flask with a reflux cooler, 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 added to the obtained resin solution (a-1)-2 containing the diol compound (70.00 g, 0.07 mol), and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)-9 containing an unsaturated group. The obtained resin solution had a solid content concentration of 55.3% by mass, an acid value (solid content conversion) of 134 mgKOH / g, and a Mw of 2900 by GPC analysis.

[0202] [Synthesis Example 10]

[0203] In a 300 mL four-necked flask with a reflux cooler, 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 added, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)'-10 containing an unsaturated group. The solid content concentration of the obtained resin solution was 55.2% by mass, the acid value (solid content conversion) was 89 mgKOH / g, and the Mw of the GPC analysis was 3000.

[0204] [Synthesis Example 11]

[0205] 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 added to a 300 mL four-necked flask with a reflux cooler, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)'-11 containing an unsaturated group. The solid content concentration of the obtained resin solution was 55.2% by mass, the acid value (solid content conversion) was 156 mgKOH / g, and the Mw of the GPC analysis was 1900.

[0206] [Synthesis Example 12]

[0207] In a 300 mL four-necked flask with a reflux cooler, 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 added, and stirred at 115 to 120° C. for 8 hours to obtain a polymerizable resin (A)'-12 containing an unsaturated group. The solid content concentration of the obtained resin solution was 55.6% by mass, the acid value (solid content conversion) was 140 mgKOH / g, and the Mw of the GPC analysis was 2100.

[0208] [Synthesis Example 13]

[0209] PTMA (20.00 g, 0.19 mol of mercapto group), DPHA (212.00 g, 2.12 mol of acryloyl group), PGMEA (58.00 g), HQ (0.1 g) and BzDMA (0.01 g) were added to a 1 L four-necked flask and reacted at 60° C. for 12 hours to obtain a dendrimer solution (B)-2. The disappearance of the mercapto group was confirmed by iodine titration (iodimetry) for the obtained dendrimer. The solid content concentration of the obtained dendrimer solution was 80.0% by mass, and the Mw of the GPC analysis was 10,000.

[0210] The curable resin compositions of Examples 1 to 13 and Comparative Examples 1 to 3 were prepared in the blending amounts (unit: mass %) described in Tables 1 and 2. The blending components used in Tables 1 and 2 are as follows.

[0211] (hardening resin containing unsaturated groups)

[0212] (A)-1: Resin solution obtained in Synthesis Example 1 (solid content concentration 55.3 mass %)

[0213] (A)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration 55.6 mass %)

[0214] (A)-3: Resin solution obtained in Synthesis Example 3 (solid content concentration 55.3 mass %)

[0215] (A)-4: Resin solution obtained in Synthesis Example 4 (solid content concentration 55.6 mass %)

[0216] (A)-5: Resin solution obtained in Synthesis Example 5 (solid content concentration 55.0 mass %)

[0217] (A)-6: Resin solution obtained in Synthesis Example 6 (solid content concentration 55.4 mass %)

[0218] (A)-7: Resin solution obtained in Synthesis Example 7 (solid content concentration 55.5 mass %)

[0219] (A)-8: Resin solution obtained in Synthesis Example 8 (solid content concentration 55.1 mass %)

[0220] (A)-9: Resin solution obtained in Synthesis Example 9 (solid content concentration 55.3 mass %)

[0221] (A)'-10: Resin solution obtained in Synthesis Example 10 (solid content concentration 55.2 mass %)

[0222] (A)'-11: Resin solution obtained in Synthesis Example 11 (solid content concentration 55.2 mass %)

[0223] (A)'-12: Resin solution obtained in Synthesis Example 12 (solid content concentration 55.6 mass %)

[0224] (Polymerizable compound)

[0225] (B)-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)

[0226] (B)-2: Dendritic polymer solution obtained in Synthesis Example 13 (solid content concentration 80.0 mass %)

[0227] (C): Biphenyl type epoxy resin (jER YX4000, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190 g / eq)

[0228] (Photopolymerization Initiator)

[0229] (D): 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) ("Irgacure OXE-01" manufactured by BASF, "Irgacure" is a registered trademark of the same company)

[0230] (Solvent)

[0231] (E): Propylene glycol monomethyl ether acetate (PGMEA)

[0232] [Table 1]

[0233]

[0234]

[0235] [Table 2]

[0236]

[0237] [Evaluate]

[0238] The compositions described in Tables 1 and 2 were evaluated as follows.

[0239] (Production of a substrate with a cured resin film for evaluating initial transmittance, transmittance after light resistance test, and adhesion strength with a glass substrate)

[0240] The curable resin composition shown in Table 1 and Table 2 was applied to a 125 mm × 125 mm glass substrate "#1737" using a spin coater so that the film thickness after heat curing was 10.0 μm. The glass substrate was previously irradiated with a low-pressure mercury lamp at a wavelength of 254 nm and an illumination of 1000 mJ / cm 2 The surface was washed with ultraviolet rays. A hot plate was used to pre-bake at 90°C for 3 minutes to prepare a dry film. Then, a hot air dryer was used to perform main curing (post-bake) at 230°C for 30 minutes to obtain substrates with resin cured films of Examples 1 to 13 and Comparative Examples 1 to 3.

[0241] [Evaluation of initial penetration rate]

[0242] The transmittance at a wavelength of 400 nm of the substrate with the resin cured film after the main curing and before the light resistance test was measured using an ultraviolet visible infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.).

[0243] [Evaluation of changes in transmittance caused by light resistance test]

[0244] A blue filter "IEB400" (manufactured by Isuzu Seiko Glass Co., Ltd., 50mm×50mm×5mmt, the transmittance of wavelengths below 340nm and above 480nm is less than 10%) is placed on the substrate with the resin cured film after the main curing, and light irradiation is performed for 1000 hours in a Xe test chamber "Q-SUN Xe-1" (manufactured by Q-Lab Corporation). The transmittance of light with a wavelength of 400nm in the area irradiated with light through the blue filter in the substrate with the resin cured film is measured using an ultraviolet visible infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.). Next, the transmittance change caused by the photosensitivity test is evaluated using the following criteria based on the change in transmittance before and after light irradiation relative to the transmittance before light irradiation (change in transmittance / transmittance before light irradiation). In addition, △ or above is qualified.

[0245] ◎: The change in transmittance before and after the light resistance test is less than 10%

[0246] ○: The change in transmittance before and after the light resistance test is 10% or more and less than 15%

[0247] △: The change in transmittance before and after the light resistance test is 15% or more and less than 20%

[0248] ×: The change in transmittance before and after the light resistance test is 20% or more

[0249] [Evaluation of adhesion strength with glass substrate]

[0250] A 2.7 mm Φ stud pin with epoxy adhesive was placed on the resin cured film of the above-mentioned substrate with resin cured film that had been cut into 15 mm × 20 mm, dried in an oven at 80°C for 30 minutes, and then heat-cured at 150°C for 60 minutes using a hot air dryer to bond the stud pin to the resin cured film to form an adhesion test piece.

[0251] Next, the adhesion strength between the glass substrate and the cured resin film was measured using a stud pull peel strength tester (ROMULUS, manufactured by Quad Group).

[0252] (Evaluation Criteria)

[0253] ◎: Adhesion strength is more than 160kgf / cm 2

[0254] ○: Adhesion strength is more than 150kgf / cm 2 And 160kgf / cm 2 the following

[0255] △: Adhesion strength is more than 140kgf / cm 2 And 150kgf / cm 2 the following

[0256] ×: Adhesion strength is 140kgf / cm 2 the following

[0257] (Preparation of a substrate with a resin cured film for evaluating the initial pattern transmittance and development adhesion)

[0258] The curable resin composition shown in Table 1 and Table 2 was applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing was 10.0 μm, and pre-baked at 90°C for 3 minutes using a hot plate to prepare a dry film. Next, the dry film was irradiated with i-ray at an intensity of 30 mW / cm 2 Ultra-high pressure mercury lamp irradiation 100mJ / cm 2The ultraviolet rays cause the photohardening reaction of the dry film.

[0259] Next, the exposed film was developed by passing through a 2.38% TMAH (tetramethylammonium hydroxide) developer at 23° C. and a temperature of 1 kgf / cm 2 After 60 seconds of development treatment with a spray pressure of 5kgf / cm 2 The unexposed part was removed by spray water washing to form a dot pattern with a diameter of 5 to 40 μm. Finally, a hot air dryer was used for main curing (post-baking) at 230° C. for 30 minutes to obtain the substrates with resin cured films of Examples 1 to 13 and Comparative Examples 1 to 3.

[0260] [Pattern initial transmittance evaluation]

[0261] The transmittance of the substrate with the resin cured film after development / primary curing at a light wavelength of 400 nm was measured using an ultraviolet visible infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.).

[0262] [Development Adhesion]

[0263] The dot pattern of the cured resin film on the obtained cured resin film-attached substrate was observed using an optical microscope to determine whether the pattern was peeled off.

[0264] (Evaluation Criteria)

[0265] ⊚: The minimum dot pattern size that can be formed without peeling is less than 10 μm.

[0266] ○: The size of the minimum dot pattern that can be formed without peeling is 10 μm or more and less than 20 μm.

[0267] △: The size of the minimum dot pattern that can be formed without peeling is 20 μm or more and less than 40 μm.

[0268] ×: The dot pattern of 40 μm peeled off.

[0269] The evaluation results are shown in Tables 3 and 4.

[0270] [Table 3]

[0271]

[0272] [Table 4]

[0273]

[0274] From the comparison between Examples 1 to 13 and Comparative Examples 1 to 3, it can be seen that by using a curable resin composition containing a polymerizable resin (A) containing an unsaturated group in which the molar ratio [(a-2) / (a-1)] of the diol compound (a-1) to the diol compound (a-2) is greater than 0.5 and less than 5.0, the yellowing of the resin cured film caused by light of 340nm to 480nm can be suppressed, and the adhesion to the glass substrate and the development adhesion can be achieved.

[0275] From the comparison of Examples 3, 5 to 7, it can be seen that the aforementioned component (a-2) has at least one alicyclic structure, which can suppress the developer from penetrating into the photocured portion during development, and can suppress the peeling of fine patterns or the yellowing of the resin cured film after the main curing. In addition, by using a high molecular weight polymerizable compound as the aforementioned component (B), the penetration of the developer can also be suppressed, and the yellowing of the resin cured film can be further suppressed.

[0276] Comparison between Examples 3 and 8 shows that the toughness of the cured resin film can be improved and the adhesion to a substrate such as glass can be improved by using an acid dianhydride having at least one aromatic ring structure as the component (a-3).

[0277] (Industrial Applicability)

[0278] The present invention can provide a polymerizable resin containing an unsaturated group 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 is suitable for use in various fields requiring low absorption of light having the above wavelengths or various fields requiring suppression of degradation caused by light having the above wavelengths.

Claims

1. A polymerizable resin containing an unsaturated group, which is a 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 the aforementioned (a-1) to the aforementioned (a-2) [(a-2) / (a-1)] is 0.5 or more and 5.0 or less, In the general formula (1), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, a portion of the hydrogen atoms constituting Ar may be substituted by 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 a number from 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 the general formula (2), R2 is a divalent saturated hydrocarbon group having 2 to 20 carbon atoms, In the general formulae (3) and (4), R3 is independently a hydrogen atom or a methyl group, R4 is independently an alkylene group or an alkylarylene group having a carbon number of 2 to 10, R5 is independently a saturated or unsaturated hydrocarbon group having a carbon number of 2 to 20, p is a number of 0 to 10, and * represents the site of bonding to the structure represented by the general formula (1).

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

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

4. The unsaturated group-containing polymerizable resin according to claim 1, which has a weight average molecular weight of 1,000 to 40,000, and an acid value of 20 to 200 mgKOH / g.

5. A curable resin composition comprising: (A) the polymerizable resin containing an unsaturated group 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) Solvent. 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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